DE4041808A1 - Fibre-reinforced polycarbonate-co:polyether-ester laminates - useful esp. for prodn. of structural panels with improved flexural modulus - Google Patents

Abstract

Fibre-reinforced composite (I) contains (a) a layer of polycarbonate resin (PC) and (b) a layer of copolyether-ester resin (PEE). (I) contains a layer of aromatic PC, a layer of PEE and glass fibre (GF), pref. a layer of PEE between two layers of PC, pref. reinforced with GF; (I) is produced by hot-pressing a lay-up comprising an outer thin film of PC, a first layer of GF mat, an inner layer of PEE film, a second layer of GF mat and a second outer layer of thin PC film: (I) is 0.75-19.05 (pref. 1,27-6.35) mm thick; the PEE is derived from the reaction prods. of diol(s), dicarboxylic acid(s) and and long chain ether glycol(s), and the PC is produced from Bisphenol A and a carbonate precursor. USE/ADVANTAGE - The invention provides a fibre-reinforced laminate with a higher flexural modulusa than prior-art reinforced polycarbonate laminates; (I) is useful esp. for the prodn. of structural panels.

Description

The invention relates to polycarbonate composites and it relates in particular to polycarbonate Composites that are a layer of one Contain copolyether ester resin.

Polycarbonate resin composites with glass mats are already known and can be strengthened by Pressing alternate layers of poly together carbonate resin films and glass mats can be obtained.

Although these composites are suitable for use as Building boards to be used, so it is for numerous applications desirable, the bending module to increase such plates. It is consequently Object of the present invention polycarbonate To create composites which have increased values in the Have reference to the bending module.

The present invention thus comprises a poly carbonate resin composite by press-melting laminating layers of polycarbonate foils, Glass fiber mats and copolyether ester resin films obtained has been. The composite has improved Bending modulus values, and can be used as a building board.

The polycarbonate composites have a layer of copolyether ester resin. The preferred composite is produced by melt lamination of a layer structure of 0.254 mm (10 mils) bisphenol-A poly carbonate resin film / 0.254 mm (10 mils) bisphenol-A poly carbonate resin film / randomly distributed glass fiber mat with a density of 0.06 g / cm ² (2 ounces per square foot) / 0.508 mm film copolyether ester resin (20 mils), statistically distributed glass fiber mat with a density of 0.06 g / cm ² (2 ounces per square foot) / 0.254 mm (10 mils) bisphenol-A polycarbonate Film / 0.254 mm (10 mils) bisphenol-A polycarbonate film.

The polycarbonate resins that are used in the Composites are suitable include high molecular weight thermoplastic, aromatic polycarbonates such as Homopolycarbonates and copolycarbonates as well as mixtures the same, which have average molecular weights of about 8,000 to more than 200,000, preferably from about 20,000 to 80,000 and a basic molar viscosity number I.V. from 0.40 to 1.0 dl / g measured in methylene have chloride at 25 °. These polycarbonates conduct from dihydric phenols such as 2,2-bis (4-hydroxyphenyl) propane, bis (4- hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3- methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2- (3,5,3 ′, 5′-tetrachloro-4,4′-dihydroxyphenyl) - propane, 2,2- (3,5,3 ′, 5′-tetrabromo-4,4′-dihy droxydiphenyl) propane and 3,3'-dichloro-4,4'-dihydroxydiphenyl) methane.

Other dihydric phenols, also for the Use in the manufacture of the above Polycarbonates are suitable, for example, in the U.S. Patents 29 99 835; 30 28 365, 33 34 154 and 41 31 575 disclosed.

These aromatic polycarbonates can according to known Processes are produced such as by Reaction of a dihydric phenol with a carbonate precursors like phosgene according to the procedures as in the above literature and U.S. Patents 40 18 750 and 41 23 436 are described or by Transesterification processes as described in US Pat. Nos. 3,153,008 are disclosed as well as others known to the person skilled in the art Method.  

The aroma used in the present invention Tables polycarbonates also include the polymers Derivatives of a dihydric phenol, a dicarbon acid and carbonic acid as described in the US patent 31 69 131 are disclosed.

