CA1117531A - Polymers containing imidyl groups and silyl groups - Google Patents
Polymers containing imidyl groups and silyl groupsInfo
- Publication number
- CA1117531A CA1117531A CA000310791A CA310791A CA1117531A CA 1117531 A CA1117531 A CA 1117531A CA 000310791 A CA000310791 A CA 000310791A CA 310791 A CA310791 A CA 310791A CA 1117531 A CA1117531 A CA 1117531A
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- CA
- Canada
- Prior art keywords
- group
- formula
- atoms
- compound
- radicals
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
Abstract
Abstract of the Disclosure The compounds according to the invention are polymers, containing imidyl groups and silyl groups, of the formula in which Yl snd Y2 are Si-organic radicals, a is an in teger from 1 to 50 and Z, Zl and Z2 independently of one another are each divalent organic radicals, but at least one of the radicals Zl and Z2 is a group which contains an ausubtituted or substituted imidyl group.
The products according to the invention may be prepared, for example, by a multi-stage reaction of m-phenylenediamine, 5 dimethylmaleimidyl-lsophthalic acid dichloride, 3,3'-4,4'-benzophenonetetracaboxylic acid dianhydride and Y-aminopropyl-di-n-propoxymethylsilane in solution The products are used as adhesion promoters, for example between inorganic solids and organic resins
The products according to the invention may be prepared, for example, by a multi-stage reaction of m-phenylenediamine, 5 dimethylmaleimidyl-lsophthalic acid dichloride, 3,3'-4,4'-benzophenonetetracaboxylic acid dianhydride and Y-aminopropyl-di-n-propoxymethylsilane in solution The products are used as adhesion promoters, for example between inorganic solids and organic resins
Description
~ 3~ ~
The present invention relates -to novel poly~ers, containing imidyl groups and silyl groups, to a process for -their preparation and to their use as adhesion pro-moters, for example between inorganic solids and organic resins, or for the preparation of crosslinked mouldings The literature discloses -that various silanes, for example vinyltrichlorosilane, vinyl-tris-(2-me-thoxyethoxy)-~ilane and Y-aminopropyltrie~hoxysilane, may be used as adhesion promoters ~or various applications, for example for the production of glass fibre-rein~orced plas-tics, for sealants, ~or lacquers and for adhesives ~compare, for example, Defazet, 28, 207-211 (1974) and Kunststoffe, 55, 909-912 (1965)~. However, the properties of the pro-ducts obtained using these known adhesion promoters in part leave something to be desired, especially in respect of water absorption, resis-tance to thermal oxidation and/or dielectric properties.
German Of~enlegungsschrift 2,426,885 describes silicon-modified crosslinkable polyamide prepolymers and polyamidoacid prepolyrners as polymeric base materials.
In these prepolymers, crosslinking takes place via -the two terminal silyl groups. Accordingly, the degree o~
crosslinking of these prepolymers is limited.
The present invention relates to novel polymers, containing imidyl groups and silyl groups, which on the one hand, when used as adhesion promoters, give products with improved properties, especially improved resistance ' ~
to thermal oxidation, improved electrical properties and/
or lo~wer water absorp~ion and, on the o~her 'nand, may be used ~o produce highly crosslinked poly~eric mouldings, The novel polymers, containing imirl~l gro~ps and silyl groups, correspond to the formula I
1 L----~--Z2--co ~--z--lr.~--co ~ z _ ~ 2 (I) in which Yl and Y2 independently of one another are a IQl -CO~ R- J - Q -Co-NH z - ~ C ~ H~-Si-Q , ~roup, ~Q2 R is ~CH2 ~, ~ 2~ ~ Cl~2~x (IH2i~3 ~Ql (IH2 ~
l iS--~CH2 ~ ~ -N-~CH2 ~ ~~Q or --N-- X , X is alkyl with 2-7 C atoms, cycloalkyl with 5-7 C atoms or benzyl, Q is methyl, phenyl ~r -Q3, Ql' Q2 and Q3 lndependentl-~of one another are alk~fl with 1-6 C ato~s or phenyl, x is an integer ~rom 2 to 4, a is an integer from l to 50, the individual radicals Z indepe~dently o~ one another are an aliphatic radical with at least 2 C atoms, or a cyclo-t aliphatic, araliphatic or a carbocyclic-aromatic radical and Zl and the individual radicals Z2 independently of one another are a ~1 .
Z ,~C~)O~ n~'L
o~ /
OC CO ( Jlo~)c~
group, but at leas-t one of Zl and Z2 is a \~
y ~T
QC CO
group, A is a ra~ical ~C = C -, - C CH2t ~
~ ~ or ~ , R2 ~nd R3 in-dependently of one ~nother are hydrogen or methyl, ~che individual values m and n independently of one another are 1 or 2 and the individual ralicals Z3 independently of one another are an aliphatic radical with at least 2 C atoms, or a cycloali~h~tic or a carboc~clic-aromatic radical in which the carboxamide and carboxyl groups are bonded to different C atoms ~nd carboxyl groups bonded to cyclic radicals Z3 are each in the ortho-position to a carboxamid~ group.
The invention further relates to the derivative~
which have been cyclised to the corresponding imides.
The polymers of the formula I and the corres-pon~ing cyclised derivatives can be prepared b~. a me~hod wherein, if a is 1, a co~pound ol the formul~ II
I~OC' ~ ~ C01~
( ~1 ), /
and, if a ~ 1, a compound oi~ the formula X:[I
ZL~C0~ Z-N~I-C0-~~Z2-C0-~rX--Z-NH~CO~a-~r~Z5 (ILI) in which ZL~ and Z~ inclepen(lentl~ o~ one ano-ther are .J.
R40C ~ (CO~)m~l or æ3 N \ (~IOOC)~ 5 A
group, is reac~ed with an essentially stoichiometric amount of a compound ol the formula IV or V
IQl H2~--R - Si~
or OC ~ Rl Si - Q (V) or of a mix~ure of such compound3, m, n, A, R, Rl, Q, Ql~ Q2~ Z~ Z~2 and Z3 in the above ~ormulae II to V being as delined ~l~er formula I, whilst one f Z2 Z~ and Z5 is a ~"
7~
N or N
OC ~0 OC C~
A A
group, al is an integer from 1 to 49, the radicals R~ in-dependently of one another are -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -NH Z-NH2 and R5 is -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -~-Z-NH2 or, if Z3 is a cyclic radical and m is 2, R5 togeth~r with R6 are a -O- group, the groups COR5, ~COR6 and -COOH are bonded to differen-t C atoms and if Z3 is a cyclic radical and m and/
or n are ?, the -COR5 or -COOH group is in the ortho-position to the -COR6 group or to the adjoining carboxamide group, after which the reaction product may or may not be cyclised to the corresponding imide.
Alkoxy groups R4 and R5 and alkyl groups X, Ql' Q2 or Q3 may be straight-chain or branched. Examples of alkoxy and alkyl groups according to the definition are the methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy group, and the methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl, n-hexyl and n-heptyl group.
Preferred alkoxy groups R4 and R5 are methoxy and ethoxy.
Preferred alkyl groups X have 2-4 C atoms, the ethyl and isopropyl group being particularly preferred.
Preferred alkyl groups Ql' Q2 and Q3 are straight-chain groups with 1-6 C atoms.
Yl and Y2 may have different meanings, but advan-tageously are groups according -to the same definition~
R is preferably a ~ ~ radical, but especially a -~-CM2 ~ or ~ O-~CH2 ~ radical.
,Ql The radical -Rl-Si-Q is advan~ageously bonded to ~7~3-.~
the bell;;c~llo rln~ 1n t~e o]lho-LjoJ:it:icJn ~o t.he ~OOH ~roup o.r to t~le -CO~ %~ C'O- ~J~OU~. Pre~frab~.y, Rl i~
(C~ 3 ~
~O~Cf~~r~ ~:r ~ __(C~ L~QI b~ especially ( 2 t3 Ql -~ (CH ~ ~ ~ Q~
Particularly pref`erentis.lly, Yl and Y2 are each a --CO~N~I-Z~ CO
~ IQl ~ooa Ql group or a -C~-NH-R-~i-Q grQup, ln whlch ~R Si-Q is bonded in the ortho-po3ition to the COOH or 1, -CO-NH~Z-NH CO- group, R is ~ CH2~3 or ~ -0-~-CH
(CH2~ ,Ql Rl i.S _O~CH2~ bQ2 alko.cy with 1-4 C atoms ~nd Ql and Q2are each alk~Jl with 1 to 4 carbon atoms.
~ ery particul~rly preferred compounds are polymers o~ the formul~ I ~nd the corresponding cyclised imid~
deriva~ives, in ~hich Y1 and '~2 are each a 5~1 -Co-NH-R-$i-Q
' Q2 group, and R and Rl have the above pre~erred meaning, Q is methyl, ethoxy or n--propoxy and Ql and Q2 are each ethyl or n-propyl.
.
~117~
- 6.1.
A is advantageously ~ , -C _ C- , and especially -CH--CH-, The radicals R4 are preferably each chlorine.
If m is 1, R5 is also preferably chlorine, If m i8 2, R5 together with R6 are the -O- group, in accordance with the definition given.
Preferred products ~or use as adhesio~ promoters are polymers of the formula I, and the correspondin~
~,~
__ i s~
cyclised deriva-tives, in w~ch a is an integer from 1 to 15, especially app~o~i~ately frol~ 1 to 10. For the produc-tion of` crosslinked mouldings, it is preferred -to use polyrners o~ the formula I, or corresponding cyclised ! derivatives, in which a is greater than 15, and in partic-ular equal to or greater than 20.
The proportion, in -the polymers rnentioned, of groups Zl and/or Z2 which are OC ~0 A
may be up to 100 mol % but it advantageously about 5-50 mol % and especially about 10-30 mol %, based on the total number of mols of acid components employed In formula I, the individual symbols Z, Zl~ Z2~ Z3 m and n may ha~e different meanings.
- Radicals Z may be unsubstituted or substituted, for example by halogen atoms, ~or instance fluorine~
chlor~ne or bromine, or by alkyl or alkoxy groups each with 1-4 C atoms.
Suitable aliphatic radicals Z are in particular straight-chain or branched alkylene groups with 2-12 car-bon atoms, especially unsubstituted alkylene groups with
The present invention relates -to novel poly~ers, containing imidyl groups and silyl groups, to a process for -their preparation and to their use as adhesion pro-moters, for example between inorganic solids and organic resins, or for the preparation of crosslinked mouldings The literature discloses -that various silanes, for example vinyltrichlorosilane, vinyl-tris-(2-me-thoxyethoxy)-~ilane and Y-aminopropyltrie~hoxysilane, may be used as adhesion promoters ~or various applications, for example for the production of glass fibre-rein~orced plas-tics, for sealants, ~or lacquers and for adhesives ~compare, for example, Defazet, 28, 207-211 (1974) and Kunststoffe, 55, 909-912 (1965)~. However, the properties of the pro-ducts obtained using these known adhesion promoters in part leave something to be desired, especially in respect of water absorption, resis-tance to thermal oxidation and/or dielectric properties.
German Of~enlegungsschrift 2,426,885 describes silicon-modified crosslinkable polyamide prepolymers and polyamidoacid prepolyrners as polymeric base materials.
In these prepolymers, crosslinking takes place via -the two terminal silyl groups. Accordingly, the degree o~
crosslinking of these prepolymers is limited.
The present invention relates to novel polymers, containing imidyl groups and silyl groups, which on the one hand, when used as adhesion promoters, give products with improved properties, especially improved resistance ' ~
to thermal oxidation, improved electrical properties and/
or lo~wer water absorp~ion and, on the o~her 'nand, may be used ~o produce highly crosslinked poly~eric mouldings, The novel polymers, containing imirl~l gro~ps and silyl groups, correspond to the formula I
1 L----~--Z2--co ~--z--lr.~--co ~ z _ ~ 2 (I) in which Yl and Y2 independently of one another are a IQl -CO~ R- J - Q -Co-NH z - ~ C ~ H~-Si-Q , ~roup, ~Q2 R is ~CH2 ~, ~ 2~ ~ Cl~2~x (IH2i~3 ~Ql (IH2 ~
l iS--~CH2 ~ ~ -N-~CH2 ~ ~~Q or --N-- X , X is alkyl with 2-7 C atoms, cycloalkyl with 5-7 C atoms or benzyl, Q is methyl, phenyl ~r -Q3, Ql' Q2 and Q3 lndependentl-~of one another are alk~fl with 1-6 C ato~s or phenyl, x is an integer ~rom 2 to 4, a is an integer from l to 50, the individual radicals Z indepe~dently o~ one another are an aliphatic radical with at least 2 C atoms, or a cyclo-t aliphatic, araliphatic or a carbocyclic-aromatic radical and Zl and the individual radicals Z2 independently of one another are a ~1 .
Z ,~C~)O~ n~'L
o~ /
OC CO ( Jlo~)c~
group, but at leas-t one of Zl and Z2 is a \~
y ~T
QC CO
group, A is a ra~ical ~C = C -, - C CH2t ~
~ ~ or ~ , R2 ~nd R3 in-dependently of one ~nother are hydrogen or methyl, ~che individual values m and n independently of one another are 1 or 2 and the individual ralicals Z3 independently of one another are an aliphatic radical with at least 2 C atoms, or a cycloali~h~tic or a carboc~clic-aromatic radical in which the carboxamide and carboxyl groups are bonded to different C atoms ~nd carboxyl groups bonded to cyclic radicals Z3 are each in the ortho-position to a carboxamid~ group.
