JPH05506051A - High temperature styrenic copolymer blend with improved tensile properties - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to certain rubber-modified monovinylidene aromatics that exhibit a moderate combination of physical properties. Regarding polymers.

Various monovinylidene aromatic monomers and ethylenically unsaturated nitrile monomers Various types of elastomers with small amounts of relatively stiff and/or brittle interpolymers - Materials such as various rubbers can be added to the matrix or continuous phase of the interpolymer. It is a matter of ordinary skill in the art to know that it is possible to make the product more impact resistant by incorporating it into the material. It is well known in the art. Elastomeric materials typically consist of discrete particles, e.g. A variety of interpolymers or similar mutual or homogeneous polymers The particles are in the form of graft-polymerized particles. These kinds of rubber modified impact resistance Polymer compositions are well known and are called graft copolymers or polyblends. It's been revealed. Among the best known compositions of these types are ABS or ABS There is a type composition. Compositionally, ABS or ABS-type compositions generally contain The elastomer usually contains polymerized butadiene with a monovinylidene aromatic monomer. in combination with a rigid interpolymer of polymers and ethylenically unsaturated nitrile monomers include. Structurally ABS or ABS-type compositions typically contain elastomeric particles, e.g. usually varying amounts of rigid interpolymers or similar mutual or homogeneous polymers. A rigid matrix or a continuous phase in which particles grafted with particles are dispersed. Consists of

The physical properties of these types of combinations are similar to those of elastomers with different dimensions and grain structures. – by the relative amounts of particles as well as by the structure of individual rubber particles (i.e. rubber particle shape). It is also well known in the art that . These include either of the two main types of rubber particles in rubber-modified polymer compositions. There are well-known advantages and disadvantages associated with the use of of the two main rubber particles Contains a matrix polymer absorbed inside, which is one of the types. Grafted rubber particles contain the same amount of rubber particles as other major particle types. Greater impact resistance than similarly grafted forms as solid rubber particles It is generally believed that it gives Grafted occluded rubber particles Polymers are usually produced and grafted in bulk or bulk-suspension polymerization methods. Ru.

There, a pre-prepared rubber is prepared in one or more polymerizable monomers, optionally with a diluent. These monomers are then polymerized. This kind of lump- Occlusion-containing particles produced by solution or bulk-suspension methods or variations of these methods is hereafter referred to as ``bulk particles''. 0 using the device. To produce a group of agglomerated particles with a volume average diameter of less than 5μ It is difficult to

Other major types of rubber forms (i.e. solids as described above) or non-occluded grafted rubber particles rubber) is usually achieved by emulsion polymerization of rubber in the form of an aqueous latex. of rubber After production, polymerizable and graftable monomers (e.g. styrene and acrylate) rylonitrile) is usually added to rubber-containing latex and polymerized to form grafted parts and Make the amount of matrix polymer. Non-occlusion type rubber particles produced by emulsion polymerization will be referred to as "emulsified particles" hereinafter. Graph of relatively rigid polymers with different emulsion particles However, if the rubber concentration is low (approximately 30% by weight) When having a concentration, these compositions may contain additional amounts of the same or or blended with different rigid polymers to achieve the desired rubber content in the resulting composition. It is very suitable for Such blendable intermediates are often Referred to as rafted rubber concentrates, a wide variety of rubber-modified polymer compositions are produced. It can be used to

The heat distortion temperature or softening point of ABS or ABS-type compositions is the phenylmaleimide, 0-methylstyrene, and styrene and maleic anhydride This can be increased by incorporating substances such as copolymers. is also known. However, the incorporation of these materials into ABS or ABS-type compositions is Compounding is usually achieved by some reduction in other physical properties. For example, styrene The use of maleic anhydride results in uncontrolled cross-linking at temperatures above 230°C. may result in unpredictable reductions in impact and melt flow rates. same Similarly, the use of α-methylstyrene as a comonomer also makes the composition difficult to process. There are times when

Specifically, the use of α-methylstyrene lowers the critical temperature of the product composition. As a result, depolymerization occurs and physical properties deteriorate. Therefore, some materials Although the use of ABS improves the heat distortion temperature of ABS or ABS-type compositions, This is done at the expense of other physical properties. In this way, high heat distortion temperatures can be achieved. The production of ABS or ABS-type compositions that also exhibit impact and tensile strength properties has been a long process. This is a tragic issue for the time being.

