WO2001055233A1 - Verfahren zur herstellung schlagzäher kunststoffe - Google Patents
Verfahren zur herstellung schlagzäher kunststoffe Download PDFInfo
- Publication number
- WO2001055233A1 WO2001055233A1 PCT/EP2001/000898 EP0100898W WO0155233A1 WO 2001055233 A1 WO2001055233 A1 WO 2001055233A1 EP 0100898 W EP0100898 W EP 0100898W WO 0155233 A1 WO0155233 A1 WO 0155233A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer mixture
- grafted
- rubber particles
- crosslinked rubber
- particles
- Prior art date
Links
Classifications
-
- 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
- C08L51/04—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 rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Definitions
- the invention relates to a method for producing impact-resistant plastics based on grafted, crosslinked rubber particles and to an impact-resistant plastic obtainable by the method.
- Impact-resistant plastics show an increased load capacity against mechanical influences, which they have for many applications such. B. for everyday items, makes it particularly suitable. These special properties are achieved through the structure of these plastics, in which domains of elastomers, e.g. Rubbers, embedded in a matrix made of a thermoplastic.
- the multiphase nature and thus also the domain structure of such impact-resistant plastics is based on their construction from various polymer components, which are immiscible or only partially miscible with one another.
- Their impact strength results from an increased energy absorption during the deformation up to the break. The energy is used to form micro-voids or to initiate sliding processes of the matrix polymer chains.
- the multi-phase is therefore a necessary prerequisite for achieving high impact strength.
- the two different chemical polymer components form a dispersion which shows little phase separation during processing and does not tend to homogenize with the formation of a macromolecular solution when the temperature is more intense;
- US Pat. No. 3,957,912 describes a process for producing an acrylonitrile-butadiene-styrene plastic.
- a nylkiene rubber is first polymerized with styrene and / or acrylonitrile monomers by emulsion polymerization to give a grafted rubber.
- Styrene and / or acrylonitrile is then added to this rubber, as is at least one solvent for the styrene-acrylonitrile copolymer.
- the rubber is transferred into the solvent, the water is separated off and the mixture of rubber, solvent and monomer is polymerized. This process is expensive to carry out because of the transfer of the rubber into the solvent.
- US 3,903,199 and US 3,903,200 describe processes for the preparation of acrylonitrile-butadiene-styrene polymers.
- Particles of a first grafted rubber are dispersed in a mixture of a monovinylidene-aromatic monomer and an ethylene-nitrile-monomeric. This mixture is either first partially polymerized and then particles of a second grafted rubber are added and the matrix is polymerized out, or the particles of the second grafted rubber are added directly to the mixture of the monomers and the matrix is polymerized out. In both cases, a plastic with a bimodal size distribution of the rubber particles is obtained.
- the two processes each use rubbers that are soluble in the monomer mixtures of the matrix.
- DE-N 24 00 659 describes a process for the production of impact-resistant plastics, wherein rubber particles of Nlkadien rubber grafted with monovinylidene aromatic monomers and Nlkennitrile monomers in one
- Basic copolymer of monovinylidene aromatic monomers and Alkenitrile monomers are uniformly dispersed.
- the components are mixed at 120 - 180 ° C in the presence of an organic solvent and 0 - 15% water.
- the object of the invention is therefore to provide a method for producing impact-resistant plastics and an impact-resistant plastic obtainable by this method.
- This object is achieved with a method for producing impact-resistant plastic based on grafted, crosslinked rubber particles, wherein
- (a) particles of a crosslinked rubber are produced from a first monomer mixture which has a proportion of diene compounds of at least 50% by weight, preferably at least 90% by weight, particularly preferably at least 98% by weight,
- the process is very simple to carry out, since it is not necessary, for example, to separate the water phase when producing the rubber particles by emulsion polymerization.
- the properties of the impact-resistant plastic can be modified in a further area. Due to the intensive connection between the rubber particles and the matrix surrounding them, impact-resistant plastics with a very high potential for energy absorption are obtained.
- the rubber particles have a glass transition temperature Tg ⁇ 0 ° C, preferably Tg ⁇ - 10 ° C, particularly preferably Tg ⁇ - 20 ° C.
- a rubber is produced in particle form, onto which the second monomers or the second monomer mixture are grafted in the second step (b).