The invention further relates to the derivative~
which have been cyclised to the corresponding imides.
The polymers of the formula I and the corres-pon~ing cyclised derivatives can be prepared b~. a me~hod wherein, if a is 1, a co~pound ol the formul~ II
I~OC' ~ ~ C01~
( ~1 ), /
and, if a ~ 1, a compound oi~ the formula X:[I
ZL~C0~ Z-N~I-C0-~~Z2-C0-~rX--Z-NH~CO~a-~r~Z5 (ILI) in which ZL~ and Z~ inclepen(lentl~ o~ one ano-ther are .J.
R40C ~ (CO~)m~l or æ3 N \ (~IOOC)~ 5 A
group, is reac~ed with an essentially stoichiometric amount of a compound ol the formula IV or V
IQl H2~--R - Si~
or OC ~ Rl Si - Q (V) or of a mix~ure of such compound3, m, n, A, R, Rl, Q, Ql~ Q2~ Z~ Z~2 and Z3 in the above ~ormulae II to V being as delined ~l~er formula I, whilst one f Z2 Z~ and Z5 is a ~"
7~
N or N
OC ~0 OC C~
A A
group, al is an integer from 1 to 49, the radicals R~ in-dependently of one another are -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -NH Z-NH2 and R5 is -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -~-Z-NH2 or, if Z3 is a cyclic radical and m is 2, R5 togeth~r with R6 are a -O- group, the groups COR5, ~COR6 and -COOH are bonded to differen-t C atoms and if Z3 is a cyclic radical and m and/
or n are ?, the -COR5 or -COOH group is in the ortho-position to the -COR6 group or to the adjoining carboxamide group, after which the reaction product may or may not be cyclised to the corresponding imide.
Alkoxy groups R4 and R5 and alkyl groups X, Ql' Q2 or Q3 may be straight-chain or branched. Examples of alkoxy and alkyl groups according to the definition are the methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy group, and the methyl, ethyl, n-propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl, n-hexyl and n-heptyl group.
Preferred alkoxy groups R4 and R5 are methoxy and ethoxy.
Preferred alkyl groups X have 2-4 C atoms, the ethyl and isopropyl group being particularly preferred.
Preferred alkyl groups Ql' Q2 and Q3 are straight-chain groups with 1-6 C atoms.
Yl and Y2 may have different meanings, but advan-tageously are groups according -to the same definition~
R is preferably a ~ ~ radical, but especially a -~-CM2 ~ or ~ O-~CH2 ~ radical.
,Ql The radical -Rl-Si-Q is advan~ageously bonded to ~7~3-.~
the bell;;c~llo rln~ 1n t~e o]lho-LjoJ:it:icJn ~o t.he ~OOH ~roup o.r to t~le -CO~ %~ C'O- ~J~OU~. Pre~frab~.y, Rl i~
(C~ 3 ~
~O~Cf~~r~ ~:r ~ __(C~ L~QI b~ especially ( 2 t3 Ql -~ (CH ~ ~ ~ Q~
Particularly pref`erentis.lly, Yl and Y2 are each a --CO~N~I-Z~ CO
~ IQl ~ooa Ql group or a -C~-NH-R-~i-Q grQup, ln whlch ~R Si-Q is bonded in the ortho-po3ition to the COOH or 1, -CO-NH~Z-NH CO- group, R is ~ CH2~3 or ~ -0-~-CH
(CH2~ ,Ql Rl i.S _O~CH2~ bQ2 alko.cy with 1-4 C atoms ~nd Ql and Q2are each alk~Jl with 1 to 4 carbon atoms.
~ ery particul~rly preferred compounds are polymers o~ the formul~ I ~nd the corresponding cyclised imid~
deriva~ives, in ~hich Y1 and '~2 are each a 5~1 -Co-NH-R-$i-Q
' Q2 group, and R and Rl have the above pre~erred meaning, Q is methyl, ethoxy or n--propoxy and Ql and Q2 are each ethyl or n-propyl.
.
~117~
- 6.1.
A is advantageously ~ , -C _ C- , and especially -CH--CH-, The radicals R4 are preferably each chlorine.
If m is 1, R5 is also preferably chlorine, If m i8 2, R5 together with R6 are the -O- group, in accordance with the definition given.
Preferred products ~or use as adhesio~ promoters are polymers of the formula I, and the correspondin~
~,~
__ i s~
cyclised deriva-tives, in w~ch a is an integer from 1 to 15, especially app~o~i~ately frol~ 1 to 10. For the produc-tion of` crosslinked mouldings, it is preferred -to use polyrners o~ the formula I, or corresponding cyclised ! derivatives, in which a is greater than 15, and in partic-ular equal to or greater than 20.
The proportion, in -the polymers rnentioned, of groups Zl and/or Z2 which are OC ~0 A
may be up to 100 mol % but it advantageously about 5-50 mol % and especially about 10-30 mol %, based on the total number of mols of acid components employed In formula I, the individual symbols Z, Zl~ Z2~ Z3 m and n may ha~e different meanings.
- Radicals Z may be unsubstituted or substituted, for example by halogen atoms, ~or instance fluorine~
chlor~ne or bromine, or by alkyl or alkoxy groups each with 1-4 C atoms.
Suitable aliphatic radicals Z are in particular straight-chain or branched alkylene groups with 2-12 car-bon atoms, especially unsubstituted alkylene groups with
2-10 carbon atoms. The alkylene chain may also be interrupted by hetero-atoms, for example 0 9 S or N atoms.
If Z is a cycloaliphatic radical it may be, for example, the 1,3- or 1,4-cyclohexylene, 1,4-bis-(methyl-- ene)-cyclohexane or dicyclohexylmethane group, whilst suitable araliphatic radicals Z are especially 1,~-, 1,4-or 2,4-bis-alkylenebenzene, 4,4'~bis-alkylenediphenyl and 4,4'-bis-alkylene-diphenyl-ether radicals.
: If Z is a carbocyclic-aromatic radical, it is pre-ferably a monocyclic, fused polycyclic or non-fused bi-cyclic aromatic radical, and in the latter case the aroma-
If Z is a cycloaliphatic radical it may be, for example, the 1,3- or 1,4-cyclohexylene, 1,4-bis-(methyl-- ene)-cyclohexane or dicyclohexylmethane group, whilst suitable araliphatic radicals Z are especially 1,~-, 1,4-or 2,4-bis-alkylenebenzene, 4,4'~bis-alkylenediphenyl and 4,4'-bis-alkylene-diphenyl-ether radicals.
: If Z is a carbocyclic-aromatic radical, it is pre-ferably a monocyclic, fused polycyclic or non-fused bi-cyclic aromatic radical, and in the latter case the aroma-
3~
tie n~lel t~l rr,ay be h~ led -1 c) one enc~ ~he.r by a h~ idF,e mernb e r .
~xa~nples ol su.i. table br:iclge merrbers are:
QL~ Q4 -0~, ~C~I2Cri2 , --C'~ 'T~ , ~Cw~ -S~S , ~SO~, S02~, Q~
Q~
-S02NH-, ~CO-, -CO-, -C-C-, ~CON~ N~I-CO~ Si~ or .. ....
O O O - Ql~
Q~ .
-O Si-O-, .in which Q~ is an alk~l group ~ith 1-6, prefer ably 1-4, carbon a toms or a phenyl grcup, Non-~used bicyclic aromatic radicals Z may also be bonded to one another by two bridge rnembers, such ~s two S02_ ~r,r~oups, ~ Z3 is an alipha~ic radical, it ls preferably an unsubstituted, straight-chain or branched alkylene group with 1-12 carbon atoms, especially an unsubstituted alkyl-ene group with 2-10 carbon atoms.
Cycloaliphatic radicals Z3 are especially S-member-- ed or 6-membered cycloalkylene groups.
If Z3 is a carbocyclic-aromatic radical, the latter preferably contains at least one 6~membered ring; in par-ticular, such radicals ~re monocyclic radicals, fused poly-cyclic rad~cals t or polycyclic radica~ with se~eral cyclic, fused or nor.-fused, s~stems,, which may be bonded to one another directly or by bridge members. Suitable bridge members are those mentioned above in discussing Z, . . :.
L7S;~L
Ca~ ocye:l,ic~arc,lli.J-ti.c radicals ~ .nay also be ~,ubstitll.ted ".Ol ex,~)-nple by r!itro groups, a:!kyl gro~ll)s ~t/.it,h 1-4 carbo-~l atoms, hQ L ogen c'ltO7~1,5, espec,ially ch:l.ori~e, silyl g~roups, su.l.phonic ~.cil groups or s~ ?hau~oyl groups.
Preferably, the ln~iv~.dual rad.icals Z c~re, lndep~
endelltly of one a~lother, an ~lsubs-~ituted alkylene group with 2~10 carbon a-toms or; a monocycli.c., or non-fuxed bi~
cyclic, ~rom~-tic radi.cal which is unsubstitutecl or ~ubs-ti--tuted by halogen, or by alkyl or alko~cy groups, each ~ith 1-4 ca.rbon at.oms (the aromatic nuclel, in a non-:eused bi-cyclic arornatic radi.cal, being boncled to one ~nother direc~ly or via a -0-, -C~12- or ~,S02- bridge ~ernber), or an unsubstituted monocyclic aral~phatic radical, T~e individual radicals Z3 a:re preferably, indep~
endently of one another, an unsubs~itu~;ed alkylerle group with 2 10 C a-toms or an unsubstltu~ed ~onocycllc, fus~d polycyclic or non-*used bicyclic aromatic radical, (the aromatic nuclei, in a non-fused bicycli~ a~oma.tic radical, being bonded to one ano~hcr via a ~0-, -S0 or -C0~ bridge member), Preferred compounds of the ~ormula I, c~nd ~he corresponding cyclised derivatives, are those in ~Ihich a is an integer ~rom 1 to 50, the radicals Yl c~nd Y2 are each a ~CO~Nr~--Z~~ CO~
HOOC ~ L~Si--Q
, - . ~1 .
group or a -CO-NH~ Q group, the group Ql 2 -Rl-Si-Q b~ing bonded in the ortho-position to the ~COOH
or -CO~N~-Z-NH-CO- group, R is ~ CH
i~. ' , ~7~
LO -3 ~O~-O~ -CE~2- ~ 3 ( C}~2 ,~ r 0(),,~
; CH2 ~ ~ I2-~ Sl-Q, (~.:is meth~l o~ alkoxy with 1-l~ C atorns and (~ and Q2 ~r~ each al~yl ~lth 1-4 C atoms, esp~c.ially th~se in which a, Y~, Y~J R, R1, Q, Ql and Q~ have the abo~ementioned preferr~d meaning and -th~ radlcals Z are each a 1,3- or 15~phen~Jlerle group, or a 4~4~-diphenylmetharle~ l~,4'-diphenyl~e~her or 4,4 I _ diphenylculphone radica:l., the r~clicals Z3 ~re each a 1,3-phenylene or l,4-phenylene group or unsubsti.tuted alk~lene with L~-lo C atoms, if m and n are 1, or are each a benzene-~riyl group if m is 1 and n is 2, or are each a benzene-tetrayl group or the benzophenone ring system i~ m and n are 2, and one or both oE the radicals Zl and Z2~ and about 5-50 mol % of these, is a ~C ~0 A
group, in which A is ~ , C - C- or -CH=CH-~ CH3 CH3 Particularly preferred compounds, amongst the above, are those in which ~ is -CH=C~ .
Especially preferred cormpounds, amongst the above, are those in which a is an integer from 1 to 15.
Especially preferred compounds of the formula I
and the corresponding cyclised irnide derivatives, are those in which Yl and Y2 are each a ..
.
~17~
. , ~, I
~)Q.~
, .
- C'0-~ ]~ ~i -Q
0~?~
~ro~lp, 1~ i.s - ~C~I;?)~ or --~ 0-(('11~-~-,~, Q :is lliethy:l o~
alko~ wltll 1 - 4 C cltc)m~; and Q1 ~rld Q2 ar~ ch a.Lkyl ~ith 1 - 4 C ~t:oms.
Particulclrly preferred cor~.pounds of -the formula I, and the corresponding cyclised imide derivatives, are ~ 1~ Y2, R~F~l~ Q~ Ql and Q~ have the above mentioned preferIed meanings, a i.s an in~eger frorn 1 ~o 50, and rn and n are each 1, ~ i.s a 1,3- or 1,4--phenylene group, or a L" L~ '-cliphenylme-tharle or ~+,4'~di.phen~Jl~ether radical and Z~ is a 1,3-phenylene or 1,4-phenylene group, but only nne of Z and Z3 is a 1,4-phenylene group; or m is 1 and n i.s 2, Z ls a 1~3- or 1,4-phenylene group, or a 4,4'-diphenylr.lethane or 4,4'~dlphenyl-e-ther ~3L75i~L
.~dic~ r~l Z~ .i; a 'L~ r~ c~
or m arid n ~lre eac~l 2, ~. is a :!, 3- or :1. ,L~-phen~ rie ~ro~ , o~ ?r~ Lh~ o~ i.r)~en ~ h~
racli cal alld Z~ i.s a berlz,enctetr a~:l L-~rc~llp or the benzophen-one ri.n~, system~
and in ~rhich ~hout 10-30 mc)l % ~f Zl and ~2~ is a ~ or OC _ CO OC ~<CO
C~ H3 group. Pc~r~icularly pr~fcrrcd comF)o~ln~ls, 2mongst tho above, are t~lOSC in which ~ i~ an inteyer ~rom 1 to 10.