U.S. Pat. No. 4,567.233 discloses a rubber-modified styrene resin containing up to four components. Fat compositions are described. One component is a specific matrix resin and 0.1 to 0.5 and emulsion rubber particles having an average particle size of μ.

Another component is a specific matrix resin and a block or A graft copolymer comprising bulk-suspended rubber particles. The components of small particles are It should be between 50 and 97% of the total weight of the two rubber-containing components. The third component is A combination of a vinyl aromatic compound, a maleimide compound, and optionally a copolymerizable vinyl compound. Contains polymers. The optional fourth component is a bond between a vinyl aromatic compound and an unsaturated nitrile. It's Rimmer. This US patent states that such compositions have good thermal stability and drop resistance. It is described that it has high impact resistance. However, the issue of tensile strength has not been discussed. stomach.

The use of small rubber particles improves tensile strength for a given rubber content It is well known that this sacrifices impactability. Additionally, breasts that are generally smaller Compared to the use of bulk particles, the use of solidified particles has lower thermal properties, especially the Vicat softening point. bring down. This requires high rubber levels to achieve a given impact value. This is for the purpose of The Vicat softening point is further reduced by the presence of residues from the emulsification process. do. That is, the use of emulsified particles in ABS and ABS-type polymers has some Although conventional for quality improvement, such use may affect the thermal and It is detrimental to tensile strength properties.

The above problems are somewhat commonly encountered in the plastic molding industry, so Particularly if a rubber-modified molding composition with superior tensile properties is provided. compositions such as at the expense of other important properties such as impact strength and heat resistance. It would be highly desirable if it could be achieved without any problems.

Certain rubber-modified monovinylidene aromatic polymer compositions meet certain key parameters. Through appropriate and careful control and selection of data and criteria, very high tensile properties can be achieved. It is possible to maintain the desired combination of heat resistance and impact strength while still retaining the desired combination of heat resistance and impact strength. has now been discovered. In particular, in order to suitably achieve the above, in the context of the present invention, It has been discovered that within the range the following must be used: lump rubber and the total rubber is 0.09 to 0. 4; lump rubber is less than 1 micron flat Uniform particle size: As part of the composition, the copolymer has a weight of at least 120,000 The copolymer has a weight average molecular weight of monovinylidene aromatic monomer and ethylene. It is copolymerized from a sexually unsaturated nitrile monomer and a maleimide monomer; and the total rubber content in such compositions is from 8.5 to 13, based on the weight of the total composition. It is 5% by weight. Therefore, the present invention provides an improved method comprising the following components: A rubber modified, stiff, heat and impact resistant polymer blend composition.

(1) 7 to 76% by weight of monovinylidene aromatic moiety based on the rubber modified composition. Interaction between monomer, maleimide monomer and ethylenically unsaturated nitrile monomer polymer: (2) 7 to 25% by weight based on the rubber modified composition, produced by an emulsification method. a first graft copolymer composition: and (3) 1 based on the rubber modified composition. 7 to 85% by weight of the second graphite produced by the mass-type method. Futocopolymer composition: However a) the weight average molecular weight of the interpolymer is at least 120.000; , (b) the first graft copolymer composition has an average particle diameter of 0.05 to 0.65 microns; 30 to 70% by weight of the emulsified rubbery base polymer having a particle size is at least partially glued. 30 to 701% by weight of the rafted copolymer (A); (C) the copolymer; (A) is 10-60% by weight of ethylenically unsaturated nitrile monomer and 40-90% by weight % of a copolymerizable monovinylidene aromatic monomer in polymerized form; (d) the second graft copolymer composition is a bulk polymer having an average particle size of less than 1 micron; a copolymer (B) at least partially grafted onto a mu-like base polymer; , (e) the copolymer (B) is an ethylenically unsaturated nitrile monomer containing 15 to 36% by weight; A form obtained by polymerizing 64 to 85% by weight of copolymerizable monovinylidene aromatic monomer with Contain in the body, (f) the total rubber content of the rubber modified composition is from 8.5 to 13.5% by weight, and (g) rubber particles produced by bulk polymerization of the rubber modified composition and total rubber content; The weight ratio of is 0.09 to 0.4.

