CA2427431C - Pmma moulding compositions with improved low-temperature impact resistance - Google Patents
Pmma moulding compositions with improved low-temperature impact resistance Download PDFInfo
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- CA2427431C CA2427431C CA2427431A CA2427431A CA2427431C CA 2427431 C CA2427431 C CA 2427431C CA 2427431 A CA2427431 A CA 2427431A CA 2427431 A CA2427431 A CA 2427431A CA 2427431 C CA2427431 C CA 2427431C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
Abstract
The invention relates to a molding material, which is provided with impact resistance and which is characterized by exhibiting a particularly high impact resistance at low temperatures (-20 ~C, -40 ~C). This low-temperature impact resistance is achieved by using a silicon elastomer.
Description
a PMMA moulding compositions with improved low-temperature impact resistance Technical field of the invention The invention relates to impact-resistant polymeth-acrylate moulding compositions (PMMA moulding compositions) with improved low-temperature impact resistance.
Prior art For PMMA moulding compositions (MCs) the impact modifiers generally used are core-shell (C/S) or core-shell-shell (C/S1/S2) particles (particle size from 100 to 1000 nm), which are usually prepared by emulsion polymerization. In the case of C/S structure, the core is composed of an elastomeric phase, while in C/S1/S2 particles the elastomeric phase is generally the shell (S1) which has been grafted onto the core. Besides emulsion polymers, suspension polymers may also be used. Here, the elastomeric phase is in grafted form, with MMA for example, and is present in relatively finely divided form in the beads (matrix material, e.g.
PMMA).
The elastomeric phase is mostly composed of crosslinked copolymer, which is in most cases prepared using butyl acrylate. However, an example of another elastomeric phase used is polybutadiene.
The literature describes impact modifiers which include silicone rubber.
In relation to the structure of the graft copolymers, a broad distinction may be drawn between C/S and C/S1/S2 particles. The C/S particles are grafted silicone particles, examples of graft monomers used being MMA, styrene and acrylonitrile. C/S particles in which the core is composed of a mixture of silicone rubber and acrylic rubber (no grafting) are a special case (for example EP 430 134). C/S1/S2 particles are described in DE 3 617 267, DE 3 720 475, DE 3 801 537, DE 3 822 667, - 5 DE 3 839 587, DE 4 040 986, DE 4 342 048 and EP 433 906, for example. The following structure is mostly involved here: C-silicone/S1-acrylic rubber or other silicone layer/S2-various copolymers (for binding to the matrix). In the case of the C/S1/S2 particles in DE
Prior art For PMMA moulding compositions (MCs) the impact modifiers generally used are core-shell (C/S) or core-shell-shell (C/S1/S2) particles (particle size from 100 to 1000 nm), which are usually prepared by emulsion polymerization. In the case of C/S structure, the core is composed of an elastomeric phase, while in C/S1/S2 particles the elastomeric phase is generally the shell (S1) which has been grafted onto the core. Besides emulsion polymers, suspension polymers may also be used. Here, the elastomeric phase is in grafted form, with MMA for example, and is present in relatively finely divided form in the beads (matrix material, e.g.
PMMA).
The elastomeric phase is mostly composed of crosslinked copolymer, which is in most cases prepared using butyl acrylate. However, an example of another elastomeric phase used is polybutadiene.
The literature describes impact modifiers which include silicone rubber.
In relation to the structure of the graft copolymers, a broad distinction may be drawn between C/S and C/S1/S2 particles. The C/S particles are grafted silicone particles, examples of graft monomers used being MMA, styrene and acrylonitrile. C/S particles in which the core is composed of a mixture of silicone rubber and acrylic rubber (no grafting) are a special case (for example EP 430 134). C/S1/S2 particles are described in DE 3 617 267, DE 3 720 475, DE 3 801 537, DE 3 822 667, - 5 DE 3 839 587, DE 4 040 986, DE 4 342 048 and EP 433 906, for example. The following structure is mostly involved here: C-silicone/S1-acrylic rubber or other silicone layer/S2-various copolymers (for binding to the matrix). In the case of the C/S1/S2 particles in DE
3 720 475, the core is composed of a vinyl rubber, S1 of silicone rubber and S2 of various copolymers.
The graft copolymers prepared are used as impact modifiers for certain plastics (often PC, SAN, polystyrene) or polymer blends.
EP 430 134: Here, a core composed of a silicone rubber and of an acrylic rubber (these intertwined rubbers being prepared by using acrylate derivatives to swell the silicone latex and then polymerizing them) is grafted with vinyl monomers. The material is also described for impact modification of moulding compositions, but here only polycarbonate (PC) and/or polyester moulding compositions are mentioned.
US 4,690,986: Here, an impact-resistant moulding composition (ir) is claimed, prepared from a graft copolymer (via emulsion polymerization). The graft copolymer is a C/S product. The core is composed, inter alia, of a crosslinking agent (siloxane bonded to a methacrylate group via a number of CH2 groups) and of tetrafunctional silane as crosslinking agent. The moulding composition (ir) per se is described, as is the associated preparation process.