Very particularly preferred compounds, amongs-t the above ? are those in which Q is methyl, ethoxy or n-propoxy and Ql and Q2 are each ethyl or n-propyl The reaction of a co,npound of the formula II or III
with a co;npound o. the formula IV and/or V is carried out in a manner known per se, preferably in an anhydrous i.nert organic solvent at temperatures between about -20C and *150C, especially about -15C to ~50C
Examples of organic solvents ~hich may be employed are Ghlorinated or non-chlorinated aromatic hy~rocarbons, for exc~mple benzene, toluene, xylenes and chloro~enzene;
chlorinated or non-chlorinated aliphatic hydrocarbons, for example n-pentane, n-'nexane, methylene chloride, chloroform, tetrachloroethane and tetrachloroethylene; aliphatic and cycloaliphatic ketones, for examp.le acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; cyclic ethers, for example tetrahydrofuran, tetrahydropyran and dioxane;
cyclic amides, for example N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-~-c~prolactarn; N,N-dialkylamides of aliphatic monocar~oxylic acids with 1-3 carbon atoms in the acid part, for example N,N-dimethyl-formamide, N,N-dimethylacetamide, N,N-diethylacetamide and ~.
5~
N,N-dimethylme-thoxyace-tamide, hexame~hylphosphorotriamide (hexametapol); N,N,N',N' ~e-trarfle-thylurea, -tetrahydrothio-phene dioxide (sulpholan); dialkylsulphoxides, for example dimethylsulphoxide and d:ie-thylsulphoxide; phenol and cresols.
The reaction can also be carried out in mixtures of such solven-ts.
Preferred solvents are N,N-dialkylamides of ali~
phatic monocarboxylic acids with 1-3 carbon atoms in the acid part, especially N,N~dimethyl*ormamide and N,N-dime-thylacetamide, and cyclic amides, for example N-methyl~
2-pyrrolidone.
The compounds of the formula III are reac-ted with the compounds of the formula I~ and/or V in a molar ratio of at least 2:1. If al in formula III is -l, the com-pound of the formula III is advantageously used in the stoichiometric amount or in a slightly smaller amount than this. For the reaction with oligomers or polymers of the formula III (al greater than or equal to 1), the re-actants are preferably employed in the stoichiometric amount.
If the compounds of the formula IV or V are re-acted with oligomers or polymers of the formula III, the latter are advantageously used in the form of their solu-tions, as ob-tained from their preparation.
To prepare compounds of the formula I, in which Y
Ql and Y2 are each a -CO-NH-R-Si-Q group, a compound of the formula II or III, in which R4 and/or R5 are not -NH-Z-NH2 and R~ is preferably alkoxy with 1-4 C atoms or phenoxy and especially chlorine, and if m and n are 1 or m is 1 and n is 2, R5 is alkoxy with 1-4 C atoms or phenoxy and especially chlorine, and if m and n are 2, R5 together with R6 is the -O- group, is reacted with a compound of the formula IV or with a mixture of two different com-pounds of the formula IV.
5;~
To prepare compounds of the forrnula I, in which Y
and Y2 are each a ~CO~ Z-N~-CO
~ IQl HOOC Rl- Si-Q?
group, a compound of the formula V or a mixture of two different compounds of the formula V is reacted wi-th a compound of the formula II or III, in which R4 or R5 is _ 2 Analogously, compounds of the formula I, in which . ~Ql one of Yl and Y2 is a -CO-NH-R-Si-Q group and the other is a Q2 --C~NH--Z--NH~O
HOOC ~ Rl- Si- Q
group, areprepared by reacting a compound of the XI or III, in which one of the terminal functional groups R4 and R5 is not -NH-Z-NH2 and the other is -OH, alkoxy with 1-4 C atoms, phenoxy or chlorine, or, if m is 2, R5 together with R6 is -O-, with a mixture of a compound of the formula IV and a compound of the formula V.
In all these cases, the compound of the formula IV
and/or V is preferably employed in the stoichiometric amount.
After completion of the reaction, the solvents can, if desired, be removed in the usual manner, for example by distilling off, if appropriate under reduced pressure.
The starting compounds o~ the ~ormula II are in the , , ... ~ ............. . . . . . ... ,. ., . .. . ... ..... ........ , .. . . .. .. , ....... ........ . . _~
~7S;~
majority o~ cases described in Gerrnan Offenlegungsschriften 2,626,768 and 2,626,795 and may all be prepared in accord-ance with the method disclosed there Compounds of the forrnula III can be prepared in a manner known per se, by reacting a compound of the formula VI
H2N-Z~-NH-CO-Z2-CO_NH_Z ~ MH2 ~VI) with an excess of a compound o~ the formula II and/or of a compound of the formula VII
R50C~ ~(C0~6)m-l (VII) (R60C)n_l CO 5 al, m~ n~ Z, Z2~ Z3, R5 and R6 being as defined above.
The compounds of the formula VI can, for their part, be obtained by reacting an excess of diamine H2N-Z-NH2 with a dicarboxylic, tricarboxylic or tetra-carboxylic acid derivative of the formulaeVIII and/or IX
R 'OC ~ C0~4~ X5'0C~ ~(OOR6 )m-l N and/or ~R6~0C)~_l COR5 .
(IX~
(VIII) in which m, n, A and Z3 are as defined above, the radicals R4' independently of one another are ~OH, chlorine, alk-oxy with 1-4 C atoms or phenoxy and the radicals R5' in-dependently of one another are -OH, chlorine, alkoxy with 1-4 C atoms or phenoxy, or, if m and/or n is l, R5' to-gether with R6' is -O-, the groups COR5' and -COR6' are bonded to different C atoms and, if Z3 is a cyclic radi-7S~
cal and m and/or n is 2, the -COR5' group or groups are each in the ortho-posi-tion -to a -COR6' group Compounds of -the ~ormula III, in which R4 and R5 i are not -NH-Z-NH2, can also be prepared by reac-ting a diamine H2N-Z-NH2 with an excess of a mixture of different compounds of the formulae VIII and IX.
The condensation of a compound of the formula VI
with a compound of the formula II and/or a compound of the formula VII, and the preparation of compounds of the ~ormula III or VI from diamines H2N-Z-~2 and dicarboxylic, tricarboxylic or tetracarboxylic acid derivatives of the formulae VIII and/or IX is carried out in-a manner known per se, advantageously at temperatures from about -50C
to ~300C. The condensation can be carried out in the melt or, preferably, in an inert organic solvent or a solvent mixture. For condensation in solution, temp-eratures of about -20C to +200C, very particularly about -20C to +50C, are preferred. In the said reactions, it may under certain circumstances be advantageous to add known polymerisation inhibitors, for example hydroquinones, pyrocatechol or cresols, for example di-tert.-butylcresol.
Examples of suitable inert organic solvents are those mentioned above in connection with the reaction of compounds of the formula II or III with the compounds of the formula IV and/or V.
The hydrochloric acid formed during the conden-sation or polycondensation of compounds of the formulae II, VII, VIII or IX, in which R4, R4', Rs or Rs' is chlorine~
with the diamines H2N-Z-NH2 or the diamines of the formula III can be removed by neutralisation with basic compounds, - for example calcium hydroxide or trie-thylamine, or by re-action with an epoxide compound, for example ethylene oxide or propylene oxide, and by washing out with a suit-able solvent, for example water~ - The condensation reactions are advantageously carried out with exclusion of moisture, for example in an iner-t gas atmosphere, for instance nitrogen.
~ 7 The ami~osilanes of the formula IV are kno~ or can be prepared in a manner kno~ per se. The com-pounds of the ~`ormula V can be prepare~ by reacting a com-pound of the formula X
/0 (X) Rl ~ CO
which R ' is -O-CH2CH =CH2 or -N-CH2CH 2 ~.
alkyl with 2-7 C atoms, cycloalkyl with 5-7 C atoms, benzyl or allyl 9 with a silane of the formula XI
Ql H-Si-Q (XI) ~Q2 in which Q, Ql and Q2 are as defined under formula I.
The reaction is advantageously carried out in an anhydrous organic medium and in the presence of a catalyst.
Examples of catalysts which can be used are organic per-oxides, for instance tert.-butyl hydroperoxide, di-tert.-butyl peroxide, benzoyl peroxide, diacyl peroxides and cumene hydroperoxide, or platinum and palladium catalysts, for example platinum/charcoal catalysts or PtC16H2 cata-lysts.
Examples of suitable inert organic solvents are aromatic hydrocarbons, for instance benzene, toluene and xylenes, cyclic ethers, for instance tetrahydrofuran, tetrahydropyran and dioxane, or ethylene glycol monoalkyl ethers and dialkyl ethers, wi-th 1-4 C atoms in each alkyl par-t, for instance ethylene glycol monomethyl ether, mono-ethyl ether, diethyl ether and di-n-butyl ether. Aroma-tic hydrocarbons are pre~erred ~ ~ 7 The reaction is advan-tageously carried out under a protective gas, for example nltrogen or argon.
The reaction temperatures are in general approx-imately between 80 and 150C; reaction tempera-tures be-tween approximately 90 and 120C are preferred, The compounds of -the formula XI are known.
Compounds of the formula X, in which Rl' is a diallylamino group, can be prepared, for example, by re-acting aminophthalic acid or the corresponding alkali metal salts or alkaline earth metal salts with allyl hal-ides and cyclising the resulting N,N-diallylaminophthalic acid. Compounds of the formula X, in which Rl' is an allyloxy group, can be obtained by reacting hydroxyphth-alic anhydride with an allyl halide. Finally, com-pounds of the formula X, in which Rl' is a -N-CH2CH=CH2 X~
group and X" is alkyl with 2-7 C atoms, cycloalkyl with 5-7 C atoms or benzyl, can be prepared by reacting a com-pound of the formula XII
CO
~ ~0 (XII) X" CO
in which X" has the abovementioned meaning, with an allyl halide.
These reactions with allyl halides, especially allyl bromide or allyl chloride, are advantageously carried out in a polar medium, especially in an aqueous medium, at temperatures between about 0 and 100C and pre-ferably in the presence of a base, for instance an alkali metal carbonate or hydroxide, for example potassium carbon-ate, potassium hydroxide or sodium hydro~ide.
The cyclisation of polymers according -to the in~
vention, of the polyamidoacid category or polyamide-amido-acid category, to the corresponding polyimides or poly~
, .~ .. _. .. . .. -- . - - - ~-~* r amide-imides, can be carried out in a manner kno~ per se, chemically or therrrially Chemical cyc]isation is advantageously effected by treatment with a dehydrating agent, used by itself or mixed with a -tertiary amine. Examples o~ suitable de-hydrating agen-ts are acetic anhydride, propionic anhy-dride and dicyclohexylcarbodiimide, used by themselves, or as a mixture with, ~or example, triethylamine Thermal cyclisation is effected by hea-ting to temperatures of about 50~250C, preferably about 100-150C, in the presence or absence of an inert organic solvent and/or an azeotropic entraining agent, for example xylenes or toluene. At temperatures above 150C, at least partial crosslinking also generally occurs.
Compounds of the formula I, and the corresponding cyclised imide derivatives, in which a is an integer having a value of about 1-15, especially about l-10, are valuable adhesion promoters, especially between inorganic solids and organic resins, and may be used for a large number of applications in the adhesives industry and in the lacquer-using and plastics-processing industries.
The following are examples of some fields of use:
improving the adhesion of special sealants, for example polysulphides, polyurethanes and polyacrylates, to various substrates, for example glass, aluminium and ceramics;
encapsulating mineral fillers so as to improve the mechan-ical properties of the products prepared therewith, for example in the case of sand-filled masks and cores used in the foundry industry, mineral-filled cable mixtures or other mineral filled plastics, for e~ample filled thermo-setting resins, for instance quartz-filled epoxide resins and filled unsaturated polyesters, filled thermoplastics, for instance polyamide-6,6 and polye-thylene terephthalate, and filled elastomers, for instance natural rubber and synthetic rubber; and incorporation in adhesives, adhes-ive compositions and lacquers, for example adhesive com-positions containing epoxide resins, and lacquers based ~ ~7~3~
~ 19 --on epoxides, polyacr~lates, polyurethanes and vinyl chlor-ide copolymers. However, -the compounds men-tioned are especially suitable for the manufacture of reinforced plastics, especially glass fibre-rein~orced plastics, in particular composite materials, ~or instance l~ninates, in order to improve -the adhesion between the substrate or ma-trix and the plastic applied thereto The substra-te per se may be in any desired form, for example in -the form of fibres, fabrics or nonwovens, and preferably consists of glass or of mineral materials, for example quartz 9 mineral wool, asbestos~ mica or metal fibres and foils.
Examples of suitable plastics for the manufacture of such laminates are acrylates and polyester, epoxide, silicon, melamine, phenolic and furan reslns, and also polyamides, polyamidoacids and polyimides, but especially polymers crosslinkable via C--C double bonds, for instance unsatura-ted polyesters, homopolymers and copolymers containing maleimidyl and nadicimidyl groups, their precursors and their mixtures with o-ther polymers.