- an effective phase coupling can be achieved at the interfaces between the elastomer particles and the polymer matrix produced in a third step (c) from a third monomer mixture.
- Due to the high proportion of conjugated diene compounds in the rubber a better resistance to mechanical effects is achieved, which also applies at comparatively low temperatures. It is not necessary that the dispersion of the grafted crosslinked rubber particles be stable. In many cases, gelation occurs due to the swelling of the grafted rubber particles in the third monomer mixture. A phase separation occurs during the polymerization of the third monomer mixture in step (d), so that the product becomes flowable.
- Conjugated diene compounds suitable for the production of the rubber are, for example, butadiene, isoprene, 2-chloro-l, 3-butadiene, l-chloro-l, 3-butadiene and other substituted butadienes and isoprene.
- the rubber dispersion can e.g. with the emulsion, mini-emulsion and microsuspension procedure.
- the graft shell is preferably also formed in dispersion. The methods are known per se to the person skilled in the art.
- the dispersion of the grafted rubber particles in the third monomer mixture in step (c) can be added in various ways.
- the grafted rubber can be added directly as an aqueous dispersion, but it is also possible to separate off the water and to add the rubber particles with a water content of ⁇ 5% by weight to the third monomer mixture.
- the rubber particles can are also initially coagulated and, after the water has been partially separated off, are added to the third monomer mixture with a water content of 5-60% by weight.
- the water can be separated from the grafted rubber particles, for example by pressure filtration, centrifugation or by drawing off the water under reduced pressure.
- the water can suitably be distilled off, for example, during the polymerization of the third monomer mixture.
- agglomerate or coagulate the grafted rubber particles after adding the aqueous dispersion to the third monomer mixture.
- the mixture of third monomer mixture and grafted rubber particles which are optionally in the form of a dispersion, is advantageously homogenized by intensive agitation. This can be done, for example, using a rotor-stator system, the rotor being rotated at high speed, that is to say more than 500 rpm.
- a protective colloid is advantageously added to stabilize the dispersion of the rubber particles and the monomers of the third monomer mixture in water.
- the addition of the grafted rubber particles to the third monomer mixture can also be carried out in such a way that only part of the third monomer mixture is initially introduced, then the dispersion of the grafted rubber particles is added and the water is removed, whereupon the remaining portion of the third monomer mixture is added.
- the third monomer mixture contains monomers that are easily separated off with the water.
- the less volatile monomers of the third monomer mixture are initially introduced, the aqueous dispersion of the grafted rubber particles are added and the water is removed, whereupon the more volatile monomers of the third monomer mixture are added before the third monomer mixture is polymerized by adding a radical initiator.
- the grafted rubber particles can be swollen in the third monomer mixture for a certain time, preferably more than five minutes, before the polymerization of the third monomer mixture is started in step (d).
- the polymerization of the third monomer mixture can be carried out in one reaction step, after which solvent or monomers still present are subsequently removed by blowing in nitrogen.
- the polymerization of the third monomer mixture can first be started in bulk and continued in suspension at a later point in time after the addition of water.
- the reaction mixture is transferred into a suspension before more than 15% of the monomers of the third monomer mixture have polymerized.
- the weight ratio of graft shell to crosslinked rubber particles of the grafted crosslinked rubber particles is advantageously chosen between 5:95 and 80:20, preferably 5:95 and 60:40, in particular 5:95 and 40:60.
- the particle size of the grafted crosslinked rubber particles is advantageously ⁇ 10 ⁇ m, preferably ⁇ 5 ⁇ m, particularly preferably ⁇ 4 ⁇ m.
- the second monomer or the second monomer mixture preferably contains at least one monomer which is selected from the group formed by styrene, acrylonitrile and methyl methacrylate.
- the third monomer mixture preferably contains at least one monomer selected from the group consisting of styrene, acrylonitrile and methyl methacrylate.
- the third monomer mixture can also contain at least one further polymer which is preferably compatible or partially compatible with the polymer obtained from the third monomer mixture.
- Compatibility is understood to mean that there is no phase separation between the at least one further polymer and the polymer obtained from the third monomer mixture.
- the further polymer can be produced, for example, by partially polymerizing the third monomer mixture, then adding the dispersion of the grafted rubber particles to the partially polymerized monomer mixture and then completing the polymerization of the third monomer mixture.