It is still possible to distinguish two or more Liche dihydric phenols or a copolymer of one dihydric phenol with a glycol or with hydroxy or acid-terminating polyester or with a dibasic acid in the event that a carbonate copolymer or interpolymer instead of a homopolymer for the Use in the production of the aromatic Polycarbonate in the practical implementation of Invention is desired.

It can also be put into practice of the invention mixtures of any of the aforementioned materials are used to to deliver aromatic polycarbonate.

Branched polycarbonates as described in the US patent 40 01 184 are described in the practical Implementation of the invention can also be used in same way as mixtures of a linear Polycarbonate and a branched polycarbonate.

Suitable thermoplastic copolyether esters include both random and block copolymers. in the generally they are replaced by conventional ones Esterification / polycondensation process from (a) one or more diols, (b) one or more Dicarboxylic acids, (c) one or more long chain Ether glycols and optional (d) one or more Caprolactones or polycaprolactones produced.  

The diols (a) used in the preparation of the Copolyether esters can be used both saturated and unsaturated aliphatic, cycloaliphatic dihydroxy compounds and aromatic dihydroxy compounds. Have these diols preferably a low molecular weight, for example a molecular weight of about 300 or fewer. If in the present application should be used under the designations "Diols" and "low molecular weight diols" such can be understood which equivalent ester-forming Derivatives thereof include, however, provided that the molecular weight requirements only affect that Refer to diol and not its derivatives. As Examples of ester-forming derivatives can be the acetates the diols and, for example, ethylene oxide or Ethylene carbonate be listed for ethylene glycol.

Preferred saturated and unsaturated aliphatic and cycloaliphatic diols are those that are about 2-19 Have carbon atoms. As examples of this Diols can be ethylene glycol, propanediol, butanediol, Pentanediol, 2-methyl-propanediol, 2,2-dimethyl-propane diol, hexanediol, decanediol, 2-octyl undecanediol, 1,2-, 1,3- and 1,4-dihydroxy cyclohexane, 1,2-, 1,3- and 1,4- Cyclohexane dimethanol; Butanediol, hexanediol, etc. be called. 1,4-Butanediol is particularly preferred and mixtures thereof with hexanediol or butanediol.

Aromatic diols for use in Production of thermoplastic elastomers suitable are generally those from 6 to about 19 Carbon atoms. From the aromatic dihydroxy compounds include: resorcinol, hydroquinone, 1,5-dihydroxy-naphthalene, 4,4'-dihydroxy-diphenyl, bis (p-hydroxyphenyl) methane and 2,2-bis (p-hydroxyphenyl) propane.  

Particularly preferred diols are saturated aliphatic Diols, mixtures thereof and mixtures of one saturated diol (diols) with an unsaturated diol (Diols) wherein each diol has 2 to about 8 carbon contains atoms. If more than 1 diol is used, then it is preferred that at least about 60 mole%, most preferably at least 80 mole% of the same Diol are based on the total diol content. How The preferred ones have already been mentioned above thermoplastic elastomers those in which 1,4- Butanediol is present in a predominant amount.

Dicarboxylic acids (b) suitable for use in the manufacture Position of the copolyether are suitable include aliphatic, cycloaliphatic and / or aromatic Dicarboxylic acids. These acids preferably have one low molecular weight, d. H. a molecular weight less than about 350; however, it can also be higher molecular weight dicarboxylic acids, especially dimers Acids can also be used. The label "Dicarboxylic acids" as used herein includes equivalents of dicarboxylic acids with 2 functional Carboxyl groups, which are involved in the formation of the Polyester polymers essentially like dicarboxylic acids behave when reacting with glycols and diols. These equivalents include esters and ester-forming Derivatives such as acid halides and anhydrides. About that In addition, the dicarboxylic acids can also have one or more any substituent groups or combinations contain which with the polymer formation reaction and the use of the polymer in practical Do not interfere with the implementation of the invention.

Aliphatic dicarboxylic acids relate to the present disclosure on carboxylic acids with 2 car boxyl groups, each of which is a saturated carbon  atom is bound. If the carbon atom, on which is the carboxyl group is saturated and arranged in a ring, then the acid cycloaliphatic.