JP 612 135 462: Here, a moulding composition (ir) is claimed, prepared from a graft copolymer (via emulsion polymerization). The graft copolymer is composed of siloxane grafted with vinyl monomers.
EP 308 198: Here, a moulding composition is claimed, composed of PMI and grafted polysiloxane. The grafted polysiloxane is prepared by grafting of monomers and of at least one "graft-crosslinking agent". It is clear from the subclaims that the graft-crosslinking agent is the crosslinking agent (siloxane bonded to a methacrylate group via a number of CHZ groups) in US
The graft copolymers prepared are used as impact modifiers for certain plastics (often PC, SAN, polystyrene) or polymer blends.
EP 430 134: Here, a core composed of a silicone rubber and of an acrylic rubber (these intertwined rubbers being prepared by using acrylate derivatives to swell the silicone latex and then polymerizing them) is grafted with vinyl monomers. The material is also described for impact modification of moulding compositions, but here only polycarbonate (PC) and/or polyester moulding compositions are mentioned.
US 4,690,986: Here, an impact-resistant moulding composition (ir) is claimed, prepared from a graft copolymer (via emulsion polymerization). The graft copolymer is a C/S product. The core is composed, inter alia, of a crosslinking agent (siloxane bonded to a methacrylate group via a number of CH2 groups) and of tetrafunctional silane as crosslinking agent. The moulding composition (ir) per se is described, as is the associated preparation process.
JP 612 135 462: Here, a moulding composition (ir) is claimed, prepared from a graft copolymer (via emulsion polymerization). The graft copolymer is composed of siloxane grafted with vinyl monomers.
EP 308 198: Here, a moulding composition is claimed, composed of PMI and grafted polysiloxane. The grafted polysiloxane is prepared by grafting of monomers and of at least one "graft-crosslinking agent". It is clear from the subclaims that the graft-crosslinking agent is the crosslinking agent (siloxane bonded to a methacrylate group via a number of CHZ groups) in US
4,690,986. The subclaims also mention the tetrafunctional silane as crosslinking agent.
EP 332 188 a Here, a graft copolymer similar to that in EP 430134 is used to modify an MC. In the example, particles are grafted with styrene and these are used to modify a polyether/polysulphone blend.
DE 4 342 048: Here, a graft copolymer in the form of C/S1/S2 particles is claimed. A silicone rubber functions as core, S1 is prepared mainly from acrylates (min. 70%), and there is a wide choice of monomers for S2 (e. g. 50-100 of methyl methacrylate). The subclaims also describe it MCs based on the claimed graft polymer, and here again there is a very wide choice of polymer for the matrix.
DE 3839287: Here, a MC is claimed, composed of from 20-80~ of conventional polymers and from 80-20~ of graft copolymers. The graft copolymer is composed of C/S1/S2 particles, the core being composed of silicone rubber and S1 being composed of acrylate rubber. S2 is prepared by redox polymerization (emulsion) of a very wide variety of monomers. Only one ir-modified SAN
moulding composition is listed as an example.
X10 99/41315: Here, a dispersion is claimed, comprising a mixture of particles composed of vinyl copolymers and particles composed of PMMA-sheathed silicone rubber.
This dispersion can be used as an impact modifier, for example.
Object and achievement of object Preparation of impact-resistant moulding compositions - 5 (ir MCs) based on PMMA is widely practised. The impact resistance of the moulding composition is increased by using what are known as impact modifiers. These modifiers are compounded into the appropriate standard PMMA moulding compositions.
Acceptable impact resistances extending to -10°C in PMMA MCs are achieved with the aid of the conventional modifiers, which comprise butyl acrylate rubber as elastomeric phase. In order to achieve acceptable impact resistances at even lower temperatures, another rubber (with a lower glass transition temperature (Tg) than butyl acrylate rubber) has to be used as elastomeric phase. An example of an elastomeric phase used here is polybutadiene. These polybutadiene-based modifiers have a very disadvantageous effect on the weathering resistance of the moulding compositions in whose preparation they are used.
The object was then to find a modifier which achieves acceptable impact resistance of the PMMA moulding compositions or of the PMMA/SAN blends at relatively low temperatures (<-10°C) and which, when comparison is made with PMMA moulding compositions or PMMA/SAN blends prepared using polybutadiene-based modifiers, gives the moulding composition or blend better weathering resistance. At the same time, however, the melt viscosity, die swell, heat distortion temperature and Vicat softening point of the appropriate moulding compositions cannot be permitted to suffer through the use of the new modifiers. A composition according to the patent claims achieves these objects and other objects not explicitly specified here.
The moulding compositions thus modified are to be used for producing useful products which have to remain impact-resistant even at lower temperatures (extending to -40°C) These useful products are to be suitable for both indoor and outdoor applications. Examples of these applications are: mouldings for the automotive industry (e.g. mirror housings and spoilers), for the construction industry (e.g. coloured pipes and protective covers) and for the household industry (e. g.
refrigerators).