- the grafted crosslinked rubber particles preferably have a swelling index between 2 and 100, preferably between 3 and 70, in particular between 3 and 60.
- the source index is determined in the following way:
- a film is cast with the dispersion of the grafted, crosslinked rubber particles and the water is evaporated at 23 ° C. The film is then dried at 50 ° C. and reduced pressure. Approximately 0.5 g of the film is swollen in a solvent such as tetrahydrofuran or dimethylformamide for 24 hours. The polymer gel is then separated from the solvent not incorporated into the gel by centrifugation. The gel is weighed, then dried and weighed again.
- the swelling index (QI) is calculated using the following equation:
- the rubber particles can have a hard core made of a copolymer, which preferably has a glass transition temperature of Tg> 0 ° C, particularly preferably Tg> 10 ° C, particularly preferably Tg> 20 ° C.
- This hard core can consist of polystyrene, for example.
- the hard core preferably has a refractive index of> 1.53, preferably> 1.56, in particular> 1.57.
- Impact-resistant plastics that contain rubber particles are usually opaque. This makes it very difficult to color them in. Due to the hard core, the refractive index of the rubber particles can be matched to the surrounding polymer matrix, which reduces light scattering. This balance is achieved particularly well with a hard core that contains polymerized styrene or a styrene derivative. These polymers show a particularly high refractive index.
- the impact-resistant plastic obtainable with the method according to the invention has a high mechanical strength. It can also be in a mixture with at least one additional polymeric plastic.
- Suitable as an additional polymer plastic are polycarbonates, polyesters, polyamides, polyalkyl methacrylates, including homopolymers and copolymers, and also high-temperature-resistant poly (ether) sulfones.
- Other suitable polymers are polypropylene, polyethylene, polytetrafluoroethylene (PTFE) and polystyrene-acrylonitrile.
- Polyphenylene ether PPE
- syndiotactic polystyrene styrene-diphenylethylene copolymers and copolymers with a styrene content of more than 65% by weight are preferred.
- Copolymers with a proportion of more than 80% by weight of styrene are preferred if the polymer forming the matrix is polystyrene or a copolymer of styrene with a proportion of the comonomer of less than 10% by weight.
- Polycarbonates, polyesters, styrene-acrylonitrile copolymers and poly styrene-acrylonitrile-methyl methacrylate copolymers are particularly preferred when the polymer forming the matrix is a polystyrene-acrylonitrile copolymer or a polystyrene-acrylonitrile-methyl methacrylate copolymer.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020027009639A KR20020071972A (ko) | 2000-01-27 | 2001-01-26 | 내충격성 플라스틱의 제조 방법 |
EP01946874A EP1261653A1 (de) | 2000-01-27 | 2001-01-26 | Verfahren zur herstellung schlagzäher kunststoffe |
AU2001228505A AU2001228505A1 (en) | 2000-01-27 | 2001-01-26 | Method for producing impact resistant plastics |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10003511.6 | 2000-01-27 | ||
DE10003511A DE10003511A1 (de) | 2000-01-27 | 2000-01-27 | Verfahren zur Herstellung schlagzäher Kunststoffe |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001055233A1 true WO2001055233A1 (de) | 2001-08-02 |
Family
ID=7628894
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/000898 WO2001055233A1 (de) | 2000-01-27 | 2001-01-26 | Verfahren zur herstellung schlagzäher kunststoffe |
Country Status (6)
Country | Link |
---|---|
US (1) | US20020198324A1 (de) |
EP (1) | EP1261653A1 (de) |
KR (1) | KR20020071972A (de) |
AU (1) | AU2001228505A1 (de) |
DE (1) | DE10003511A1 (de) |
WO (1) | WO2001055233A1 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102088404B1 (ko) * | 2010-08-23 | 2020-03-12 | 주식회사 쿠라레 | 태양 전지용 봉지재 및 합판 유리용 중간막 |