Aromatic dicarboxylic acids are, within the scope of the present disclosure, dicarboxylic acids with 2 carboxyl groups, each of which is bonded to a carbon atom in an isolated or a fused benzene ring system. It is not necessary that both functional carboxyl groups be bonded to the same aromatic ring and in cases where there is more than one ring, they can be substituted by aliphatic or aromatic divalent radicals or by divalent radicals such as -O- or -SO ₂ - be connected.

Representative examples of aliphatic and cyclo aliphatic acids that can be used are sebacic acid 1,2-cyclohexanedicarboxylic acid, 1,3- Cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, Adipic acid, glutaric acid, succinic acid, oxalic acid, Azelaic acid, diethylmalonic acid, allylmalonic acid, Dimer acid, 4-cyclohexene-1,2-dicarboxylic acid, 2-ethyl suberic acid, tetramethylsuccinic acid, cyclopentane dicarboxylic acid, decahydro-1,5-naphthalene-dicarboxylic acid, 4,4'-bicyclohexyl-dicarboxylic acid, decahydro-2,6- naphthalene-dicarboxylic acid, 4,4'-methylene-bis- (Cyclohexane carboxylic acid), 3,4-furan dicarboxylic acid and 1,1-cyclobutane dicarboxylic acid. Preferred aliphatic Acids are cyclohexane dicarboxylic acids, sebacic acid, Dimer acid, glutaric acid, azelaic acid and adipine acid.

Representative examples of aromatic dicarbon acids that can be used include  Terephthalic acid, phthalic acid and isophthalic acids, Di benzoic acid, substituted dicarboxy compounds with two benzene cores such as bis (p-carboxyphenyl) methane, Oxybis- (benzoic acid), ethylene-1,2-bis- (p- Oxybenzoic acid), 1,5-naphthalenedicarboxylic acid, 2,6- Naphthalene-dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, anthracene dicarboxylic acid, 4,4'-sulfonyl-dibenzoic acid and halogen and C₁-C₁₂ alkyl, alkoxy and aryl ring substituted Derivatives of the same. Hydroxy acids such as p- (α-hydroxy ethoxy) benzoic acid can also be used provided that an aromatic dicarboxylic acid is also present.

Preferred for the preparation of the polyether esters Dicarboxylic acids the aromatic dicarboxylic acids, Mixtures of the same and mixtures of one or several dicarboxylic acids with an aliphatic and / or cycloaliphatic dicarboxylic acid, most prefers the aromatic dicarboxylic acids. Among the aromatic acids are those with 8-16 coals Preferred atoms, especially the benzene dicarboxylic acids, d. H. Phthalic acid, terephthalic acid and Isophthalic acids and their dimethyl derivatives. Especially dimethyl terephthalate is preferred.

When using mixtures of dicarboxylic acid, it is finally preferred that at least about 60 Mol% preferably at least about 80 mol% based on 100 mol% of the dicarboxylic acids (b) the same dicarbon acid or ester derivative thereof. As above the preferred copolyether esters have already been mentioned those in which dimethyl terephthalate predominant dicarboxylic acid.

Suitable long-chain ether glycols (c) from Her position of the thermoplastic elastomers used  are preferably poly (oxyalkylene) -gly kole and copoly (oxyalkylene) glycols with the molecular weight from about 400 to 1200. Preferred poly (oxyal kylen) units are derived from long-chain ether glycols with molecular weights from about 900 to about 4000 off and have a carbon to oxygen ratio of about 1.8 to about 4.3 excluded existing side chains.

As representative examples of suitable poly (oxyalkylene glycols) can be named: poly (ethylene ether) glycol, poly (propylene ether) glycol, Poly (tetramethylene ether) glycol, arbitrary or Block copolymers of ethylene oxide and propylene oxide including ethylene oxide and capped poly (propylene ether) glycol and predominantly poly (ethylene ether) main chain, copoly (propylene ether) ethylene ether) glycol and statistical or Block copolymers of tetrahydrofuran with low Amounts of a second monomer such as ethylene oxide, Propylene oxide or methyltetrahydrofuran (used in such proportions that the carbon / oxygen ratio does not exceed 4.3. Polyformal glycols, the by reacting formaldehyde with diols such as 1,4- Butanediol and 1,5-pentanediol are produced also usable. Particularly preferred "poly (oxyalkylene) glycols are poly (propylene ether) glycol, Poly (tetramethylene ether) glycol and predominantly poly (Ethylene ether) backbone copoly (propylene ether) ethylene ether) glycol.