EP 492 376 claims a graft copolymer (and also the process for preparing this graft copolymer), composed of C/S or C/S1/S2 particles. The core and the optional intermediate shell are more precisely defined and are composed of silicone rubber, and the outer shell is prepared by emulsion polymerization of a very wide variety of monomers (without further emulsifier). The particle size is restricted to 10-300 nm, and the polydispersity index is not more than 0.2. In the examples, the claimed graft copolymer is, inter alia, blended with PMMA and the NIS at 23°C is measured.
The preparation of the product SLM 44 59 06 is described in EP 492 376, and the preparation of the product SLM 44 50 06 is described in EP 492 376. The difference between the products lies in their work-up.
All of the products are obtainable from blacker-Chemie GmbH.
The copolymer is composed of a core a) composed of an organosilicon polymer and of an organopolymer shell c) or two shells b) and c) where the inner shell b) is composed of an organosilicon polymer, characterized in that the copolymer is composed of a) from 0.05 to 95~ by weight, based on the total weight of the copolymer, of a core polymer of the general formula (RZSiOzi2)X ~ (Si04iz)Z, where x -from 0 to 99.5 mold, y = from 0.5 to 100 mold, z -from 0 to 50 mold, b) from 0 to 94.5 by weight, based on the total weight of the copolymer, of a polydialkylsiloxane shell of (R2Si02,2) units, and c) from 5 to 95~ by weight, based on the total weight of the copolymer, of a shell of an organopolymer of monoolefinically unsaturated monomers, where R
are identical or different alkyl or alkenyl radicals having from 1 to 6 carbon atoms, aryl radicals or substituted hydrocarbon radicals, and the particles have a particle size of from 10 to 300 nm and a monomodal particle size distribution with a polydispersity index of not more than 0.2.
EP 492 376 describes the preparation of the silicone graft copolymers and describes their use for the impact-modification of polyvinyl chloride (PVC), PMMA, polystyrene (PS) and styrene-acrylonitrile copolymer ( SAN ) .
In the case of PMMA mixtures, notched impact resistance was determined only at 23°C, and nothing at all is said concerning use or indeed any particular effects at lower temperatures.
EXAMPLES:
Blending of moulding compositions A standard PMMA-based moulding composition, PLEXIGLAS~
EP 332 188 a Here, a graft copolymer similar to that in EP 430134 is used to modify an MC. In the example, particles are grafted with styrene and these are used to modify a polyether/polysulphone blend.
DE 4 342 048: Here, a graft copolymer in the form of C/S1/S2 particles is claimed. A silicone rubber functions as core, S1 is prepared mainly from acrylates (min. 70%), and there is a wide choice of monomers for S2 (e. g. 50-100 of methyl methacrylate). The subclaims also describe it MCs based on the claimed graft polymer, and here again there is a very wide choice of polymer for the matrix.
DE 3839287: Here, a MC is claimed, composed of from 20-80~ of conventional polymers and from 80-20~ of graft copolymers. The graft copolymer is composed of C/S1/S2 particles, the core being composed of silicone rubber and S1 being composed of acrylate rubber. S2 is prepared by redox polymerization (emulsion) of a very wide variety of monomers. Only one ir-modified SAN
moulding composition is listed as an example.
X10 99/41315: Here, a dispersion is claimed, comprising a mixture of particles composed of vinyl copolymers and particles composed of PMMA-sheathed silicone rubber.
This dispersion can be used as an impact modifier, for example.
Object and achievement of object Preparation of impact-resistant moulding compositions - 5 (ir MCs) based on PMMA is widely practised. The impact resistance of the moulding composition is increased by using what are known as impact modifiers. These modifiers are compounded into the appropriate standard PMMA moulding compositions.
Acceptable impact resistances extending to -10°C in PMMA MCs are achieved with the aid of the conventional modifiers, which comprise butyl acrylate rubber as elastomeric phase. In order to achieve acceptable impact resistances at even lower temperatures, another rubber (with a lower glass transition temperature (Tg) than butyl acrylate rubber) has to be used as elastomeric phase. An example of an elastomeric phase used here is polybutadiene. These polybutadiene-based modifiers have a very disadvantageous effect on the weathering resistance of the moulding compositions in whose preparation they are used.
The object was then to find a modifier which achieves acceptable impact resistance of the PMMA moulding compositions or of the PMMA/SAN blends at relatively low temperatures (<-10°C) and which, when comparison is made with PMMA moulding compositions or PMMA/SAN blends prepared using polybutadiene-based modifiers, gives the moulding composition or blend better weathering resistance. At the same time, however, the melt viscosity, die swell, heat distortion temperature and Vicat softening point of the appropriate moulding compositions cannot be permitted to suffer through the use of the new modifiers. A composition according to the patent claims achieves these objects and other objects not explicitly specified here.
The moulding compositions thus modified are to be used for producing useful products which have to remain impact-resistant even at lower temperatures (extending to -40°C) These useful products are to be suitable for both indoor and outdoor applications. Examples of these applications are: mouldings for the automotive industry (e.g. mirror housings and spoilers), for the construction industry (e.g. coloured pipes and protective covers) and for the household industry (e. g.
refrigerators).