Tensile strength is applied to automotive interior trim, lights, cowl exhaust, air directional grilles, and requires molded parts capable of withstanding the loads and forces associated with mechanical fastening. Properties that are important depending on the end use, such as other uses.

The compositions of the present invention demonstrate the tensile strength, heat resistance and impact properties exhibited by these compositions. Considering the combination of strength and strength, it is well suited for such applications.

The present invention includes the following three essential components. (a) Monovinylidene aromatic/maleimide/ Ethylenically unsaturated nitrile interpolymer: (b) Emulsified particles dispersed inside a first graft copolymer containing; and (C) agglomerated particles (rubber) inside; A second graft copoly-copolymer dispersed therein comprising a "polymer" as used herein and [ The term "polymerization" is general and includes the more specific types of "homo-, co-, and "terpolymers" and "homogeneous, co-, and interpolymerized" respectively.

The first component of the above three essential components of the present invention is a maleimide monomer and a monovinyl monomer. Polymerizes nylidene aromatic monomer and ethylenically unsaturated nitrile monomer inside. Contains interpolymers. For the purposes of this invention, these interpolymers is hereinafter referred to as "rMSAN type". The most common example of these polymers is maleimide This is because it is manufactured from monomers, styrene, and acrylonitrile. MSAN type Interpolymer or 15 to 43% by weight of ethylenically unsaturated nitrile polymer monomer and 14 to 75% polymerization of monovinylidene aromatic monomer and 8 to 40% by weight of monovinylidene aromatic monomer. Manufactured from maleimide monomer. The weight average molecular weight of MSAN type polymers is moderate. the sum is at least 120,000, preferably at least 150,000 . Preferably, the compositions of the invention contain 7 to 76% by weight of MSAN type polymer.

Examples of monovinylidene aromatics included in polymeric form in the compositions of the invention include styrene. : α-alkyl monovinylidene aromatic monomer (e.g. α-methylstyrene, α-ethylstyrene, α-methylvinyltoluene, α-methyldialkylstyrene ring-substituted alkylstyrenes (e.g., ortho-, meta-, and Vinyltoluene: 0-ethylstyrene: p-ethylstyrene; 2,4-dimethyl styrene, pt-butylstyrene; etc.); ring-substituted halostyrene ( For example, 0-chlorostyrene, p-chlorostyrene, 0-bromostyrene, 2. 4-dichlorostyrene): ring-alkyl, ring halo-substituted styrene ( For example, 2-chloro-4-methylstyrene, 2,6-dichloro-4-methylstyrene, vinyl naphthalene; vinyl anthracene; and the like.

Alkyl substituents generally have 1 to 4 carbon atoms, isopropyl and isobutyl It can contain a chill group. If desired, monovinylidene aromatic monomers such as Mixtures of mers can also be used. Typically, monovinylidene aromatic mono MSAN type interpolymer to about 75% by weight, preferably 50-7 It constitutes 0% by weight.

Maleimide, N-alkyl as a maleimide monomer suitably used in the present invention Mention may be made of maleimide and N-arylmaleimide compounds.

In preferred N-arylmaleimides, the aryl substituent is halo or lower aryl. may have one or more atoms replaced by other inert moieties such as can. Suitable N-arylmaleimides are described in U.S. Pat. No. 3,652,726. It is listed. As the aryl group present in N-arylmaleimide, For example, phenyl, 4-diphenyl, ■-naphthyl, mono- and di-methylphenylphenyl all isomers, 2,6-ethylphenyl, 2-13- and 4-chlorophenyls halophenyl, 4-bromophenyl and other mono- and di-halophenyl isomers, 2 ．． 4. 6-Dolichlorophenyl, 2. 4. 6-dribromophenyl, 4 -n-butylphenyl, 2-methyl-4-n-butylphenyl, 4-benzylphenyl phenyl, 2-13- and 4-methoxyphenyl, 2-methoxy-5-chlorophenyl phenyl, 2-methoxy-5-bromophenyl, 2,5-dimethoxy-4-chloro Phenyl, 2-13- and 4-ethoxyphenyl, 2,5-jethoxyphenyl 4-phenoxyphenyl, 4-methoxycarbonylphenyl, 4-cyanophenyl phenyl, 2-13- and 4-nitrophenyl, and methyl-chlorophenyl (2,3-12, 4-12,5- and 4,3-isomers). preferred The N-arylmaleimide monomer is N-phenylmaleimide. Maleimi Mixtures of domonomers can also be used. Preferably maleimide monomer is an MSAN type interpolymer of 50% by weight, preferably 8 to 36% by weight. be.