Optionally, these copolyether esters can be one or incorporated several caprolactones or polycaprolactones contain.  

For use in the present invention suitable caprolactones (d) are widely available Available commercially. For example, from Union Carbide Corporation and Aldrich Chemicals. While Epsilon Caprolactone is particularly preferred, so it is still possible in substituted caprolactones which the Epsilon Caprolacton by a lower Alkyl group such as a methyl or ethyl group in the alpha, beta, gamma, delta or epsilon position sub is to use. Beyond that it is possible polycaprolactone including the Homopolymers and copolymers of the same with one or several components as well as hydroxy end Polycaprolactones as block units in the To use copolyether esters. Suitable polycapro lactones and processes for their preparation for example in U.S. Patents 37 61 511, 37 67 627 and 38 06 495, whose disclosure content by this reference in the present application is taken. Generally suitable ones Copolyetherester elastomers (A) those in which the Percentage by weight of long chain Ether glycol component (c) or the combined Weight percentage of (c) the long chain Ether glycol component and (d) the caprolactone component in the copolyetherester from about 5 to about 70 Weight percent is. Preferred compositions are those in which the weight percentage of (c) or (c) and (d) from about 10 to about 50 weight percent. In cases where (c) that long chain ether glycol and (d) caprolactone are present, each of these components comprises about 2 up to about 50 percent by weight, preferably about 5 to about 30 weight percent of the copolyetherester.

As already described above, the Co polyetherester according to conventional esterification / con  condensation reactions for the production of polyesters getting produced. Typical examples of these processes can be found in US Patents 30 23 192, 37 63 109, 36 51 014, 36 63 653 and 38 01 547, their open content by this reference in the present Registration is included. These compositions can additionally by such procedures and others known processes are produced in which statistical copolymers, block copolymers or hybrids the same in which statistical and block units are present. That's the way it is for example possible that any two or several of the aforementioned monomers / reaction stock divide before polymerizing the final copoly ether esters are prereacted. Alternatively a two-part synthesis can be used, in which two different diols and / or carboxylic acids are each prereacted in separate reactors in order to to give two low molecular weight prepolymers that then with the long chain ether glycol to form the Tri-block copolyether ester end product combined will.

The reinforcing fiber layers are preferably in the form of non-woven long glass fiber mats. Preferably, the glass fiber mat layer has a density of 0.015 g / cm ² (0.5 ounce / square foot) to 0.122 g / cm ² (4 ounce / square foot), and most preferably 0.06 g / cm ² (2 ounce / square foot) foot). The glass fiber reinforcing agent can also be in various other forms, including chopped glass, glass bundles and individual glass fibers. Carbon fibers, metal fibers and aramid fibers can also be used as reinforcing fibers.

The preferred fiber reinforced composite has outer layers of polycarbonate resin and an inner layer of a copolyether ester resin. More preferably, the composite is obtained by compressing at elevated temperatures a layer structure consisting of an outer aromatic polycarbonate resin layer, a glass fiber mat layer, an inner copolyether ester resin layer, a glass fiber mat layer, and an outer aromatic polycarbonate resin layer. The composites can have a total thickness of 0.762 to 19.5 mm (30 mils to 750 mils), preferably 1.27 to 6.35 mm (50 mils to 250 mils). The reinforcing fibers are preferably present in amounts of 5% to 50% by weight based on the total weight of the composite. The composites are preferably formed by compressing the layers together at pressures of 0.35 to 7.0 kg / cm ² (5 to 100 pounds per square inch), more preferably under pressures of 0.7 to 4.9 kg / cm ² (10 to 70 pounds per square inch) at temperatures of preferably between 230 ° C to 400 ° C and more preferably at about 280 ° C. The composites can then be punched at elevated temperatures to give corresponding building boards. The copolyether ester resin has good impregnation properties for the adjacent glass fiber mat.

Examples:

The following examples illustrate the present Invention without, however, its scope restrict.  