EP 492 376 claims a graft copolymer (and also the process for preparing this graft copolymer), composed of C/S or C/S1/S2 particles. The core and the optional intermediate shell are more precisely defined and are composed of silicone rubber, and the outer shell is prepared by emulsion polymerization of a very wide variety of monomers (without further emulsifier). The particle size is restricted to 10-300 nm, and the polydispersity index is not more than 0.2. In the examples, the claimed graft copolymer is, inter alia, blended with PMMA and the NIS at 23°C is measured.
The preparation of the product SLM 44 59 06 is described in EP 492 376, and the preparation of the product SLM 44 50 06 is described in EP 492 376. The difference between the products lies in their work-up.
All of the products are obtainable from blacker-Chemie GmbH.
The copolymer is composed of a core a) composed of an organosilicon polymer and of an organopolymer shell c) or two shells b) and c) where the inner shell b) is composed of an organosilicon polymer, characterized in that the copolymer is composed of a) from 0.05 to 95~ by weight, based on the total weight of the copolymer, of a core polymer of the general formula (RZSiOzi2)X ~ (Si04iz)Z, where x -from 0 to 99.5 mold, y = from 0.5 to 100 mold, z -from 0 to 50 mold, b) from 0 to 94.5 by weight, based on the total weight of the copolymer, of a polydialkylsiloxane shell of (R2Si02,2) units, and c) from 5 to 95~ by weight, based on the total weight of the copolymer, of a shell of an organopolymer of monoolefinically unsaturated monomers, where R
are identical or different alkyl or alkenyl radicals having from 1 to 6 carbon atoms, aryl radicals or substituted hydrocarbon radicals, and the particles have a particle size of from 10 to 300 nm and a monomodal particle size distribution with a polydispersity index of not more than 0.2.
EP 492 376 describes the preparation of the silicone graft copolymers and describes their use for the impact-modification of polyvinyl chloride (PVC), PMMA, polystyrene (PS) and styrene-acrylonitrile copolymer ( SAN ) .
In the case of PMMA mixtures, notched impact resistance was determined only at 23°C, and nothing at all is said concerning use or indeed any particular effects at lower temperatures.
EXAMPLES:
Blending of moulding compositions A standard PMMA-based moulding composition, PLEXIGLAS~
7 N (producer: Rohm GmbH) is blended with different amounts of various Wacker silicone modifiers, by means of an extruder. The compositions of each of the examples are documented in Appendix 1.
Silicone modifier:
A.) SLM 445906 core-shell modifier, Wacker, Germany:
Precipitated emulsion polymer composed of silicone elastomer particles with PMMA shell. The material is substantially free from emulsifiers. Preparation described in EP 492 376. Particle size about 100 nm, distribution monomodal.
B.) SLM 445006 core-shell modifier, blacker, Germany:
Spray-dried emulsion polymer composed of silicone elastomer particles with PMMA shell. Preparation described in EP 492 376. Particle size about 100 nm, distribution monomodal.
Two impact-modified moulding compositions serve as comparison.
Table of blends Matrix Modifier C
Blend A Plexiglas 7N
80.3 by weight 19.7 by weight Blend B Plexiglas 7N: 36.7 by weight 63.3 by weight (Comparative examples) C.) Acrylic rubber modifier, Rohm Composition:
Core: Copolymer of methyl methacrylate (95.7 by weight), ethyl acrylate (4~ by weight) and allyl methacrylate (0.3~ by weight) S1: Copolymer of butyl acrylate (81.2 by weight), styrene (17.5 by weight) and allyl methacrylate (1.3~ by weight) S2: Copolymer of methyl methacrylate (96~ by weight) and ethyl acrylate (4~ by weight) C/S1/S2 ratio by weight: 23/47/30 The preparation of the modifiers is based on the process disclosed in DE 33 00 526.
Testing of moulding compositions Test specimens were produced from the blended moulding compositions. The following methods were used to test the moulding compositions or the corresponding test specimens:
Viscosity ~S (220C/ Determination of melt viscosity, 5 MPa: Test standard:DIN 54811: (1984) Die swell B: Determination of die swell, Test standard:DIN 54811: (1984) MVR (230C/3.8 kg): Determination of volume flow index, Test standard ISO 1133: (1997) Vicat softening point Determination of Vicat softening (16h/80C): point Test standard ISO 306 (method B50):
1994) HDT (16h/80C A Determination of distortion 1.8 MPa): temperature, Test standard:ISO 75 (Sept. 1993) NIS (Izod 180/leA): Determination of Izod notched impact resistance, Test standard:ISO 180: (1993) Modulus of elasticity Determination of modulus of elasticity, Test standard:ISO 527-2 Tensile strength Determination of tensile strength, Test standard:ISO 527-2 Yield stress Determination of yield stress, Test standard:ISO 527-2 Nom. tensile strain Determination of nominal tensile at break strain at break, Test standard:ISO 527-2 The results of the tests are seen in Appendix 2.