Examples of unsaturated nitrile monomers include acrylonitrile and methacrylate. ethacrylonitrile, and mixtures thereof. Unsaturated nitrile is one In general, the polymer used for MSAN-type interpolymers containing three types of monomers is Reimide monomer and monovinylidene aromatic monomer and ethylenically unsaturated nitrile An amount of 15 to 43% by weight, preferably 20 to 25% by weight, based on the total weight of used in MSAN-type interpolymers.

Maleimide monomer, monovinylidene aromatic monomer and ethylenically unsaturated monomer In addition to the tolyl monomer, various additional monomers can be added to the rubber-modified polymer according to the invention. It can desirably be included in the composition in polymerized form. Additional models such as An example of nomers is conjugate 1. 3-diene (e.g. butadiene, isoprene, etc.) ; α- or β-unsaturated monobasic acids and their derivatives (e.g. acrylic acid , methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl Hexyl acrylate, methacrylic acid and its corresponding esters such as vinyl methacrylate, acrylamide, methacrylamide, etc.); Rides such as vinyl chloride, vinyl bromide, etc.: vinylidene chloride vinylidene, vinylidene bromide, etc.; vinyl esters such as vinyl acetate , vinylpropionate, etc.; dialkylmalates or fumarates, e.g. Methyl maleate, diethyl maleate, dibutyl maleate, and corresponding fumarates etc. Preferred examples of these additional monomers include C1-4 alkylmeth acrylates (including mixtures thereof). known in the art The amount of these monomers that can be included is a result of various factors, as shown in change. The amount of such monomer used is determined based on the non-rubber polyester of the rubber modified product of the present invention. Generally 10% by weight, based on the total weight of the monomers used to make the polymer part. % skinless.

Various additional monomers can be added to the present invention in all or some of the ways. It can be incorporated into compositions according to the invention. e.g. one or more additional monomers can be interpolymerized into the MSANu interpolymer. Also, one or more The additional monomers above can be grafted onto the rubber particles, and the bulk weight In this case, it can also be incorporated by polymerization within the rubber particles. Also, one or more additional The additive monomer is polymerized into a polymerization component, which is then converted into a rubber-modified polymer according to the present invention. They can also be mixed, eg, blended, into the composition.

The first graft copolymer includes at least one type of rubber particles produced by an emulsion polymerization method. include. The particles contain 10-60% by weight of ethylenically unsaturated nitrile monomer and 4% by weight of ethylenically unsaturated nitrile monomer. SAN or SAN type containing 0 to 90% by weight monovinylidene aromatic monomer Grafted onto interpolymers. Advantageously, the composition according to the invention weighs between 7 and 25 wt. % of the first graft copolymer. Some preferred compositions of the invention are The second graft copolymer is included in an amount greater than the graft copolymer. For example, the original One preferred embodiment of the invention is based on the total weight of the first and second graft copolymers. The following first graft copolymer is included in 49 parts by weight. Emulsified rubber particles are unimodal It is preferable to have a bimodal particle size distribution. In other words, the first graph The phytocopolymer can contain emulsified particles with different morphologies. first graph The phytocopolymer preferably contains 30 to 70% by weight of SAN or SAN-type ifinter. - Contains 30-70% by weight of emulsified rubber particles. Preferably the first graft The copolymer contains 35-55% by weight emulsified rubber particles. Preferably emulsified rubber particles contains polybutadiene rubber. The first graft copolymer is preferably 005-0 ．． It has a rubber particle size of 65μ.