Relative to comparable composite materials which have been manufactured using known silicon-containing ad-hesion promoters, especially those of the type mentioned at the outset, glass fibre~reinforced composite materials manufactured using the adhesion promoters according to the invention are distinguished especially by improved resist-ance to thermal oxidation, improved dielectric properties a~ter exposure to moisture, and/or lower water absorption.
The adhesion promoters of the invention are also dis-tinguished by good wetting of the substrates.
The adhesion promoters according to the inven-tion are advantageously applied in the form of solutions in suitable organic solvents, for example N,N-dimethyl-formamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, tetrahydrofuran or dioxane, using conventional techniques.
Polymers of the formula I, and the corre.sponding cyclised imide derivatives, in which a is greater than 15, ... _ . . .. . .
5;~ .
.~nd in ~a3~-t:iculclr i~, a~ e~ C"J" ~'(J 9 me~r be u~ed ;f:or th~ pro-l~cti.orl of~ shclp~cl ar-l::ic;.l(,s h~ particul~rly h.i~,h de~rxee of cro.c;~:linlsirig, for e,;~n)~ :E`ihres, f'il.ms ~shee-ts), coclting c,o:rJ~os1.t~ n;,:Lo.~lr~ r~li.n~t,~s5 cor.,-pr~ssion rno~lldin~rs cln(.l the ~.i.l~e, in a manrler kno~Jrl per se,by heating to temp~ra1;ures ~e-tt,;een a'~out 50 and 350C~
desired in -the pr~sen~e o* convent;:ic)n~l acad:iti.ves, for ex~nple plgments, .t`illers and the lik . The resul~r~
crosslinlce~ polymers containing imidyl groups ~ld s~lo~,ane groups are insolu~le ln organ.ic so~vents~ They are di.stinguished by good mechanical, elec~ricaL and thermal properties, irl par-ticular good corona resistanc,e and high resistanc,e to thermal o~icla-tion, ~on-cyclis~ polymera of the forMula I with a grea-ter -than abou-t l~ and especi~
ally with a at leas-k equal -t,o 20, are dist:ingu:L,shed by good process~billty ~rorn correspondirlg solu~ions. Cross-linking vi.a the imidy:L groups can also be effec-ted by exposure to light, especially UV light, and th:is permits selective s~epwise crosslink.i.ng, in that prelin~irlary cross-linking, via t.he imidyl groups, is ~irst effeeJ~ed under the action of ligh-t, after which crosslinking via the silyl groups is effected thermally. Such stepwise crosslink.ing can under appropriate circumstances also be carried out thermally.
~ a-tion Exa __ . ~1_ In a sulphonation flask, 3.24 g (0.0~ mol) of m phenylenediamine are dissolved in 160 ml of anhydrous N,N~
dimethylaoetamide (D~A) under a nitrogen atmosphere, and the solutio~ is cooled to between 15C and -20C.
6.52 g (0.02 mol) of 5~dimethylmaleimidyl isophthalic acid dichloride are added in portions, with stirring, under conditions such that the temperature does no~ exceed -15C.
The reaction mixture is stirred ~or a further 30 minutes at -15C and then for one hour at 20~25C and thereafter is again cooled to -15C, whereupon a solution of 4 .o4 g Æ
..... ... .. ~ .. ... .
, ~ .. ... ............ .
(0 04 mol) of -trie-thylamine in 20 ml of DMA is added drop~
wise. A fi~e white precipitate forrns. After stirring for one hour a-t 20-25C, the mixture is cooled to 0C. 6.44 g (0.02 rnol) of 3,3',4,4'-benzophenonetetra-carboxylic acid dianhydride are then added in portions.
After stirring for 1 hour at 20-25C, the mixture is again cooled to 0C, after which a solution of 4.39 g (0 02 mol) of ~-aminopropyl-di-n-propoxymethylsilane in 20 ml of DMA
is added dropwise. Stirring is then continued for 1 hour at 20-25C, after which the reaction mixture is fil-tered to remove -the triethylamine hydrochloride which has precipitated. The 10% polyamidoacid solution obtained can be used for finishing glass fibres, from which laminates can be produced.
Example 2 In a sulphonation flask, 4 87 g (0.045 mol) of m-phenylenediamine are dissolved in 160 ml of anhydrous DMA under a nitrogen atmosphere and the solution is cooled to between -15 and -20C. A mixture of 6.09 g (0.03 mol) of isophthalic acid dichloride and 5.96 g (0.02 mol) of 5-maleimidyl-isophthalic acid dichloride is added in portions, with stirring~ under conditions such that the reaction temperature does not exceed -15C. After stirring for one hour at this temperature, a solution of 2.19 g (0.01 mol) of r-aminopropyl-di-n-propoxy-methyl-silane in 10 ml of DMA is added dropwise and the reaction mixture is stirred for a further hour at -15C. A
solution of 10.12 g (0.1 mol) of triethylamine in 30 ml of DMA is then added dropwise, at this temperature, and stirring is continued for 1 hour. After warming to 20-25C, the triethylamine hydrochloride which has precipi-tated is filtered off and the resulting polyamide solution is used for finishing glass fibres.
Using the procedure described in Example 2, 7.07 g (0.0336 mol) of trimellitic acid anhydride chloride, 5.21 g ~0 0144 mol) of 5-nadicimidyl-isophthalic acid di-7S~
chloride, 8 01 g (o oLI mo]) of 4,4~-diaminodlphenyl-ether, 3 51 g (0 016 mol) of r-amlnopropyl di-n-propoxy-methyl-silane and 6~31 g ~0 0624 mol) of -triethylamine are re~
acted in 230 ml of anhydrous DMA. The pol~amidoacid solution ob-tained can be used for finishing glass fibres ~,~
Using the procedure described in Example 2, 3 24 g (0.03 mol) of m-phenylenediamine, 6.69 g (0.028 mol) of sebacic acid dichloride, 2 08 g (0 007 mol) of 5-male-imidyl-isophthalic acid diohloride, 2 19 g (0 01 mol) of ~-aminopropyl-di-n-propoxymethylsilane and 7.08 g (0.07 mol) of triethylamine are reacted in 140 ~1 of anhydrous DMA. The resulting polyamide solution can be used for finishing glass fibres.
- The preparation of 5-dimethylmaleimidyl-isophth-alic acid dichloride, 5-maleimidyl-isophthalic acid di-chloride and 5-nadicimidyl-isophthalic acid dichloride, used in the above examples, is described in German Offen-legungsschriften 2,626,768 and 21626,795.
~e~
In a sulphonation flask, 6.20 g (0 031 mol) of
tie n~lel t~l rr,ay be h~ led -1 c) one enc~ ~he.r by a h~ idF,e mernb e r .
~xa~nples ol su.i. table br:iclge merrbers are:
QL~ Q4 -0~, ~C~I2Cri2 , --C'~ 'T~ , ~Cw~ -S~S , ~SO~, S02~, Q~
Q~
-S02NH-, ~CO-, -CO-, -C-C-, ~CON~ N~I-CO~ Si~ or .. ....
O O O - Ql~
Q~ .
-O Si-O-, .in which Q~ is an alk~l group ~ith 1-6, prefer ably 1-4, carbon a toms or a phenyl grcup, Non-~used bicyclic aromatic radicals Z may also be bonded to one another by two bridge rnembers, such ~s two S02_ ~r,r~oups, ~ Z3 is an alipha~ic radical, it ls preferably an unsubstituted, straight-chain or branched alkylene group with 1-12 carbon atoms, especially an unsubstituted alkyl-ene group with 2-10 carbon atoms.
Cycloaliphatic radicals Z3 are especially S-member-- ed or 6-membered cycloalkylene groups.
If Z3 is a carbocyclic-aromatic radical, the latter preferably contains at least one 6~membered ring; in par-ticular, such radicals ~re monocyclic radicals, fused poly-cyclic rad~cals t or polycyclic radica~ with se~eral cyclic, fused or nor.-fused, s~stems,, which may be bonded to one another directly or by bridge members. Suitable bridge members are those mentioned above in discussing Z, . . :.
L7S;~L
Ca~ ocye:l,ic~arc,lli.J-ti.c radicals ~ .nay also be ~,ubstitll.ted ".Ol ex,~)-nple by r!itro groups, a:!kyl gro~ll)s ~t/.it,h 1-4 carbo-~l atoms, hQ L ogen c'ltO7~1,5, espec,ially ch:l.ori~e, silyl g~roups, su.l.phonic ~.cil groups or s~ ?hau~oyl groups.
Preferably, the ln~iv~.dual rad.icals Z c~re, lndep~
endelltly of one a~lother, an ~lsubs-~ituted alkylene group with 2~10 carbon a-toms or; a monocycli.c., or non-fuxed bi~
cyclic, ~rom~-tic radi.cal which is unsubstitutecl or ~ubs-ti--tuted by halogen, or by alkyl or alko~cy groups, each ~ith 1-4 ca.rbon at.oms (the aromatic nuclel, in a non-:eused bi-cyclic arornatic radi.cal, being boncled to one ~nother direc~ly or via a -0-, -C~12- or ~,S02- bridge ~ernber), or an unsubstituted monocyclic aral~phatic radical, T~e individual radicals Z3 a:re preferably, indep~
endently of one another, an unsubs~itu~;ed alkylerle group with 2 10 C a-toms or an unsubstltu~ed ~onocycllc, fus~d polycyclic or non-*used bicyclic aromatic radical, (the aromatic nuclei, in a non-fused bicycli~ a~oma.tic radical, being bonded to one ano~hcr via a ~0-, -S0 or -C0~ bridge member), Preferred compounds of the ~ormula I, c~nd ~he corresponding cyclised derivatives, are those in ~Ihich a is an integer ~rom 1 to 50, the radicals Yl c~nd Y2 are each a ~CO~Nr~--Z~~ CO~
HOOC ~ L~Si--Q
, - . ~1 .
group or a -CO-NH~ Q group, the group Ql 2 -Rl-Si-Q b~ing bonded in the ortho-position to the ~COOH
or -CO~N~-Z-NH-CO- group, R is ~ CH
i~. ' , ~7~
LO -3 ~O~-O~ -CE~2- ~ 3 ( C}~2 ,~ r 0(),,~
; CH2 ~ ~ I2-~ Sl-Q, (~.:is meth~l o~ alkoxy with 1-l~ C atorns and (~ and Q2 ~r~ each al~yl ~lth 1-4 C atoms, esp~c.ially th~se in which a, Y~, Y~J R, R1, Q, Ql and Q~ have the abo~ementioned preferr~d meaning and -th~ radlcals Z are each a 1,3- or 15~phen~Jlerle group, or a 4~4~-diphenylmetharle~ l~,4'-diphenyl~e~her or 4,4 I _ diphenylculphone radica:l., the r~clicals Z3 ~re each a 1,3-phenylene or l,4-phenylene group or unsubsti.tuted alk~lene with L~-lo C atoms, if m and n are 1, or are each a benzene-~riyl group if m is 1 and n is 2, or are each a benzene-tetrayl group or the benzophenone ring system i~ m and n are 2, and one or both oE the radicals Zl and Z2~ and about 5-50 mol % of these, is a ~C ~0 A
group, in which A is ~ , C - C- or -CH=CH-~ CH3 CH3 Particularly preferred compounds, amongst the above, are those in which ~ is -CH=C~ .
Especially preferred cormpounds, amongst the above, are those in which a is an integer from 1 to 15.
Especially preferred compounds of the formula I
and the corresponding cyclised irnide derivatives, are those in which Yl and Y2 are each a ..
.
~17~
. , ~, I
~)Q.~
, .
- C'0-~ ]~ ~i -Q
0~?~
~ro~lp, 1~ i.s - ~C~I;?)~ or --~ 0-(('11~-~-,~, Q :is lliethy:l o~
alko~ wltll 1 - 4 C cltc)m~; and Q1 ~rld Q2 ar~ ch a.Lkyl ~ith 1 - 4 C ~t:oms.
Particulclrly preferred cor~.pounds of -the formula I, and the corresponding cyclised imide derivatives, are ~ 1~ Y2, R~F~l~ Q~ Ql and Q~ have the above mentioned preferIed meanings, a i.s an in~eger frorn 1 ~o 50, and rn and n are each 1, ~ i.s a 1,3- or 1,4--phenylene group, or a L" L~ '-cliphenylme-tharle or ~+,4'~di.phen~Jl~ether radical and Z~ is a 1,3-phenylene or 1,4-phenylene group, but only nne of Z and Z3 is a 1,4-phenylene group; or m is 1 and n i.s 2, Z ls a 1~3- or 1,4-phenylene group, or a 4,4'-diphenylr.lethane or 4,4'~dlphenyl-e-ther ~3L75i~L
.~dic~ r~l Z~ .i; a 'L~ r~ c~
or m arid n ~lre eac~l 2, ~. is a :!, 3- or :1. ,L~-phen~ rie ~ro~ , o~ ?r~ Lh~ o~ i.r)~en ~ h~
racli cal alld Z~ i.s a berlz,enctetr a~:l L-~rc~llp or the benzophen-one ri.n~, system~
and in ~rhich ~hout 10-30 mc)l % ~f Zl and ~2~ is a ~ or OC _ CO OC ~<CO
C~ H3 group. Pc~r~icularly pr~fcrrcd comF)o~ln~ls, 2mongst tho above, are t~lOSC in which ~ i~ an inteyer ~rom 1 to 10.