The advantages of the moulding compositions blended with silicone modifier over the moulding compositions with conventional impact-modification (blends A and B) are clearly visible:
At comparable content of impact modifiers (Comparative Example 1, Example 3, Example 5), the notched impact resistance of each of the moulding compositions at 23°C
is at the same level. At -20°C the notched impact resistance of the moulding compositions blended with silicone modifier is markedly higher (better), while melt viscosity, die swell, distortion temperature and Vicat softening point remain at the same level for all of the moulding compositions compared.
The relatively small addition (10.5 by weight) of silicone modifier to a moulding composition with conventional impact-modification (Example 1) can markedly raise notch impact strength, achieving the level of blend B (Comparative Example 2), which has markedly higher modifier content, at 23°C. At -20°C the notched impact resistance of the moulding composition blended with silicone modifiers is markedly higher (better). It is also apparent that when comparison is made with blend B the Vicat softening point and distortion temperature of the moulding compositions blended with silicone modifier are higher (better), while melt viscosities and die swells are at a comparable level.
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Silicone modifier:
A.) SLM 445906 core-shell modifier, Wacker, Germany:
Precipitated emulsion polymer composed of silicone elastomer particles with PMMA shell. The material is substantially free from emulsifiers. Preparation described in EP 492 376. Particle size about 100 nm, distribution monomodal.
B.) SLM 445006 core-shell modifier, blacker, Germany:
Spray-dried emulsion polymer composed of silicone elastomer particles with PMMA shell. Preparation described in EP 492 376. Particle size about 100 nm, distribution monomodal.
Two impact-modified moulding compositions serve as comparison.
Table of blends Matrix Modifier C
Blend A Plexiglas 7N
80.3 by weight 19.7 by weight Blend B Plexiglas 7N: 36.7 by weight 63.3 by weight (Comparative examples) C.) Acrylic rubber modifier, Rohm Composition:
Core: Copolymer of methyl methacrylate (95.7 by weight), ethyl acrylate (4~ by weight) and allyl methacrylate (0.3~ by weight) S1: Copolymer of butyl acrylate (81.2 by weight), styrene (17.5 by weight) and allyl methacrylate (1.3~ by weight) S2: Copolymer of methyl methacrylate (96~ by weight) and ethyl acrylate (4~ by weight) C/S1/S2 ratio by weight: 23/47/30 The preparation of the modifiers is based on the process disclosed in DE 33 00 526.
Testing of moulding compositions Test specimens were produced from the blended moulding compositions. The following methods were used to test the moulding compositions or the corresponding test specimens:
Viscosity ~S (220C/ Determination of melt viscosity, 5 MPa: Test standard:DIN 54811: (1984) Die swell B: Determination of die swell, Test standard:DIN 54811: (1984) MVR (230C/3.8 kg): Determination of volume flow index, Test standard ISO 1133: (1997) Vicat softening point Determination of Vicat softening (16h/80C): point Test standard ISO 306 (method B50):
1994) HDT (16h/80C A Determination of distortion 1.8 MPa): temperature, Test standard:ISO 75 (Sept. 1993) NIS (Izod 180/leA): Determination of Izod notched impact resistance, Test standard:ISO 180: (1993) Modulus of elasticity Determination of modulus of elasticity, Test standard:ISO 527-2 Tensile strength Determination of tensile strength, Test standard:ISO 527-2 Yield stress Determination of yield stress, Test standard:ISO 527-2 Nom. tensile strain Determination of nominal tensile at break strain at break, Test standard:ISO 527-2 The results of the tests are seen in Appendix 2.
The advantages of the moulding compositions blended with silicone modifier over the moulding compositions with conventional impact-modification (blends A and B) are clearly visible:
At comparable content of impact modifiers (Comparative Example 1, Example 3, Example 5), the notched impact resistance of each of the moulding compositions at 23°C
is at the same level. At -20°C the notched impact resistance of the moulding compositions blended with silicone modifier is markedly higher (better), while melt viscosity, die swell, distortion temperature and Vicat softening point remain at the same level for all of the moulding compositions compared.
The relatively small addition (10.5 by weight) of silicone modifier to a moulding composition with conventional impact-modification (Example 1) can markedly raise notch impact strength, achieving the level of blend B (Comparative Example 2), which has markedly higher modifier content, at 23°C. At -20°C the notched impact resistance of the moulding composition blended with silicone modifiers is markedly higher (better). It is also apparent that when comparison is made with blend B the Vicat softening point and distortion temperature of the moulding compositions blended with silicone modifier are higher (better), while melt viscosities and die swells are at a comparable level.
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Claims (11)
1. Impact-resistant PMMA moulding composition com-posed of a) a matrix of .cndot. from 75 to 100% by weight of methyl meth-acrylate .cndot. from 0.1 to 15% by weight of acrylate and .cndot. from 0 to 15% by weight of other copolymer-izable compounds and b) another matrix of .cndot. from 70 to 92% by weight of styrene .cndot. from 8 to 30% by weight of acrylonitrile .cndot. from 0 to 22% by weight of other comonomers c) an impact modifier of silicone elastomer parti-cles with PMMA shell and d) an impact modifier based on acrylate rubber, where the contents of c) are from 5 to 95% by weight and of d) are from 95 to 5% by weight, based on the entirety of components c) and d), and where, based on the entirety a), b), c) and d), from 0 to 45% by weight of component b), from 5 to 30% by weight of component c), and from 1 to 30% by weight of component d) are added, and the moulding composition has the following properties:
.cndot. a Vicat softening point to ISO 306 (B50) of at least 95°C, .cndot. a notched impact strength NIS (Izod 180/leA, 1.8 MPa) to ISO 180 of at least 3.0 kJ/m2 at -20°C and of at least 2.5 kJ/m2 at -40°C, .cndot. a modulus of elasticity to ISO 527-2 of at least 2000 MPa.