Various base rubbers (base polymers are deposited on the base rubber during polymerization in the presence of such rubbers) - or grafted vines) are used as emulsifying particles. As these rubbers Rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) Rubber, acrylate rubber and mixtures thereof and rubber-forming monomers and others interpolymers or polymers with copolymerizable monomers (ASTM method test D74) Second glass transition below 0°C, preferably below -20°C, measured at 6-52T It is a polymer with points). Conjugated as such rubber 1. 3-diene homo one or more copolymerizable monoethylenes up to the same weight as the polymer and the conjugated 3-diene Renically unsaturated monomers such as monovinyl aromatic hydrocarbons (e.g. styrene: Ring-substituted alkylstyrenes such as 〇-1m- and p-vinyltoluene or 2 , 4-dimethylstyrene, ring-substituted ethylstyrene, p-t~butylstyrene, etc. .

α-alkylstyrenes such as α-methylstyrene, α-ethylstyrene, α- methyl-p-methylstyrene, etc.; vinylnaphthalene, etc.); ring-substituted halomonobili Nylidene aromatic hydrocarbons (e.g. 0-1 m-1 and p-chlorostyrene, 2 ．． 4-dipromostyrene, 2-methyl-4-chlorostyrene, etc.): acryloni Tolyl: Methacrylonitrile: Alkyl acrylate (e.g. methyl acrylate) (butyl acrylate, 2-ethylhexyl acrylate, etc.): Corresponding Alkyl methacrylates; acrylamides (e.g. acrylamide, methacrylates) (acrylamide, N-butylacrylamide, etc.), unsaturated ketones (such as metal), methyl vinyl ketone, methyl isopropyl ketone, etc.); α-olefins (and (e.g. ethylene, propylene, etc.); Pyridines: Vinyl esters (e.g. vinyl vinyl acetate, vinyl stearate): vinyl and vinylidene halide (e.g. vinyl and vinylidene chloride and bromide); Examples include interpolymers.

A preferred group of rubbers for use as emulsified rubber particles is 70-100% by weight of butadiene and/or isoprene and up to 30% by weight of monovinylidene aroma group hydrocarbons (e.g. styrene) and unsaturated nitriles (e.g. acrylonitrile). monomers selected from the group consisting of It is what it is. A particularly advantageous emulsified rubber polymer base is a butadiene homopolymer. or 90-99% by weight of butadiene and 1-10% by weight of acrylonitrile and and/or an interpolymer with styrene.

In a preferred embodiment of the invention, where the graft copolymer comprises bimodal particles, hereinafter One of the rubber components, called the small particle component, has a relatively small particle size; has a volume average particle size of 0.05 to 0.25μ, preferably 0.013 to 0.1 It has a number average particle size of 7μ. As previously mentioned, these small size particles are rubber-forming monomers. most conveniently prepared by emulsion polymerization of a mixture of to form a dispersion of uniformly sized particles of the desired size. For example, rice National Patent No. 3,509,237: National Patent No. 3,928.494; National Patent No. 4,243; No. 769: and 4.250,271. These US patents teaches a preferred method. This component preferably has a volume of 0.08 to 0.20μ Found to have a product mean diameter and preferably a number mean diameter of 0.02 to 0.13μ It was. Another rubber component to be included in this preferred rubber modified composition is a large emulsifier. called particle component. This component is 0.35-0.65μ, preferably 0.4-0 ．． It has a volume average particle size of 6μ. Most emulsion polymerization methods use the large emulsion particle size range mentioned above. The particles of this component are made from an emulsion of small rubber particles, as they do not inherently produce rubber particles. The dispersion may be subjected to agglomeration or coagulation during or after grafting the particles. It can be manufactured by

For example, US Pat. No. 3,551,370: 3.666.704.

See No. 3,956.218: and No. 3,825.621. these rice A national patent teaches a suitable method. Controlled emulsification of rubber particles in aqueous dispersions Particularly desirable techniques for performing controlled agglomeration, E. Henton and T. M. O'Brien, U.S. Pat. No. 4, entitled "Agglomeration of Particles in Rubber Latex," No. 419.496.

The small and large emulsified rubber particles mentioned above preferably have a weight ratio of 0.33. -4, preferably 0.4-1. As mentioned above, regarding emulsifying ingredients, Relatively large particles in this component, within the range of particle types and amounts specified in The use of and/or the use of a large percentage of this component typically Provides better impact resistance in objects.