Very particularly preferred compounds, amongs-t the above ? are those in which Q is methyl, ethoxy or n-propoxy and Ql and Q2 are each ethyl or n-propyl The reaction of a co,npound of the formula II or III
with a co;npound o. the formula IV and/or V is carried out in a manner known per se, preferably in an anhydrous i.nert organic solvent at temperatures between about -20C and *150C, especially about -15C to ~50C
Examples of organic solvents ~hich may be employed are Ghlorinated or non-chlorinated aromatic hy~rocarbons, for exc~mple benzene, toluene, xylenes and chloro~enzene;
chlorinated or non-chlorinated aliphatic hydrocarbons, for example n-pentane, n-'nexane, methylene chloride, chloroform, tetrachloroethane and tetrachloroethylene; aliphatic and cycloaliphatic ketones, for examp.le acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; cyclic ethers, for example tetrahydrofuran, tetrahydropyran and dioxane;
cyclic amides, for example N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-~-c~prolactarn; N,N-dialkylamides of aliphatic monocar~oxylic acids with 1-3 carbon atoms in the acid part, for example N,N-dimethyl-formamide, N,N-dimethylacetamide, N,N-diethylacetamide and ~.
5~
N,N-dimethylme-thoxyace-tamide, hexame~hylphosphorotriamide (hexametapol); N,N,N',N' ~e-trarfle-thylurea, -tetrahydrothio-phene dioxide (sulpholan); dialkylsulphoxides, for example dimethylsulphoxide and d:ie-thylsulphoxide; phenol and cresols.
The reaction can also be carried out in mixtures of such solven-ts.
Preferred solvents are N,N-dialkylamides of ali~
phatic monocarboxylic acids with 1-3 carbon atoms in the acid part, especially N,N~dimethyl*ormamide and N,N-dime-thylacetamide, and cyclic amides, for example N-methyl~
2-pyrrolidone.
The compounds of the formula III are reac-ted with the compounds of the formula I~ and/or V in a molar ratio of at least 2:1. If al in formula III is -l, the com-pound of the formula III is advantageously used in the stoichiometric amount or in a slightly smaller amount than this. For the reaction with oligomers or polymers of the formula III (al greater than or equal to 1), the re-actants are preferably employed in the stoichiometric amount.
If the compounds of the formula IV or V are re-acted with oligomers or polymers of the formula III, the latter are advantageously used in the form of their solu-tions, as ob-tained from their preparation.
To prepare compounds of the formula I, in which Y
Ql and Y2 are each a -CO-NH-R-Si-Q group, a compound of the formula II or III, in which R4 and/or R5 are not -NH-Z-NH2 and R~ is preferably alkoxy with 1-4 C atoms or phenoxy and especially chlorine, and if m and n are 1 or m is 1 and n is 2, R5 is alkoxy with 1-4 C atoms or phenoxy and especially chlorine, and if m and n are 2, R5 together with R6 is the -O- group, is reacted with a compound of the formula IV or with a mixture of two different com-pounds of the formula IV.
5;~
To prepare compounds of the forrnula I, in which Y
and Y2 are each a ~CO~ Z-N~-CO
~ IQl HOOC Rl- Si-Q?
group, a compound of the formula V or a mixture of two different compounds of the formula V is reacted wi-th a compound of the formula II or III, in which R4 or R5 is _ 2 Analogously, compounds of the formula I, in which . ~Ql one of Yl and Y2 is a -CO-NH-R-Si-Q group and the other is a Q2 --C~NH--Z--NH~O
HOOC ~ Rl- Si- Q
group, areprepared by reacting a compound of the XI or III, in which one of the terminal functional groups R4 and R5 is not -NH-Z-NH2 and the other is -OH, alkoxy with 1-4 C atoms, phenoxy or chlorine, or, if m is 2, R5 together with R6 is -O-, with a mixture of a compound of the formula IV and a compound of the formula V.
In all these cases, the compound of the formula IV
and/or V is preferably employed in the stoichiometric amount.
After completion of the reaction, the solvents can, if desired, be removed in the usual manner, for example by distilling off, if appropriate under reduced pressure.
The starting compounds o~ the ~ormula II are in the , , ... ~ ............. . . . . . ... ,. ., . .. . ... ..... ........ , .. . . .. .. , ....... ........ . . _~
~7S;~
majority o~ cases described in Gerrnan Offenlegungsschriften 2,626,768 and 2,626,795 and may all be prepared in accord-ance with the method disclosed there Compounds of the forrnula III can be prepared in a manner known per se, by reacting a compound of the formula VI
H2N-Z~-NH-CO-Z2-CO_NH_Z ~ MH2 ~VI) with an excess of a compound o~ the formula II and/or of a compound of the formula VII
R50C~ ~(C0~6)m-l (VII) (R60C)n_l CO 5 al, m~ n~ Z, Z2~ Z3, R5 and R6 being as defined above.
The compounds of the formula VI can, for their part, be obtained by reacting an excess of diamine H2N-Z-NH2 with a dicarboxylic, tricarboxylic or tetra-carboxylic acid derivative of the formulaeVIII and/or IX
R 'OC ~ C0~4~ X5'0C~ ~(OOR6 )m-l N and/or ~R6~0C)~_l COR5 .
(IX~
(VIII) in which m, n, A and Z3 are as defined above, the radicals R4' independently of one another are ~OH, chlorine, alk-oxy with 1-4 C atoms or phenoxy and the radicals R5' in-dependently of one another are -OH, chlorine, alkoxy with 1-4 C atoms or phenoxy, or, if m and/or n is l, R5' to-gether with R6' is -O-, the groups COR5' and -COR6' are bonded to different C atoms and, if Z3 is a cyclic radi-7S~
cal and m and/or n is 2, the -COR5' group or groups are each in the ortho-posi-tion -to a -COR6' group Compounds of -the ~ormula III, in which R4 and R5 i are not -NH-Z-NH2, can also be prepared by reac-ting a diamine H2N-Z-NH2 with an excess of a mixture of different compounds of the formulae VIII and IX.
The condensation of a compound of the formula VI
with a compound of the formula II and/or a compound of the formula VII, and the preparation of compounds of the ~ormula III or VI from diamines H2N-Z-~2 and dicarboxylic, tricarboxylic or tetracarboxylic acid derivatives of the formulae VIII and/or IX is carried out in-a manner known per se, advantageously at temperatures from about -50C
to ~300C. The condensation can be carried out in the melt or, preferably, in an inert organic solvent or a solvent mixture. For condensation in solution, temp-eratures of about -20C to +200C, very particularly about -20C to +50C, are preferred. In the said reactions, it may under certain circumstances be advantageous to add known polymerisation inhibitors, for example hydroquinones, pyrocatechol or cresols, for example di-tert.-butylcresol.
Examples of suitable inert organic solvents are those mentioned above in connection with the reaction of compounds of the formula II or III with the compounds of the formula IV and/or V.
The hydrochloric acid formed during the conden-sation or polycondensation of compounds of the formulae II, VII, VIII or IX, in which R4, R4', Rs or Rs' is chlorine~
with the diamines H2N-Z-NH2 or the diamines of the formula III can be removed by neutralisation with basic compounds, - for example calcium hydroxide or trie-thylamine, or by re-action with an epoxide compound, for example ethylene oxide or propylene oxide, and by washing out with a suit-able solvent, for example water~ - The condensation reactions are advantageously carried out with exclusion of moisture, for example in an iner-t gas atmosphere, for instance nitrogen.
~ 7 The ami~osilanes of the formula IV are kno~ or can be prepared in a manner kno~ per se. The com-pounds of the ~`ormula V can be prepare~ by reacting a com-pound of the formula X
/0 (X) Rl ~ CO
which R ' is -O-CH2CH =CH2 or -N-CH2CH 2 ~.
alkyl with 2-7 C atoms, cycloalkyl with 5-7 C atoms, benzyl or allyl 9 with a silane of the formula XI
Ql H-Si-Q (XI) ~Q2 in which Q, Ql and Q2 are as defined under formula I.
The reaction is advantageously carried out in an anhydrous organic medium and in the presence of a catalyst.
Examples of catalysts which can be used are organic per-oxides, for instance tert.-butyl hydroperoxide, di-tert.-butyl peroxide, benzoyl peroxide, diacyl peroxides and cumene hydroperoxide, or platinum and palladium catalysts, for example platinum/charcoal catalysts or PtC16H2 cata-lysts.
Examples of suitable inert organic solvents are aromatic hydrocarbons, for instance benzene, toluene and xylenes, cyclic ethers, for instance tetrahydrofuran, tetrahydropyran and dioxane, or ethylene glycol monoalkyl ethers and dialkyl ethers, wi-th 1-4 C atoms in each alkyl par-t, for instance ethylene glycol monomethyl ether, mono-ethyl ether, diethyl ether and di-n-butyl ether. Aroma-tic hydrocarbons are pre~erred ~ ~ 7 The reaction is advan-tageously carried out under a protective gas, for example nltrogen or argon.
The reaction temperatures are in general approx-imately between 80 and 150C; reaction tempera-tures be-tween approximately 90 and 120C are preferred, The compounds of -the formula XI are known.
Compounds of the formula X, in which Rl' is a diallylamino group, can be prepared, for example, by re-acting aminophthalic acid or the corresponding alkali metal salts or alkaline earth metal salts with allyl hal-ides and cyclising the resulting N,N-diallylaminophthalic acid. Compounds of the formula X, in which Rl' is an allyloxy group, can be obtained by reacting hydroxyphth-alic anhydride with an allyl halide. Finally, com-pounds of the formula X, in which Rl' is a -N-CH2CH=CH2 X~
group and X" is alkyl with 2-7 C atoms, cycloalkyl with 5-7 C atoms or benzyl, can be prepared by reacting a com-pound of the formula XII
CO
~ ~0 (XII) X" CO
in which X" has the abovementioned meaning, with an allyl halide.
These reactions with allyl halides, especially allyl bromide or allyl chloride, are advantageously carried out in a polar medium, especially in an aqueous medium, at temperatures between about 0 and 100C and pre-ferably in the presence of a base, for instance an alkali metal carbonate or hydroxide, for example potassium carbon-ate, potassium hydroxide or sodium hydro~ide.
The cyclisation of polymers according -to the in~
vention, of the polyamidoacid category or polyamide-amido-acid category, to the corresponding polyimides or poly~
, .~ .. _. .. . .. -- . - - - ~-~* r amide-imides, can be carried out in a manner kno~ per se, chemically or therrrially Chemical cyc]isation is advantageously effected by treatment with a dehydrating agent, used by itself or mixed with a -tertiary amine. Examples o~ suitable de-hydrating agen-ts are acetic anhydride, propionic anhy-dride and dicyclohexylcarbodiimide, used by themselves, or as a mixture with, ~or example, triethylamine Thermal cyclisation is effected by hea-ting to temperatures of about 50~250C, preferably about 100-150C, in the presence or absence of an inert organic solvent and/or an azeotropic entraining agent, for example xylenes or toluene. At temperatures above 150C, at least partial crosslinking also generally occurs.
Compounds of the formula I, and the corresponding cyclised imide derivatives, in which a is an integer having a value of about 1-15, especially about l-10, are valuable adhesion promoters, especially between inorganic solids and organic resins, and may be used for a large number of applications in the adhesives industry and in the lacquer-using and plastics-processing industries.
The following are examples of some fields of use:
improving the adhesion of special sealants, for example polysulphides, polyurethanes and polyacrylates, to various substrates, for example glass, aluminium and ceramics;
encapsulating mineral fillers so as to improve the mechan-ical properties of the products prepared therewith, for example in the case of sand-filled masks and cores used in the foundry industry, mineral-filled cable mixtures or other mineral filled plastics, for e~ample filled thermo-setting resins, for instance quartz-filled epoxide resins and filled unsaturated polyesters, filled thermoplastics, for instance polyamide-6,6 and polye-thylene terephthalate, and filled elastomers, for instance natural rubber and synthetic rubber; and incorporation in adhesives, adhes-ive compositions and lacquers, for example adhesive com-positions containing epoxide resins, and lacquers based ~ ~7~3~
~ 19 --on epoxides, polyacr~lates, polyurethanes and vinyl chlor-ide copolymers. However, -the compounds men-tioned are especially suitable for the manufacture of reinforced plastics, especially glass fibre-rein~orced plastics, in particular composite materials, ~or instance l~ninates, in order to improve -the adhesion between the substrate or ma-trix and the plastic applied thereto The substra-te per se may be in any desired form, for example in -the form of fibres, fabrics or nonwovens, and preferably consists of glass or of mineral materials, for example quartz 9 mineral wool, asbestos~ mica or metal fibres and foils.
Examples of suitable plastics for the manufacture of such laminates are acrylates and polyester, epoxide, silicon, melamine, phenolic and furan reslns, and also polyamides, polyamidoacids and polyimides, but especially polymers crosslinkable via C--C double bonds, for instance unsatura-ted polyesters, homopolymers and copolymers containing maleimidyl and nadicimidyl groups, their precursors and their mixtures with o-ther polymers.