.cndot. a Vicat softening point to ISO 306 (B50) of at least 95°C, .cndot. a notched impact strength NIS (Izod 180/leA, 1.8 MPa) to ISO 180 of at least 3.0 kJ/m2 at -20°C and of at least 2.5 kJ/m2 at -40°C, .cndot. a modulus of elasticity to ISO 527-2 of at least 2000 MPa.
2. Impact-resistant PMMA moulding composition accord-ing to Claim 1, characterized in that the matrix has an average molecular weight (weight average) from 90,000 to 250,000 daltons.
3. Impact-resistant PMMA moulding composition accord-ing to Claim 1, characterized in that the impact-modifier c) has a silicone content of up to 95% by weight.
4. Impact-resistant PMMA moulding composition accord-ing to Claim 1, characterized in that]
the PMMA shell of the impact modifier c) is composed of the polymer of from 30 to 100% by weight of methyl methacrylate and from 0 to 30% by weight of other copolymerizable compounds.
the PMMA shell of the impact modifier c) is composed of the polymer of from 30 to 100% by weight of methyl methacrylate and from 0 to 30% by weight of other copolymerizable compounds.
5. Impact-resistant PMMA moulding composition accord-ing to Claim 1, characterized in that the primary particle size of the impact modifier c) is a diameter of from 10 to 300 nm and the distribution of the primary particle sizes is monomodal (polydispersity index not more than 0.2).
6. Impact-resistant PMMA moulding composition according to Claim 1, characterized in that the impact modifier d) is composed either .cndot. of core-shell particles (core composed of acryl-ate rubber, particle size from 100 to 1000 nm), or of core-shell-shell (C/S1/S2) particles (S1 com-posed of acrylate rubber, particle size from 100 to 1000 nm), or .cndot. of finely divided acrylate rubber in PMMA beads (particle size from 100 to 500 µm).
7. Use of the moulding composition according to any of the preceding claims for producing mouldings by injection moulding or extrusion, which even at temperatures extending to -40°C have a notched impact strength NIS (Izod 180/1eA, 1.8 MPa) to ISO
180 of at least 2.5 kJ/m2.
180 of at least 2.5 kJ/m2.
8. Use of the mouldings according to Claim 7 in applications with periods of exposure to temperatures below -10°C.
9. Use of the mouldings according to Claim 8 characterized in that the moulding is a mirror housing for a vehicle, or is a spoiler.
10. Use of the mouldings according to Claim 8 characterized in that the moulding is a tube or a protective covering.
11. Use of the mouldings according to Claim 8 characterized in that the moulding is a refrigerator component.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10054051.1 | 2000-10-31 | ||
| DE10054051A DE10054051A1 (en) | 2000-10-31 | 2000-10-31 | PMMA molding compound with improved low-temperature impact strength |
| PCT/EP2001/012172 WO2002036682A1 (en) | 2000-10-31 | 2001-10-22 | Pmma molding materials exhibiting an improved low-temperature impact resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2427431A1 CA2427431A1 (en) | 2003-04-30 |
| CA2427431C true CA2427431C (en) | 2011-01-11 |
Family
ID=7661733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2427431A Expired - Fee Related CA2427431C (en) | 2000-10-31 | 2001-10-22 | Pmma moulding compositions with improved low-temperature impact resistance |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6890993B2 (en) |
| EP (1) | EP1330493B1 (en) |
| JP (1) | JP4060183B2 (en) |
| AT (1) | ATE315613T1 (en) |
| AU (1) | AU2002216976A1 (en) |
| CA (1) | CA2427431C (en) |
| DE (2) | DE10054051A1 (en) |
| WO (1) | WO2002036682A1 (en) |
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|---|---|---|---|---|
| DE10043868A1 (en) * | 2000-09-04 | 2002-04-04 | Roehm Gmbh | PMMA molding compounds with improved impact resistance |
| US7883721B2 (en) | 2001-01-30 | 2011-02-08 | Smithkline Beecham Limited | Pharmaceutical formulation |
| US20050175687A1 (en) * | 2001-01-30 | 2005-08-11 | Mcallister Stephen M. | Pharmaceutical formulations |
| GB0102342D0 (en) * | 2001-01-30 | 2001-03-14 | Smithkline Beecham Plc | Pharmaceutical formulation |
| AU2002247681A1 (en) | 2001-02-07 | 2002-09-12 | Rohm Gmbh And Co. Kg | Hot sealing compound for aluminum foils applied to polypropylene and polystyrene |