The emulsified particle component advantageously forms from 60 to 91% by weight of the rubber in the present invention. Naturally Therefore, it is preferable to use 60 to 88% by weight, especially 60 to 70% by weight. preferable. Within these ranges, the amount of emulsified particle rubber will vary depending on the tensile strength of the resulting polymer composition. Helps regulate nature. Increased amount of emulsified particle rubber at constant rubber content increases tensile properties. The decrease in the percentage of emulsified particle rubber slightly reduces the tensile properties. This generally results in a tough product composition with losses.

The second graft copolymer is at least one produced by a bulk or bulk-suspension polymerization method. The rubber particles also contain 15-36% by weight of ethylenically unsaturated nitrogen. Tolyl monomer and 64-84% by weight monovinylidene aromatic monomer are added inside. A raft containing SAN or SAN-type ethylene interpolymers is also used. advantageously The composition of the present invention contains from 17 to 85% by weight of the second graft copolymer. lumpy The rubber particles can have a multimodal particle size distribution, such as a bimodal distribution, but preferably have a monomodal size distribution. It has a peak particle size distribution. Advantageously, the bulk rubber particles have a volume average particle size of less than Iμ.

The rubber substrate used for the second graft copolymer is preferably a diene homopolymer. for example poly(l,3-butadiene), or at least 30% by weight, and further Preferably from 50 to 85% by weight of 1,3-butadiene and up to about 70% by weight and further Preferably 15 to 50% by weight of monovinylidene aromatic compound, preferably styrene. It is a block or random copolymer with This rubber base material is also In addition, it typically has a secondary glass transition point of 0°C or lower, preferably -20°C or lower.

A preferred rubber for use as bulk rubber particles is a homopolymer of butadiene.

The bulk particles advantageously have a volume average particle size of less than 1μ, preferably between 0.15 and 0.95μ. diameter, and 0. It has a number average particle size of 1 to 0.45μ. More preferably, this composition The volume average diameter of the particles is 0.4 to 0.9μ, and the number average diameter is about 0.2 to about It is 0.4μ. Most preferably, the volume average particle size is between 04 and 0.69 microns. mass The particulate component advantageously accounts for 9 to 40% by weight of the total rubber component in the composition of the invention, preferably % by weight, most preferably 30-40% by weight. particle size The test is carried out using a commercially available Coulter Counter. Visible phase contrast microscopy or is measured by electron microscopy techniques.

The second graft copolymer contains less than 20% by weight of the total weight of the graft copolymer. Generally, it has a rubber content and the remainder is SAN or SAN-type ethylene interpolymer. preferable. Therefore, a preferred second graft copolymer is the graft copolymer itself. Rubber contents ranging from 0.75 to 15% by weight, in particular from 4 to 9% by weight, based on It's superficial.

Within the above range, the use of this bulk rubber particle component is expected and unacceptable. Desirable water in polymer compositions produced without adversely affecting tensile properties to a degree Provides similar impact resistance. In fact, the composition according to the invention Provides an excellent combination of Vicat, tensile, and impact resistance for the amount of rubber it contains show. That is, the use of the indicated bulk rubber particles in the indicated amounts results in very high tensile properties. while still providing desirable levels of impact and Vicat heat resistance. A rubber-modified molding composition is provided.

Grafting onto the desired upper layer polymer preferably an amount of SAN or SAN type polymer. From bulk or bulk-suspension grafting methods to create particles that contain or contain particles. It is most desirable to use the resulting particles in the second graft copolymer. was discovered. As is well known in the art, such bulk methods are highly satisfactory. can be used to make rubber particles suitable for use in this component. parable See US Pat. No. 3,509,237 and US Pat. No. 4,239,863. this et al.'s US patent teaches a suitable method.

Generally, in compositions according to the invention, based on the weight of the total rubber modified polymer composition, A total of 8.5-13.5% by weight of rubber is dispersed therein in the form of particles. child Tensile properties and Vicat heat distortion temperature decrease when using higher rubber content than . Preferably, the rubber modified composition has a total weight of 10 to 13 ．． Contains 5% by weight of dispersed rubber polymer. Preferably, the lump rubber and whole rubber in the composition are The weight ratio of aluminum is 0.09 to 0.4.