Relative to comparable composite materials which have been manufactured using known silicon-containing ad-hesion promoters, especially those of the type mentioned at the outset, glass fibre~reinforced composite materials manufactured using the adhesion promoters according to the invention are distinguished especially by improved resist-ance to thermal oxidation, improved dielectric properties a~ter exposure to moisture, and/or lower water absorption.
The adhesion promoters of the invention are also dis-tinguished by good wetting of the substrates.
The adhesion promoters according to the inven-tion are advantageously applied in the form of solutions in suitable organic solvents, for example N,N-dimethyl-formamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, tetrahydrofuran or dioxane, using conventional techniques.
Polymers of the formula I, and the corre.sponding cyclised imide derivatives, in which a is greater than 15, ... _ . . .. . .
5;~ .
.~nd in ~a3~-t:iculclr i~, a~ e~ C"J" ~'(J 9 me~r be u~ed ;f:or th~ pro-l~cti.orl of~ shclp~cl ar-l::ic;.l(,s h~ particul~rly h.i~,h de~rxee of cro.c;~:linlsirig, for e,;~n)~ :E`ihres, f'il.ms ~shee-ts), coclting c,o:rJ~os1.t~ n;,:Lo.~lr~ r~li.n~t,~s5 cor.,-pr~ssion rno~lldin~rs cln(.l the ~.i.l~e, in a manrler kno~Jrl per se,by heating to temp~ra1;ures ~e-tt,;een a'~out 50 and 350C~
desired in -the pr~sen~e o* convent;:ic)n~l acad:iti.ves, for ex~nple plgments, .t`illers and the lik . The resul~r~
crosslinlce~ polymers containing imidyl groups ~ld s~lo~,ane groups are insolu~le ln organ.ic so~vents~ They are di.stinguished by good mechanical, elec~ricaL and thermal properties, irl par-ticular good corona resistanc,e and high resistanc,e to thermal o~icla-tion, ~on-cyclis~ polymera of the forMula I with a grea-ter -than abou-t l~ and especi~
ally with a at leas-k equal -t,o 20, are dist:ingu:L,shed by good process~billty ~rorn correspondirlg solu~ions. Cross-linking vi.a the imidy:L groups can also be effec-ted by exposure to light, especially UV light, and th:is permits selective s~epwise crosslink.i.ng, in that prelin~irlary cross-linking, via t.he imidyl groups, is ~irst effeeJ~ed under the action of ligh-t, after which crosslinking via the silyl groups is effected thermally. Such stepwise crosslink.ing can under appropriate circumstances also be carried out thermally.
~ a-tion Exa __ . ~1_ In a sulphonation flask, 3.24 g (0.0~ mol) of m phenylenediamine are dissolved in 160 ml of anhydrous N,N~
dimethylaoetamide (D~A) under a nitrogen atmosphere, and the solutio~ is cooled to between 15C and -20C.
6.52 g (0.02 mol) of 5~dimethylmaleimidyl isophthalic acid dichloride are added in portions, with stirring, under conditions such that the temperature does no~ exceed -15C.
The reaction mixture is stirred ~or a further 30 minutes at -15C and then for one hour at 20~25C and thereafter is again cooled to -15C, whereupon a solution of 4 .o4 g Æ
..... ... .. ~ .. ... .
, ~ .. ... ............ .
(0 04 mol) of -trie-thylamine in 20 ml of DMA is added drop~
wise. A fi~e white precipitate forrns. After stirring for one hour a-t 20-25C, the mixture is cooled to 0C. 6.44 g (0.02 rnol) of 3,3',4,4'-benzophenonetetra-carboxylic acid dianhydride are then added in portions.
After stirring for 1 hour at 20-25C, the mixture is again cooled to 0C, after which a solution of 4.39 g (0 02 mol) of ~-aminopropyl-di-n-propoxymethylsilane in 20 ml of DMA
is added dropwise. Stirring is then continued for 1 hour at 20-25C, after which the reaction mixture is fil-tered to remove -the triethylamine hydrochloride which has precipitated. The 10% polyamidoacid solution obtained can be used for finishing glass fibres, from which laminates can be produced.
Example 2 In a sulphonation flask, 4 87 g (0.045 mol) of m-phenylenediamine are dissolved in 160 ml of anhydrous DMA under a nitrogen atmosphere and the solution is cooled to between -15 and -20C. A mixture of 6.09 g (0.03 mol) of isophthalic acid dichloride and 5.96 g (0.02 mol) of 5-maleimidyl-isophthalic acid dichloride is added in portions, with stirring~ under conditions such that the reaction temperature does not exceed -15C. After stirring for one hour at this temperature, a solution of 2.19 g (0.01 mol) of r-aminopropyl-di-n-propoxy-methyl-silane in 10 ml of DMA is added dropwise and the reaction mixture is stirred for a further hour at -15C. A
solution of 10.12 g (0.1 mol) of triethylamine in 30 ml of DMA is then added dropwise, at this temperature, and stirring is continued for 1 hour. After warming to 20-25C, the triethylamine hydrochloride which has precipi-tated is filtered off and the resulting polyamide solution is used for finishing glass fibres.
Using the procedure described in Example 2, 7.07 g (0.0336 mol) of trimellitic acid anhydride chloride, 5.21 g ~0 0144 mol) of 5-nadicimidyl-isophthalic acid di-7S~
chloride, 8 01 g (o oLI mo]) of 4,4~-diaminodlphenyl-ether, 3 51 g (0 016 mol) of r-amlnopropyl di-n-propoxy-methyl-silane and 6~31 g ~0 0624 mol) of -triethylamine are re~
acted in 230 ml of anhydrous DMA. The pol~amidoacid solution ob-tained can be used for finishing glass fibres ~,~
Using the procedure described in Example 2, 3 24 g (0.03 mol) of m-phenylenediamine, 6.69 g (0.028 mol) of sebacic acid dichloride, 2 08 g (0 007 mol) of 5-male-imidyl-isophthalic acid diohloride, 2 19 g (0 01 mol) of ~-aminopropyl-di-n-propoxymethylsilane and 7.08 g (0.07 mol) of triethylamine are reacted in 140 ~1 of anhydrous DMA. The resulting polyamide solution can be used for finishing glass fibres.
- The preparation of 5-dimethylmaleimidyl-isophth-alic acid dichloride, 5-maleimidyl-isophthalic acid di-chloride and 5-nadicimidyl-isophthalic acid dichloride, used in the above examples, is described in German Offen-legungsschriften 2,626,768 and 21626,795.
~e~
In a sulphonation flask, 6.20 g (0 031 mol) of
4,4'-diaminodiphenyl-ether (DDA) are dissolved in 50 ml of anhydrous N,N'-dimethylacetamide under a nitrogen atmosphere, and the solution is cooled to between -15 and -20C 1.78 g (0 006 mol) of 5-maleimidyl-isophthalic acid dichloride (MIP) are added in portions, with stirring, under conditions such that the temperature does not exceed -15C The reaction mixture is stirred for a further 30 minutes at -15C and then for one hour at 20 to 25C, after which it is again cooled to -15C and 1.21 g (0.012 mol) of triethylamine are added dropwise. A fine, white precipitate forms. After stirring for one hour at 20 to 25C, the mixture is cooled to 0C. 5.23 g (0.024 mol) of pyromelli-tic acid dianhydride (PMDA) are then added in portions After stirring for one hour at 20 to 25C, the mixture is again cooled to 0C, after .which 1.31 g (0.002 mol) of 4-N,N'-bis-[3-(tri-n-propoxy)-.
~L7~3.~
slly:Lrp~opy:l~ .ir~o~ t~ ic -Ir~ .3~ (3d.~-~d l~opT"is~:, The re~ct:ioJI rni.~.ture :is 't;h(.,!^~ ,c,t,.irr~(l f'or a i'urlheJ:~ hour at 20C, a:f`~er ~/hicil i-t ic; I`il-lerecl ~o :remove -the~ tr.iethyl~
amine hyclroch:Lor'lde whlch has prec:i~ tatecl, The 10%
polyami.cioacid solutioll ol)lai.ne(l :is (,rlSt on a glass p:Lcl-te -l;o produce rl I' il.m ar~ ri,e~ :irl a vacuum oven for 2~ hours at 60 to :L50C, :~or 2 hours at 150 t;o 250C and for ~ ~lours at 250C, h tr~nsparen'G, flex~-~.ible and tough filrn is obtained, Examr,]e f~
In a sul.phona-tiorl:Clask, 14,56 g (0,04 mol) of 5 nadici.midyl isoph-thalic acid dichloride are di.ssolved in 150 ml of anhydrous N,N~-dime-thylace-'camide under a nitro-gen atmosphere, c~nd -the solution is cooled -to bet~ean -15 and -20C A solution o~ 17,6~ g (ObO8 rnol) of ~-aminopropyl trie-thoxysilane irl 25 Inl of N,N~~dim~-thylacet~
amide is added dropwise a~ ~15C, with stirring. Af-ter stirring for one hour at this temperat;ure, a solu-t;ion of 8.09 g (0.08 mol) of trie-thylcuni.rle in 28 ml of N,N'~di~
methylacetamide i.s added dropwise and the reaction mix~ure is s-tirred for a further hour, Af-ter warming to 20-25C, the triethylamine hydrochloride which has pre-cipitatèd is ~iltered off. The solution of the di-amide obtained can be used for finishing glass fibres, ClOC COG1 ~ '.
~N~ ~ 2 N~12 ~ 2) 3 s i ~o~2~l5~ 3 ~C ~C--O
In a sulphona-tion flask, 3.~4 g (0 03 mol) of 1,3-phenylenediamine are dissolved in 80 ml of anhydrous N7N t _ dimethylacetamide under a nitrogen atmosphere and the solu-tion is cooled to between -15 and -20C. 3.26 g (0.01 mol) of 5-(dimethylmaleimidyl)-isophthalic acid di-chloride are added in portions, with stirring, under con-ditions such that the temperature does not exceed -15C.
The reaction mixture is stirred for a further hour at -15 C. Thereafter, 3.58 g (0.015 mol) of sebacic acid dichloride are added dropwise at this temperature, and stirring is continued for 30 minutes. 5.06 g (0.05 mol) of triethylamine are then added dropwise and a~ter stirring for one hour at 20 to 25C the mixture is cooled to 0C. A solution of 3.66 g ( 0.01 mol) of 3~
methyl-di-n-propoxy-silyl)-propoxy-phthalic anhydride in 34 ml of N,N'-dimethylacetamide is then added dropwise, the mixture is stirred for a further hour at 20 to 25C
and the triethylamine hydrochloride which has precipitated during the reaction is ~iltered off. The resulting polyamidoacid solution can be used for finishing glass ~ibres, from which laminates are produced.
Use Examples a) Im~regnation of glass fibre fabrics A glass fibre fabric made from so-called E~glass, with satin weave and weighing 280 g/m2, is first thermally desized to about 0.1% by weight residual size content and is then impregnated with 2% solutions of the adhesion pro-moters or of the commercially available adhesion promoters listed below. The adhesion promoter solutions are applied by immersion, with an impregnation speed of 005 m/minute, and the impregnated material is then dried ~r 20 minutes at 180C in a circulating air oven.
. The prepregs obtained contain ~rom 0.09 to 0.11%
by weight, based on glass, of adhesion promoter.
The following areused as a~hesionpromoters(finishes):
1) No adhesion promoter ... . . , , . .. . ... . . .: . .. ... . .. . .. ... . .
~ ~ ~ 7 2) Vinyl-tri -(2-methoxyethoxy)-silane (~Silan A 172"
from Messrs, Union Carbicle); 2% solution in N,N-dimethyl-formamide (DMF) 3) ~-Aminopropyl-triethoxysilane ("Silan A 1100" from Messrs, Union Carbide); 2% solu-tion in ~MF
4) Adhesion promoter solution according to Preparation Example 1, diluted to 2% by weight with DMF
~L7~3.~
slly:Lrp~opy:l~ .ir~o~ t~ ic -Ir~ .3~ (3d.~-~d l~opT"is~:, The re~ct:ioJI rni.~.ture :is 't;h(.,!^~ ,c,t,.irr~(l f'or a i'urlheJ:~ hour at 20C, a:f`~er ~/hicil i-t ic; I`il-lerecl ~o :remove -the~ tr.iethyl~
amine hyclroch:Lor'lde whlch has prec:i~ tatecl, The 10%
polyami.cioacid solutioll ol)lai.ne(l :is (,rlSt on a glass p:Lcl-te -l;o produce rl I' il.m ar~ ri,e~ :irl a vacuum oven for 2~ hours at 60 to :L50C, :~or 2 hours at 150 t;o 250C and for ~ ~lours at 250C, h tr~nsparen'G, flex~-~.ible and tough filrn is obtained, Examr,]e f~
In a sul.phona-tiorl:Clask, 14,56 g (0,04 mol) of 5 nadici.midyl isoph-thalic acid dichloride are di.ssolved in 150 ml of anhydrous N,N~-dime-thylace-'camide under a nitro-gen atmosphere, c~nd -the solution is cooled -to bet~ean -15 and -20C A solution o~ 17,6~ g (ObO8 rnol) of ~-aminopropyl trie-thoxysilane irl 25 Inl of N,N~~dim~-thylacet~
amide is added dropwise a~ ~15C, with stirring. Af-ter stirring for one hour at this temperat;ure, a solu-t;ion of 8.09 g (0.08 mol) of trie-thylcuni.rle in 28 ml of N,N'~di~
methylacetamide i.s added dropwise and the reaction mix~ure is s-tirred for a further hour, Af-ter warming to 20-25C, the triethylamine hydrochloride which has pre-cipitatèd is ~iltered off. The solution of the di-amide obtained can be used for finishing glass fibres, ClOC COG1 ~ '.