| DE10127134A1 (en) * | 2001-06-05 | 2002-12-12 | Roehm Gmbh | Production of injection molded shaped articles, especially for retarded drug release, by blending (meth)acrylate copolymer with plasticizer and other additives, degassing and molding |
| DE10203565C1 (en) * | 2002-01-29 | 2003-07-10 | Roehm Gmbh | Production of polymethyl methacrylate casting, used for making acoustic insulation panels and balcony cladding, involves adding impact modified of core-shell I-shell II type as masterbatch in polymethyl methacrylate |
| DE10204890A1 (en) * | 2002-02-06 | 2003-08-14 | Roehm Gmbh | Impact-resistant molding compound and molded body |
| DE10236240A1 (en) * | 2002-02-06 | 2003-08-14 | Roehm Gmbh | Silicone graft copolymers with core-shell structure, impact-modified molding compositions and moldings, and process for their preparation |
| DE10243062A1 (en) * | 2002-09-16 | 2004-03-25 | Röhm GmbH & Co. KG | A sanitary material made from thermoplastic polymethyl methacrylate molding material useful for sanitary material resistant to hot water,which is crack resistant, cheap to produce, and can be recycled |
| DE10260089A1 (en) * | 2002-12-19 | 2004-07-01 | Röhm GmbH & Co. KG | Process for the preparation of aqueous dispersions |
| DE10260065A1 (en) * | 2002-12-19 | 2004-07-01 | Röhm GmbH & Co. KG | Core-shell particles for toughening of poly (meth) acrylate molding compounds |
| DE10345045A1 (en) * | 2003-09-26 | 2005-04-14 | Röhm GmbH & Co. KG | Surface coating of materials, e.g. to form a protective layer, involves laminating with a film made from a mixture of methyl methacrylate-based polymer and an acrylic copolymer with reactive comonomer units |
| DE10349144A1 (en) * | 2003-10-17 | 2005-05-12 | Roehm Gmbh | Polymer mixture for injection mouldings with a matt surface, e.g. exterior vehicle parts, comprises an acrylic matrix, a crosslinked acrylic impact modifier and plastic particles with a specified range of particle sizes |
| MX2007008855A (en) * | 2003-10-18 | 2008-03-13 | Roehm Gmbh | Core and shell particle for modifying impact resistance of a mouldable poly(meth)acrylate material. |
| DE10351535A1 (en) * | 2003-11-03 | 2005-06-09 | Röhm GmbH & Co. KG | Multilayer film of (meth) acrylate copolymer and polycarbonate |
| DE10354379A1 (en) | 2003-11-20 | 2005-06-23 | Röhm GmbH & Co. KG | A molding composition containing a matting agent |
| TW200539903A (en) * | 2004-03-12 | 2005-12-16 | Smithkline Beecham Plc | Pharmaceutical formulations |
| DE102004022540A1 (en) | 2004-05-05 | 2005-12-08 | Röhm GmbH & Co. KG | Molding composition for moldings with high weather resistance |
| DE102004045296A1 (en) * | 2004-09-16 | 2006-03-23 | Röhm GmbH & Co. KG | Use of polyalkyl (meth) acrylate bead polymers and molding compound for the production of extruded molded parts with a matted surface |
| DE102004058083A1 (en) | 2004-12-01 | 2006-06-08 | Röhm GmbH & Co. KG | Covered colored, infrared-reflecting plastic molding compound |
| RU2409600C2 (en) * | 2005-04-18 | 2011-01-20 | Эвоник Рем ГмбХ | Moulding compound and article moulded from thermoplastic containing nanoscalar, inorganic particles, method of producing moulding compound and moulded article, as well as use thereof |
| DE102005021335A1 (en) * | 2005-05-04 | 2006-11-09 | Röhm Gmbh | Process for the preparation of bead polymers having a mean particle size in the range of 1 .mu.m to 40 .mu.m, and molding compositions and moldings comprising bead polymer |
| DE102005055793A1 (en) | 2005-11-21 | 2007-05-24 | Röhm Gmbh | Transparent TPU (thermoplastic polyurethanes) / PMMA (polymethyl (meth) acrylate) Blends with improved impact resistance |
| DE102006029613A1 (en) | 2006-06-26 | 2007-12-27 | Röhm Gmbh | Transparent plastic composite |
| US20080035703A1 (en) * | 2006-08-09 | 2008-02-14 | Daewoong Suh | Oxidation resistant solder preform |
| DE102007005432A1 (en) * | 2007-01-30 | 2008-07-31 | Evonik Röhm Gmbh | Molding material useful for making shaped products comprises a (meth)acrylate (co)polymer and ceramic beads |
| DE102007026201A1 (en) * | 2007-06-04 | 2008-12-11 | Evonik Röhm Gmbh | Colored composition with increased stress cracking resistance |