More preferably, this ratio is between 0.12 and 0.12. 4 and most preferably 0 ．． It is 3 to 0.4.

One important criterion of the present invention is that the granular rubber dispersed in the polymer matrix is This means that it contains at least two different components. Dispersed granular rubber is It is generally preferred that the particulate component consists essentially of. The term "rubber particle component" means a group of rubber particles of the same type and having approximately the same particle size. child The two main types of rubber particles are (1) occlusion particles produced by the bulk method; and (2) solid non-occlusion particles produced by an emulsion polymerization method. Each rubber component are then characterized by a combination of the average diameter of the particles and the method by which they are manufactured. It will be done. The average particle size of the rubber particle components used here means unless otherwise specified. , refers to the volume average diameter of the particle groups that make up the particle-type rubber component. Hatondo In this case, the volume average diameter of the particle group is the same as the weight average. emulsion manufacturing rubber particles In this case, measurements of average particle size are typically performed prior to polymer grafting. However, in the case of bulk particles, the particle size is generally determined by grafting onto rubber particles and and occlusion of polymers within the particles. Emulsified granules with an average particle size of less than about 1 micron The volume average diameter of the child group is high, as is the number average diameter and particle size distribution. Conveniently measured by drodynamic chromatography (HDC) can. Hydrodynamic chromatograph is U.S. Patent No. 3,865,71 No. 7, and also Journal of Co11oid and Tnterface Science, V, 89. No. I, pp. 94-106 (+982) is also discussed. Agglomerates with an average particle size greater than about 1 micron For groups of shaped particles and groups of emulsified particles, volume average particle size, number average particle size and particle size distribution by scanning particle-containing compositions by methods well known in the art. It can be determined by analysis of electron micrographs.

The various rubber particle components include particles with a range of particle sizes, and Analytical techniques have shown that particles of special rubber particle components generally have a rather narrow range of particle sizes. Showing, of course, is recognized. Same as the volume average particle diameter of a certain particle group This means that the ratio to the number average particle size of the group is approximately in the range of 1 to 3.5. It means that.

The rubber components listed above are based on the weight of the rubber-forming monomer(s). Although cross-linking can contain up to % cross-linking agents, cross-linking is a graft polymerization reaction. problems in terms of dissolving the rubber into monomers, especially for bulk or suspension polymerization reactions. therefore, it is generally preferred as a component in bulk or suspension polymerizations. Not. Also, excessive cross-linking can lead to loss of rubber properties and therefore It is generally not preferred even as an emulsion polymerization component. When using cross-linking agents, It can be any commonly used for cross-linking diene rubber, even divinylbenzene, diallyl malate, diallyl fumarate, diallyl adipe diacrylate, allyl acrylate, allyl methacrylate polyhydric alcohol salts and dimethacrylates (e.g. ethylene glycol dimethacrylate) etc.).

Amounts of other polymers and/or copolymers, such as polymers, may be present in the ABS type composition. of phenylene oxide, polycarbonate and polyester polycarbonate It may also be desirable to include polymers and/or copolymers. .

In graft polymerization reactions, as is well known in the art, the desired polymerizable moiety is The monomer is mixed with a pre-produced rubber base material, and then this monomer is polymerized and chemically Alternatively, at least a portion of the resulting polymer may be glued onto a rubber substrate. make it float. Depending on the ratio of monomer to rubber substrate and the polymerization conditions, the desired amount of polymer can be added. Achieve polymerization of both grafted and non-grafted polymers onto the rubber substrate of the remer. all or part of the matrix can be provided simultaneously.

Various types including Ziegler-Natsuta polymerization, anionic polymerization and free radical polymerization This technique is commonly used for the polymerization of rubber monomers. Free radical polymerization is graft topo To produce a latex emulsion suitable for use as a base material for emulsion polymerization of remers. Can be used for See, eg, U.S. Pat. No. 4,243,765.