~N~ ~ 2 N~12 ~ 2) 3 s i ~o~2~l5~ 3 ~C ~C--O
In a sulphona-tion flask, 3.~4 g (0 03 mol) of 1,3-phenylenediamine are dissolved in 80 ml of anhydrous N7N t _ dimethylacetamide under a nitrogen atmosphere and the solu-tion is cooled to between -15 and -20C. 3.26 g (0.01 mol) of 5-(dimethylmaleimidyl)-isophthalic acid di-chloride are added in portions, with stirring, under con-ditions such that the temperature does not exceed -15C.
The reaction mixture is stirred for a further hour at -15 C. Thereafter, 3.58 g (0.015 mol) of sebacic acid dichloride are added dropwise at this temperature, and stirring is continued for 30 minutes. 5.06 g (0.05 mol) of triethylamine are then added dropwise and a~ter stirring for one hour at 20 to 25C the mixture is cooled to 0C. A solution of 3.66 g ( 0.01 mol) of 3~
methyl-di-n-propoxy-silyl)-propoxy-phthalic anhydride in 34 ml of N,N'-dimethylacetamide is then added dropwise, the mixture is stirred for a further hour at 20 to 25C
and the triethylamine hydrochloride which has precipitated during the reaction is ~iltered off. The resulting polyamidoacid solution can be used for finishing glass ~ibres, from which laminates are produced.
Use Examples a) Im~regnation of glass fibre fabrics A glass fibre fabric made from so-called E~glass, with satin weave and weighing 280 g/m2, is first thermally desized to about 0.1% by weight residual size content and is then impregnated with 2% solutions of the adhesion pro-moters or of the commercially available adhesion promoters listed below. The adhesion promoter solutions are applied by immersion, with an impregnation speed of 005 m/minute, and the impregnated material is then dried ~r 20 minutes at 180C in a circulating air oven.
. The prepregs obtained contain ~rom 0.09 to 0.11%
by weight, based on glass, of adhesion promoter.
The following areused as a~hesionpromoters(finishes):
1) No adhesion promoter ... . . , , . .. . ... . . .: . .. ... . .. . .. ... . .
~ ~ ~ 7 2) Vinyl-tri -(2-methoxyethoxy)-silane (~Silan A 172"
from Messrs, Union Carbicle); 2% solution in N,N-dimethyl-formamide (DMF) 3) ~-Aminopropyl-triethoxysilane ("Silan A 1100" from Messrs, Union Carbide); 2% solu-tion in ~MF
4) Adhesion promoter solution according to Preparation Example 1, diluted to 2% by weight with DMF
5) Adhesion promoter solution according to Preparation Example 2, diluted to 2% by weight with DMF
6) Adhesion promoter solution according to Preparation Example 3, diluted to 2% by weigh-t with DMF
7) Adheslon promoter solution according to Preparation Example 4~ diluted to 2% by weight with DMF
8) Adhesion promo-ter solution according to Preparation Example 6, diluted to 2% by weight with DMF
9) Adhesion promoter solution according -to Preparation Example 7, diluted to 2% by weight with DMF.
b) ~
1.0 mol of N,N'-4,4'-diphenylmethane-bis-maleimide is dissolved in 500 g of furfuryl alcohol at 100C and tha solution is cooled to 25C, 0.4 mol of 4,4'-diamino-diphenylmethane is dissolved in 200 g of methylglycol at 25C. The two solutions are combined and mixed thor~
oughly. The glass fibre fabrics finished in accordance with section a) are impregnated wi-th this mixed solution - by the immersion process at 25C and are then dried in a circulating air oven for 18 minutes at 180C; the result-ing prepregs contain 39% by weight of resin. 10 layers of the impregna-ted fabric are then pressed hot between two 35 microns thick copper foils which have been pretrea-ted by electrolytic surface coating with brass. The press is first kept under light contact pressure for 2 to 3 min-utes; the pressure is then raised to 40 kp/cm2 and the assembly is pressed for 1 hour at 180Co The test specimens are then taken out of the press and post-cured for a further 6 hours in an oven at 240C; the resulting laminate sheets contain 35% by weight of resin.
.
~7 5 ~ 26 -Propert_es of -the resulting copper-covered laminate sheets Flexural stren~th in M/mm2 according to ISO/R 178 a) Initial value b) Af-ter 10 days' aging at 270C
Water absorption In % by weight at 23C after 24 hours, The measurements are carried out on flexura] test specimens according to VSM Standard Specification 77,103.
Dielectric loss factor tg ~/50 c/s according to DIN 53,483 a) Initial value measured at 23C
b) After 6 hours' storage in boiling water Dl~lestr i r c ~n~tA~: r/50 c/s according to DIN 53,483 a) Initial value measured at 23C
b) After 6 hours' storage in boiling water ISO/R = International Standards Organisation/Recommenda~ions VSM = Verein Schweizerischer Maschinenindus-trieller DIN = Deutsche Industrie Norm The results are summarised in Table I which follows~ The numbering of the experimental products is the same as under a).
.
- - ~r _, _ _ _ _ __ ~ ,~
a~ ~ ~ o o c~ u~ L~
~ ~ __ __ _ __ . .__ . r~ c~l ~ ~ ~ ~ ~
CO ~ C- o o o Lr~ L~
_~ _ ~ __ .
,Q U~ J. c~l (~ ~ O. ~J
~1 . ~ ~O ~\I O O O U~ I
~ ~; _ ~ ~ ___ x ~ o a~
O ~ ~D ~ ~ ~ _~ G~
~ ~O ~ O O O ~i 1~ U~
~) 1~ C~l ~
O _ J_ _ _ J t\l ~I ~D a~ 1 ~0 L~ ~ ~1 O O O J Lr~
~: ~ C~ ~ , J
~ _ . __ _ +' ~ ;t ~
r O O ~ ~1 ~1 ~ ~ O ~I
P~ ;t' ~ ~i O O O U~
~q . _ . - _ ' C~l O ~ 0~ ~ ~ C~J r~ L~
1~ ~O t\i O C~i ~ 1~ U~
~,q ~ 00 U~
~ - - -cc o~ : ~ ~ ~. 0 C~l O ~0 O ~ C~i u~ L~
~ r~
- ~ - - -. ~. :. ~. ~ ~
~ ~ ~ ~ O ~ ~ ~ ~D
q~
~q ~ l ~
. a) ~ ~ t~ I h )~-~ h a) ~ ~ ~
~-~ .~ ,1 rl J 1~ ~ O ~ $~ ~1 0 +' t~ ~ t~ hO ~\1 4 t~
bO O h ~q ,1 ~Q
+~ S~ rl O u~ _ bO
~q O ~d ~n+' ~ V o ^ u~ O s~
a) h ~rl ~ ~ ~o H u~ h ~1 o ~,1 h ,1 ~+' ~J h ~t~ ~ ~H ~r~
,~ ~ o ~ ~ o o ,~ C~ ^o ,~
U~ ~ .~ ,~ o ~ o ~ ~i ~r-l O t~ r~ h 0 r{~h H t~ ~10 ~ ~ ,s~ ~o +~ c) ~D
h ^ O rl 0 ~ 5: t.) ~ ~I h ~ h o u~ ~ ~ a~ h ~rl~ o a) F, ~rl I X E o~ C~Ja> ~ h ~1 ~ a) H u~
a~ F t~ +-) ~ a~ ) a) ~ ~ ~ ~ a~
~S H` . ~ +~ ~ ~ o ~ ~ b~ .r~ h~ ~ bO
E I ~ ~: P ~ . ~ O ~ ~ (1) ~
__
b) ~
1.0 mol of N,N'-4,4'-diphenylmethane-bis-maleimide is dissolved in 500 g of furfuryl alcohol at 100C and tha solution is cooled to 25C, 0.4 mol of 4,4'-diamino-diphenylmethane is dissolved in 200 g of methylglycol at 25C. The two solutions are combined and mixed thor~
oughly. The glass fibre fabrics finished in accordance with section a) are impregnated wi-th this mixed solution - by the immersion process at 25C and are then dried in a circulating air oven for 18 minutes at 180C; the result-ing prepregs contain 39% by weight of resin. 10 layers of the impregna-ted fabric are then pressed hot between two 35 microns thick copper foils which have been pretrea-ted by electrolytic surface coating with brass. The press is first kept under light contact pressure for 2 to 3 min-utes; the pressure is then raised to 40 kp/cm2 and the assembly is pressed for 1 hour at 180Co The test specimens are then taken out of the press and post-cured for a further 6 hours in an oven at 240C; the resulting laminate sheets contain 35% by weight of resin.
.
~7 5 ~ 26 -Propert_es of -the resulting copper-covered laminate sheets Flexural stren~th in M/mm2 according to ISO/R 178 a) Initial value b) Af-ter 10 days' aging at 270C
Water absorption In % by weight at 23C after 24 hours, The measurements are carried out on flexura] test specimens according to VSM Standard Specification 77,103.
Dielectric loss factor tg ~/50 c/s according to DIN 53,483 a) Initial value measured at 23C
b) After 6 hours' storage in boiling water Dl~lestr i r c ~n~tA~: r/50 c/s according to DIN 53,483 a) Initial value measured at 23C
b) After 6 hours' storage in boiling water ISO/R = International Standards Organisation/Recommenda~ions VSM = Verein Schweizerischer Maschinenindus-trieller DIN = Deutsche Industrie Norm The results are summarised in Table I which follows~ The numbering of the experimental products is the same as under a).
.
- - ~r _, _ _ _ _ __ ~ ,~
a~ ~ ~ o o c~ u~ L~
~ ~ __ __ _ __ . .__ . r~ c~l ~ ~ ~ ~ ~
CO ~ C- o o o Lr~ L~
_~ _ ~ __ .
,Q U~ J. c~l (~ ~ O. ~J
~1 . ~ ~O ~\I O O O U~ I
~ ~; _ ~ ~ ___ x ~ o a~
O ~ ~D ~ ~ ~ _~ G~
~ ~O ~ O O O ~i 1~ U~
~) 1~ C~l ~
O _ J_ _ _ J t\l ~I ~D a~ 1 ~0 L~ ~ ~1 O O O J Lr~
~: ~ C~ ~ , J
~ _ . __ _ +' ~ ;t ~
r O O ~ ~1 ~1 ~ ~ O ~I
P~ ;t' ~ ~i O O O U~
~q . _ . - _ ' C~l O ~ 0~ ~ ~ C~J r~ L~
1~ ~O t\i O C~i ~ 1~ U~
~,q ~ 00 U~
~ - - -cc o~ : ~ ~ ~. 0 C~l O ~0 O ~ C~i u~ L~
~ r~
- ~ - - -. ~. :. ~. ~ ~
~ ~ ~ ~ O ~ ~ ~ ~D
q~
~q ~ l ~
. a) ~ ~ t~ I h )~-~ h a) ~ ~ ~
~-~ .~ ,1 rl J 1~ ~ O ~ $~ ~1 0 +' t~ ~ t~ hO ~\1 4 t~
bO O h ~q ,1 ~Q
+~ S~ rl O u~ _ bO
~q O ~d ~n+' ~ V o ^ u~ O s~
a) h ~rl ~ ~ ~o H u~ h ~1 o ~,1 h ,1 ~+' ~J h ~t~ ~ ~H ~r~
,~ ~ o ~ ~ o o ,~ C~ ^o ,~
U~ ~ .~ ,~ o ~ o ~ ~i ~r-l O t~ r~ h 0 r{~h H t~ ~10 ~ ~ ,s~ ~o +~ c) ~D
h ^ O rl 0 ~ 5: t.) ~ ~I h ~ h o u~ ~ ~ a~ h ~rl~ o a) F, ~rl I X E o~ C~Ja> ~ h ~1 ~ a) H u~
a~ F t~ +-) ~ a~ ) a) ~ ~ ~ ~ a~
~S H` . ~ +~ ~ ~ o ~ ~ b~ .r~ h~ ~ bO
E I ~ ~: P ~ . ~ O ~ ~ (1) ~
__
Claims (11)
1. A compound of the formula I
(I) in which Y1 and Y2 independently of one another are a or or with 2-7 C atoms, cycloalkyl with 5-7 C atoms or benzyl, Q is methyl, phenyl or -003, Q1, Q2 and Q3 independently of one another are alkyl with 1-6 C atoms or phenyly, x is an integer from 2 to 4, a is an integer from 1 to 50, the individual radicals Z independently of one another are an aliphatic radical with at least 2 C atoms, or a cyclo-aliphatic, araliphatic or a carbocyclic-aromatic radical and Z1 and the individual radicals Z2 independently of one another are a group, but at least one of Z1 and Z2 is a group, A is a radical or , R2 and R3 in-dependently of one another are hydrogen or methyl, the individual values m and n independently of one another are 1 or 2 and the individual radicals Z3 independently of one another are an aliphatic radical with at least 2 C atoms, or a cycloaliphatic or a carbocyclic-aromatic radical, in which the carboxamide and carboxyl groups are bonded to different C atoms and carboxyl groups bonded to cyclic radicals Z3 are each in the ortho-position to a carboxamide group, and the corresponding cyclised imide derivative.