| DE102007026200A1 (en) * | 2007-06-04 | 2008-12-11 | Evonik Röhm Gmbh | Composition with increased stress cracking resistance |
| DE102007028601A1 (en) | 2007-06-19 | 2008-12-24 | Evonik Röhm Gmbh | Reactive mixture for coating moldings by means of reaction injection molding and coated molding |
| DE102007029263A1 (en) * | 2007-06-22 | 2008-12-24 | Evonik Röhm Gmbh | PMMA / PVDF film with particularly high weather resistance and high UV protection |
| DE102007051482A1 (en) * | 2007-10-25 | 2009-04-30 | Evonik Röhm Gmbh | Process for the production of coated moldings |
| JP5799371B2 (en) * | 2008-01-10 | 2015-10-21 | アルケア株式会社 | Skin adhesive, skin adhesive sheet and ostomy appliance face plate |
| DE102008001231A1 (en) * | 2008-04-17 | 2009-10-22 | Evonik Röhm Gmbh | Flameproof PMMA molding compound |
| DE102008001695A1 (en) * | 2008-05-09 | 2009-11-12 | Evonik Röhm Gmbh | Poly (meth) acrylimides with improved optical and color properties, especially under thermal stress |
| DE102008001825A1 (en) | 2008-05-16 | 2009-11-19 | Wacker Chemie Ag | Use of organosilicone copolymers as impact modifiers |
| DE102009020937A1 (en) * | 2009-05-12 | 2010-11-18 | Bayer Materialscience Ag | Cold impact coextrusion films |
| FR2969633B1 (en) * | 2010-12-23 | 2015-02-06 | Arkema France | COMPOSITION FOR RETICULATED NANOSTRUCTURED CAST PLATES |
| CN103304944A (en) * | 2013-07-11 | 2013-09-18 | 常熟市慧丰塑料制品有限公司 | Formula of modified polymethyl methacrylate |
| CN103387732A (en) * | 2013-08-01 | 2013-11-13 | 太仓市晨洲塑业有限公司 | Formula of modified polymethyl methacrylate |
| KR20150047991A (en) | 2013-10-25 | 2015-05-06 | 제일모직주식회사 | Thermoplastic resin composition with excellent colorability and mechanical properties |
| US10774208B2 (en) | 2015-03-11 | 2020-09-15 | Arkema Inc. | High impact blends of vinylidene fluoride-containing polymers |
| DE102016015356B4 (en) | 2016-12-22 | 2020-10-29 | Institut für Kunststofftechnologie und -recycling e.V. | Use of a composition for impact modification of powder coatings |
| CN110628156A (en) * | 2018-06-23 | 2019-12-31 | 深圳市宝聚合塑料有限公司 | Composite polymerized acrylate rubber and preparation method thereof |
| CN110483931B (en) * | 2019-07-12 | 2021-09-17 | 金发科技股份有限公司 | Polyacrylate polymer composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2684258B2 (en) * | 1991-04-02 | 1997-12-03 | 三菱レイヨン株式会社 | Method for producing polyorganosiloxane-based graft copolymer composition having excellent powder properties |
| DE69311463T2 (en) * | 1992-02-06 | 1998-02-05 | Mitsubishi Rayon Co | GRAFT POLYMER PARTICLES, PRODUCTION THEREOF, AND THE COMPOSITION CONTAINING THEM |
| DE19544563A1 (en) * | 1995-11-30 | 1997-06-05 | Roehm Gmbh | Color and weather-resistant impact-molding compounds based on polymethyl methacrylate and process for their production |
| JP4124863B2 (en) * | 1997-08-01 | 2008-07-23 | 三菱レイヨン株式会社 | Thermoplastic resin composition |
| DE19914605A1 (en) * | 1999-03-30 | 2000-10-05 | Roehm Gmbh | Polyalkyl methacrylate plastisols with improved flow properties |
-
2000
- 2000-10-31 DE DE10054051A patent/DE10054051A1/en not_active Ceased
-
2001
- 2001-10-22 JP JP2002539432A patent/JP4060183B2/en not_active Expired - Fee Related
- 2001-10-22 AT AT01992740T patent/ATE315613T1/en not_active IP Right Cessation
- 2001-10-22 AU AU2002216976A patent/AU2002216976A1/en not_active Abandoned
- 2001-10-22 WO PCT/EP2001/012172 patent/WO2002036682A1/en active IP Right Grant
- 2001-10-22 CA CA2427431A patent/CA2427431C/en not_active Expired - Fee Related
- 2001-10-22 EP EP01992740A patent/EP1330493B1/en not_active Expired - Lifetime
- 2001-10-22 US US10/415,106 patent/US6890993B2/en not_active Expired - Fee Related
- 2001-10-22 DE DE50108705T patent/DE50108705D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002216976A1 (en) | 2002-05-15 |
| US20040024121A1 (en) | 2004-02-05 |
| EP1330493B1 (en) | 2006-01-11 |
| EP1330493A1 (en) | 2003-07-30 |
| JP2004529992A (en) | 2004-09-30 |
| DE10054051A1 (en) | 2002-05-29 |
| JP4060183B2 (en) | 2008-03-12 |
| CA2427431A1 (en) | 2003-04-30 |
| US6890993B2 (en) | 2005-05-10 |
| ATE315613T1 (en) | 2006-02-15 |
| WO2002036682A1 (en) | 2002-05-10 |
| DE50108705D1 (en) | 2006-04-06 |
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