KR102549466B1 (ko) * | 2022-02-11 | 2023-06-28 | 엘에스전선 주식회사 | 유기 충진제 및 이를 포함하는 수지 조성물 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3879496A (en) * | 1971-05-12 | 1975-04-22 | Goodrich Co B F | Low rubber, high-flow and high impact ABS plastics, improved rubber toughener for producing same, and method of manufacture |
US3950455A (en) * | 1972-11-11 | 1976-04-13 | Toray Industries, Inc. | Method for graft polymerization of diene polymer |
US4120851A (en) * | 1977-08-22 | 1978-10-17 | Monsanto Company | Process for polymerizing high nitrile ABS polyblends |
US4141932A (en) * | 1977-10-03 | 1979-02-27 | Borg-Warner Corporation | Combined emulsion and suspension process for producing graft ABS bead-like particles |
US4151128A (en) * | 1968-07-30 | 1979-04-24 | Mobil Oil Corporation | Graft copolymers by suspension process following emulsion |
EP0592953A1 (de) * | 1992-10-12 | 1994-04-20 | BASF Aktiengesellschaft | Thermoplastische Formmasse |
EP0597275A1 (de) * | 1992-11-07 | 1994-05-18 | BASF Aktiengesellschaft | Thermoplastische Formmasse |
US5373060A (en) * | 1992-07-15 | 1994-12-13 | Basf Aktiengesellschaft | Particulate graft copolymer |
US5631323A (en) * | 1994-12-09 | 1997-05-20 | Basf Aktiengesellschaft | Composition of styrene-acrylonitrile copolymer matrix with particles of graft copolymer and crosslinked copolymer |
EP0953583A2 (de) * | 1998-04-29 | 1999-11-03 | Rohm And Haas Company | Schlagzähmodifizierer für aromatische amorphe Polyester |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4801646A (en) * | 1987-01-16 | 1989-01-31 | The Dow Chemical Company | Low gloss weather and impact resistant resins |
KR100309581B1 (ko) * | 1998-05-19 | 2001-09-26 | 구광시 | 충격보강제가 캡슐화된 아크릴 수지 및 그의 제조방법. |
-
2000
- 2000-01-27 DE DE10003511A patent/DE10003511A1/de not_active Withdrawn
-
2001
- 2001-01-26 AU AU2001228505A patent/AU2001228505A1/en not_active Abandoned
- 2001-01-26 KR KR1020027009639A patent/KR20020071972A/ko not_active Application Discontinuation
- 2001-01-26 WO PCT/EP2001/000898 patent/WO2001055233A1/de not_active Application Discontinuation
- 2001-01-26 EP EP01946874A patent/EP1261653A1/de not_active Withdrawn
- 2001-01-26 US US10/182,141 patent/US20020198324A1/en not_active Abandoned
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4151128A (en) * | 1968-07-30 | 1979-04-24 | Mobil Oil Corporation | Graft copolymers by suspension process following emulsion |
US3879496A (en) * | 1971-05-12 | 1975-04-22 | Goodrich Co B F | Low rubber, high-flow and high impact ABS plastics, improved rubber toughener for producing same, and method of manufacture |
US3950455A (en) * | 1972-11-11 | 1976-04-13 | Toray Industries, Inc. | Method for graft polymerization of diene polymer |
US4120851A (en) * | 1977-08-22 | 1978-10-17 | Monsanto Company | Process for polymerizing high nitrile ABS polyblends |
US4141932A (en) * | 1977-10-03 | 1979-02-27 | Borg-Warner Corporation | Combined emulsion and suspension process for producing graft ABS bead-like particles |
US5373060A (en) * | 1992-07-15 | 1994-12-13 | Basf Aktiengesellschaft | Particulate graft copolymer |
EP0592953A1 (de) * | 1992-10-12 | 1994-04-20 | BASF Aktiengesellschaft | Thermoplastische Formmasse |
EP0597275A1 (de) * | 1992-11-07 | 1994-05-18 | BASF Aktiengesellschaft | Thermoplastische Formmasse |
US5631323A (en) * | 1994-12-09 | 1997-05-20 | Basf Aktiengesellschaft | Composition of styrene-acrylonitrile copolymer matrix with particles of graft copolymer and crosslinked copolymer |
EP0953583A2 (de) * | 1998-04-29 | 1999-11-03 | Rohm And Haas Company | Schlagzähmodifizierer für aromatische amorphe Polyester |
Also Published As
Publication number | Publication date |
---|---|
KR20020071972A (ko) | 2002-09-13 |
EP1261653A1 (de) | 2002-12-04 |
DE10003511A1 (de) | 2001-08-02 |
US20020198324A1 (en) | 2002-12-26 |
AU2001228505A1 (en) | 2001-08-07 |
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