(I) in which Y1 and Y2 independently of one another are a or or with 2-7 C atoms, cycloalkyl with 5-7 C atoms or benzyl, Q is methyl, phenyl or -003, Q1, Q2 and Q3 independently of one another are alkyl with 1-6 C atoms or phenyly, x is an integer from 2 to 4, a is an integer from 1 to 50, the individual radicals Z independently of one another are an aliphatic radical with at least 2 C atoms, or a cyclo-aliphatic, araliphatic or a carbocyclic-aromatic radical and Z1 and the individual radicals Z2 independently of one another are a group, but at least one of Z1 and Z2 is a group, A is a radical or , R2 and R3 in-dependently of one another are hydrogen or methyl, the individual values m and n independently of one another are 1 or 2 and the individual radicals Z3 independently of one another are an aliphatic radical with at least 2 C atoms, or a cycloaliphatic or a carbocyclic-aromatic radical, in which the carboxamide and carboxyl groups are bonded to different C atoms and carboxyl groups bonded to cyclic radicals Z3 are each in the ortho-position to a carboxamide group, and the corresponding cyclised imide derivative.
2 . A compound of the formula I according to claim 1, and the corresponding cyclised imide derivative, in which a is an integer from 1 to 50, the radicals Yl and Y2 are each a group or a group, the group being bonded in the ortho-position to the -COOH
or -CO-NH-Z-NH -CO- group , R is or R 1 is or Q is methyl or alkoxy with 1-4 C atoms and Q1 and Q2 are each alkyl with 1-4 C-atoms
or -CO-NH-Z-NH -CO- group , R is or R 1 is or Q is methyl or alkoxy with 1-4 C atoms and Q1 and Q2 are each alkyl with 1-4 C-atoms
3. A compound of the formula I according to claim 2, in which a is an integer from 1-15.
4. A compound of the formula I according to claim 2, in which Y1 and Y2 are each a group, R is or ,Q is methyl or alkoxy with 1-4 C atoms and Ql and Q2 are each alkyl with 1-4 C atoms.
5. A compound of the formula I according to claim 1, and the corresponding cyclised imide deriva-tive , in which the radicals Z are each a 1,3- or 1,4-phenylelle group, or a 4,4'-diphenylmethane, 4,4' -diphenyl-ether or 4,4'-diphenylsulphone radical, the radicals Z3 are each a 1,3- or l,4-phenylene group or unsubstituted alkylene with 4-10 C atoms, if m and n are 1, or are each a benzene-triyl group if m is 1 and n is 2, or are each a benzene-tetrayl group or the benzophenone ring system if m and n are 2, and one or both of the radicals Zl and Z2' and about 5-50 mol % of these, is a group, in which A is , or -CH=CH?
6. A compound of the formula I according to claim 5, wherein A is -CH=CH-.
7. A compound of the formula I according to claim 1, in which a is an integer from 1 to 50, m and n are 1, Z is a 1,3- or a 1,4-phenylene gxoup, or a 4,4'-diphenylmethane or 4,4'-diphenylether radical and Z3 is a 1,3-phenylene or 1,4-phenylene group, but only one of Z and Z3 is a 1,4-phenylene group, and in which about 10-30 mol % of Z1 and Z2 are a or group.
8. A compound of the formula I according to claim 1, and the corresponding cyclised imide deri-vative, in which a is an integer from 1 to 50, m is 1 and n is 2, Z is a 1,3- or 1,4 phenyl-ene group, or a 4,4'-diphenylmethane or 4,4'-diphenyl-ether radical and Z3 is a benzenetriyl group, and in which about 10-30 mol % °f Z1 and Z2 are a or group.
9. A compound of the formula I according to claim 1, and the corresponding cyclised imide deri-vative, in which a is an integer from 1 to 50.
m and n are each 2, Z is a 1,3- or 1,4-phenylene group, or a 4,4'-diphenylmethane or 4,4'-diphenyl-ether radical and Z3 is a benzenetetrayl group or the benzophenone ring system, and in which about 10-30 mol % of Z1 and Z2 are a or group.
m and n are each 2, Z is a 1,3- or 1,4-phenylene group, or a 4,4'-diphenylmethane or 4,4'-diphenyl-ether radical and Z3 is a benzenetetrayl group or the benzophenone ring system, and in which about 10-30 mol % of Z1 and Z2 are a or group.
10. A compound of the formula I according to either of claims 7, 8 or 9, wherein a is an integer from 1 to 10.
11. A process for the preparation of a compound of the formula I according to claim 1 and of the corresponding cyclised imide derivative, wherein, if a is 1, a compound of the formula II
(II) and, if a >1, a compound of the formula III
( III) in which Z4 and Z5 independently of one another are a or group, is reacted with an essentially stoichiometric amount of a compound of the formula IV or V
(IV) or (V) or of a mixture of such compounds, m, n, A, R, R1, Q, Q1, Q2, Z, Z2 and Z3 in the above formu1ae II to V being as defined in claim 1, whilst one of Z2, Z4 and Z5 is a or group, a1 is an integer from 1 to 49, the radicals R4 in-dependently of one another are -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -NH-Z-NH2 and R5 is -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -NH-Z-NH2 or, Z3 is a cyclic radical and m is 2, R5 together with R6 are a -O- group, the groups -COR5, -COR6 and -COOH are bonded to different C atoms and if Z3 is a cyclic radical and m and/or n are 2, the -COR5 or -COOH group is in the ortho-position to the -COR6 group or to the adjoining carbox-amide group, after which the reaction product may or may not be cyclized to the corresponding imide.
(II) and, if a >1, a compound of the formula III
( III) in which Z4 and Z5 independently of one another are a or group, is reacted with an essentially stoichiometric amount of a compound of the formula IV or V
(IV) or (V) or of a mixture of such compounds, m, n, A, R, R1, Q, Q1, Q2, Z, Z2 and Z3 in the above formu1ae II to V being as defined in claim 1, whilst one of Z2, Z4 and Z5 is a or group, a1 is an integer from 1 to 49, the radicals R4 in-dependently of one another are -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -NH-Z-NH2 and R5 is -OH, chlorine, alkoxy with 1-4 C atoms, phenoxy or -NH-Z-NH2 or, Z3 is a cyclic radical and m is 2, R5 together with R6 are a -O- group, the groups -COR5, -COR6 and -COOH are bonded to different C atoms and if Z3 is a cyclic radical and m and/or n are 2, the -COR5 or -COOH group is in the ortho-position to the -COR6 group or to the adjoining carbox-amide group, after which the reaction product may or may not be cyclized to the corresponding imide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1106977A CH634851A5 (en) | 1977-09-09 | 1977-09-09 | METHOD FOR PRODUCING IMIDYL- AND SILYLGROUPLE-CONTAINING POLYMERS. |
| CH11069/77 | 1977-09-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1117531A true CA1117531A (en) | 1982-02-02 |
Family
ID=4369716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000310791A Expired CA1117531A (en) | 1977-09-09 | 1978-09-07 | Polymers containing imidyl groups and silyl groups |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4200724A (en) |
| JP (1) | JPS5452071A (en) |
| CA (1) | CA1117531A (en) |
| CH (1) | CH634851A5 (en) |
| DE (1) | DE2838874A1 (en) |
| FR (1) | FR2402662A1 (en) |
| GB (1) | GB2003899B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH632766A5 (en) * | 1977-09-09 | 1982-10-29 | Ciba Geigy Ag | METHOD FOR PRODUCING SILICON-MODIFIED BIS-PHTHALIC ACID DERIVATIVES. |
| DE3175510D1 (en) * | 1980-09-15 | 1986-11-27 | Ciba Geigy Ag | Use of flexible materials in printed circuits |
| US4499149A (en) * | 1980-12-15 | 1985-02-12 | M&T Chemicals Inc. | Siloxane-containing polymers |
| US4480009A (en) * | 1980-12-15 | 1984-10-30 | M&T Chemicals Inc. | Siloxane-containing polymers |
| US4499252A (en) * | 1984-03-28 | 1985-02-12 | Nitto Electric Industrial Co., Ltd. | Process for producing polyimide precursor |
| DE3715313A1 (en) * | 1986-09-02 | 1988-03-10 | Gen Electric | IMIDOPOLYSILOXANES AND METHOD FOR THEIR PRODUCTION |
| DE3714763A1 (en) * | 1987-05-04 | 1988-11-24 | Henkel Kgaa | MOISTURE CROSSLINKING MELT GLUE |
| EP0304022A3 (en) * | 1987-08-21 | 1990-12-19 | E.I. Du Pont De Nemours And Company | Polyimide coating composition |
| US5063115A (en) * | 1987-08-21 | 1991-11-05 | E. I. Du Pont De Nemours And Company | Electronic device coated with a polyimide coating composition |
| JPH02148367U (en) * | 1989-05-18 | 1990-12-17 | ||
| US5334756A (en) * | 1991-03-26 | 1994-08-02 | Sandoz Ltd. | Carboxylate of certain polyoxyalkylene amines |
| JPH04351667A (en) * | 1991-05-29 | 1992-12-07 | Shin Etsu Chem Co Ltd | Curable resin composition and protective film for electronic component |
| US5427860A (en) * | 1992-10-07 | 1995-06-27 | Zeldin; Martel | Methods and compositions for interfacially bonding mineral surfaces and the like |
| KR101543478B1 (en) * | 2010-12-31 | 2015-08-10 | 코오롱인더스트리 주식회사 | Transparent Polyimide film and Method for Preparing the Same |
| RU2606393C2 (en) * | 2012-07-27 | 2017-01-10 | Дзе Проктер Энд Гэмбл Компани | Organopolysiloxane polymers |
| US10414873B2 (en) | 2013-07-29 | 2019-09-17 | The Procter & Gamble Company | Organopolysiloxane polymers |
| US9611362B2 (en) | 2013-07-29 | 2017-04-04 | The Procter & Gamble Company | Cationic organopolysiloxanes |
| US10081910B2 (en) | 2013-07-29 | 2018-09-25 | The Procter & Gamble Company | Absorbent articles comprising organopolysiloxane conditioning polymers |
| US9701929B2 (en) | 2013-07-29 | 2017-07-11 | The Procter & Gamble Company | Consumer product compositions comprising organopolysiloxane emulsions |
| US9580670B2 (en) | 2013-07-29 | 2017-02-28 | The Procter & Gamble Company | Consumer product compositions comprising organopolysiloxane conditioning polymers |
| US9993418B2 (en) | 2013-07-29 | 2018-06-12 | The Procter & Gamble Company | Benefit agent emulsions and consumer products containing such emulsions |
| US9540489B2 (en) | 2013-07-29 | 2017-01-10 | The Procter & Gamble Company | Blocky cationic organopolysiloxane |
| US9963470B2 (en) | 2013-07-29 | 2018-05-08 | The Procter & Gamble Company | Branched blocky cationic organopolysiloxane |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL130570C (en) * | 1963-12-12 | |||
| US3689464A (en) * | 1970-12-18 | 1972-09-05 | Gen Electric | Imido-substituted polyamide compositions |
| US3738969A (en) * | 1971-04-30 | 1973-06-12 | Gen Electric | Polyimides |
| US3948835A (en) * | 1973-06-07 | 1976-04-06 | Ciba-Geigy Corporation | Silicon-modified prepolymers |
| US3950308A (en) * | 1973-06-07 | 1976-04-13 | Ciba-Geigy Corporation | Crosslinked polymers containing siloxane groups |
| US3926911A (en) * | 1973-06-07 | 1975-12-16 | Ciba Geigy Corp | Crosslinked polymers containing siloxane groups |
| FR2259833B1 (en) * | 1974-02-05 | 1978-03-10 | Rhone Poulenc Ind | |
| US4088670A (en) * | 1974-10-01 | 1978-05-09 | Rhone-Poulenc Industries | Ethylenic silicon compounds and thermoplastic elastomers obtained therefrom |
| CH617447A5 (en) * | 1975-06-18 | 1980-05-30 | Ciba Geigy Ag |
-
1977
- 1977-09-09 CH CH1106977A patent/CH634851A5/en not_active IP Right Cessation
-
1978
- 1978-08-30 US US05/938,168 patent/US4200724A/en not_active Expired - Lifetime
- 1978-09-06 DE DE19782838874 patent/DE2838874A1/en not_active Ceased
- 1978-09-07 CA CA000310791A patent/CA1117531A/en not_active Expired
- 1978-09-07 GB GB7835966A patent/GB2003899B/en not_active Expired
- 1978-09-08 FR FR7825828A patent/FR2402662A1/en active Granted
- 1978-09-09 JP JP11123978A patent/JPS5452071A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| CH634851A5 (en) | 1983-02-28 |
| DE2838874A1 (en) | 1979-03-22 |
| JPS6327357B2 (en) | 1988-06-02 |
| FR2402662B1 (en) | 1984-03-09 |
| GB2003899B (en) | 1982-04-21 |
| US4200724A (en) | 1980-04-29 |
| FR2402662A1 (en) | 1979-04-06 |
| JPS5452071A (en) | 1979-04-24 |
| GB2003899A (en) | 1979-03-21 |
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