Table I

a) The composites were pressed together from layers of 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film, glass fiber mat with a weight of 0.06 g / cm ² , 0.508 mm thick copolyether ester film, glass fiber mat with a Ge weight of 0.06 g / cm ² , 0.254 mm (10 mils) thick aromatic polycarbonate film, 0.254 mm (10 mils) thick aromatic polycarbonate film. The aromatic polycarbonate film was obtained from the reaction products of bisphenol-A and phos gene. The glass fibers were an arbitrarily distributed glass fiber mat made of Nicofibers 758 and had a density of 0.06 g / cm ² (2 ounces per square foot). The co polyetherester was a random copolyetherester consisting of 25 parts butanediol, 48 parts dimethyl terephthalate, 14 parts hexanediol and 13 parts poly (tetramethylene ether) glycol (MW 2000).

b) The flexural modulus was measured in GPa.

c) The flexural strength was measured in MPa.

d) The Izod impact strength was measured in feet pounds / inches.  

e) Composites were made from layers of 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 (10 mils) aromatic polycarbonate film, glass fiber mats with a weight of 0.06 g / cm ² (2 ounces per square foot), 0.254 mm ( 10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film, glass fiber mats weighing 0.06 g / cm ² (2 ounces per square foot, 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 (10 mils) aromatic polycarbonate film The aromatic polycarbonate film was the same as in Examples 6 to 8. The glass fibers were the same as in Examples 6 to 8. Reference is made to the improved flexural modulus of Examples 6 to 8 compared to Comparative Examples 1 to 5.

Table II

(f) Composites made from layered structures of 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film, glass fiber mat with a weight of 0.06 g / cm ² (2 ounces per square foot), 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film, glass fiber mat weighing 0.06 g / cm ² (2 ounces per square foot), 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film. The polycarbonate resin was derived from the reaction product of bisphenol-A and phosgene. The glass fiber mat was one with the designation Owens Corning 8608.

g) The composites were pressed together from layers of 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film, glass fiber mat with a weight of 0.06 g / cm ² (2 ounces per square foot), 0 5 mm (20 mils) copolyether ester film, glass fiber mat weighing 0.06 g / cm ² (2 ounces per square foot), 0.254 mm (10 mils) aromatic polycarbonate film, 0.254 mm (10 mils) aromatic polycarbonate film. The aromatic polycarbonate film was derived from the reaction products of bisphenol-A and phosgene.

The glass fibers are a glass fiber mat with the name Owens Corning 8608, which had a density of 0.06 g / cm ² (2 ounces per square foot).

The copolyether ester is a rule loose copolyether ester made from 25 parts of butanediol, 48 Parts of dimethyl terephthalate, 14 parts of hexanediol and 13 Parts poly (tetramethylene ether) glycol (MW 2000) abge was leading.

It is on the improved flexural modulus of Examples 12 and 13 compared to Comparative Examples 9 to 11 pointed.

Claims (9)

1. Fiber reinforced composite containing:

• a) a layer of polycarbonate resin and
• b) a layer of copolyether ester resin.

2. Fiber reinforced composite containing:

• a) a layer of polycarbonate resin,
• b) a layer of copolyether ester resin and
• c) a lot of reinforcing glass fibers.

3. Fiber reinforced composite containing:

• a) a first outer layer of aromatic polycarbonate resin,
• b) an inner layer of copolyether ester resin,
• c) a second outer layer of aromatic polycarbonate resin, the copolyether ester resin being arranged between the first and the second layer of aromatic polycarbonate resin.

4. Composite according to claim 3, characterized ge indicates that the composite with a glass fiber mat is reinforced. 5. Composite according to claim 3, characterized ge indicates that the composite by Compression of a layer structure from an outer one thin film of polycarbonate, a first layer Glass fiber mats, an inner layer made of copolyether ester film, a second layer of glass fiber mat and a second outer layer made of a thin poly carbonate film has been obtained under heating and pressure.   6. Composite according to claim 3, characterized ge indicates that the composite is a Thickness between 0.75 mm and 19.05 mm (30 mils and 750 mils) having. 7. Composite according to claim 3, characterized ge indicates that the composite is a Thickness between 1.27 mm and 6.35 mm. 8. Composite according to claim 7, characterized ge indicates that the copolyether ester is derived from the reaction products from (I) at least a diol (II), at least one dicarboxylic acid and little at least one long-chain ether glycol. 9. A composite according to claim 8, characterized ge indicates that the aromatic polycar bonat is derived from bisphenol-A and a carbonate precursor.