Various techniques suitable for producing the polymeric components of the present invention are well known in the art. It is knowledge. Examples of these well-known polymerization methods include bulk, bulk-solution, bulk-suspension, Suspension and emulsion polymerization methods and other variations and/or combinations of such methods A combination can be given. For example, U.S. Patent No. 3,509°237: U.S. Patent No. 3,923 , No. 494; No. 4,239,863: No. 4,243,765: and No. 4,239,863; See No. 4,250,271. These US patents teach such methods. Ru. As is well known in the art, one or more rubber components may be homo- or – the same reaction to graft the polymer or the corresponding non-grafting of the matrix portion Advantageously used for making all or part of homo- or interpolymers of can be done. In the case of production of either grafted polymers in small quantities Focused on producing uniquely non-grafted (i.e. matrix) polymers of Should. Advantageously, (1) the small emulsified particles and the large emulsified particles are simultaneously Graphing with monovinylidene aromatic monomer and ethylenically unsaturated nitrile monomer grafted and at the same time a small amount of ungrafted SAN or SAN-type IF (2) the grafting of the bulk particles is the same or Different monovinylidene aromatic monomers and ethylenically unsaturated nitrile monomers and the overall SAN desired for the matrix of the final composition. Alternatively, a SAN-type Ifin terpolymer part can also be manufactured, and (3) rubber-modified polymer The remainder of the ungrafted MSAN-type interpolymer desired as a matrix for is prepared separately, and (4) the above components are then mixed to form the subject polymer. producing a composition; Preferably, a separately manufactured MSAN type interpointer Produced by reamer or bulk-solution type polymerization method.

Generally, the matrix portion of the present invention comprises (1) an MSAN-type interpolymer; ) other comonomers interpolymerized into the MSAN-type interpolymer, (3) mixing (4) additional non-elastomeric polymeric material produced during grafting of the emulsified particles; (5) produced during grafting of bulk particles; Non-grafted, non-occluding polymer and/or pond filler type materials including. All of the matrix (non-grafted) polymers from all raw materials The weight average molecular weight (Mw) is from 40,000 to at least 300,000, preferably is 70,000 to 200,000. In other words, the rubber modified polymer of the present invention - The Mw of the non-grafted, non-occlusion polymer contained in the composition is (1) Emulsified particles (2) the vines produced during the grafting of bulk particles; , (3) is an MSAN type polymer, and/or (4) is a non-grafted matrix. is the Mw of the amount of polymer that may be from other sources of the xpolymer; It is averaged so that it is within the desired range.

MSAN type interpolymer first and second graft copolymers are shown here. When blended together, the rubber is modified to provide stiffness and resistance to heat and shock. A polymer composition is formed. Advantageously, the composition has a temperature of at least 104°C (D IN-B), preferably with a Vicat softening point of at least 112°C. present invention The impact strength of the composition of is at least 7 KJ/m2 as determined by the Charpy method. Preferably it is at least 9 KJ/m2. The tensile strength at the yield point is advantageously small. at least 5ON/mm2, preferably at least 55N/mm''.The present invention Advantageously, the composition of It has an elastic modulus of Pa.

The three polymer components of the present invention are the MSAN type polymer and the fourth and second groups. Raft copolymer, weight percentages are based on the total weight of these components. It should be noted that

The present invention will be described more specifically with reference to the following specific examples, manufacturing examples and comparative experiments. I will clarify. All parts and percentages are by weight unless otherwise specified. many kinds The physical properties of various polymer compositions were tested using standard test methods. Notsuchi Ai Shift strength was determined according to ISO 1804a. Tension at yield and failure Strength (Ty and Tr> and elongation %, respectively, according to D IN53455-6-3 Therefore, it was decided. Melt flow rate (MFR) value is]: HN33735-u Therefore, it was decided. Vicat thermal deformation was determined according to D IN53460, condition B. Ta. Charpy impact was determined according to DIN 53453. The elastic modulus is D Determined according to IN53457. Comparative experiments are not an aspect of the invention.

Manufacturing 1. MSAN, 1 8% N-phenylmaleimide, 5296 styrene, 20% acrylonitrile and 20% ethylbenzene at a temperature of 140-146°C. Feed the SAN coil reactor. React the solution of the radical-generating compound in a separate feed stream. supply to the reactor. Devolatilize the 40-70% solids polymer by using vacuum. do.

Manufacturing 2. MSAN, 2 Repeat the method of manufacture 1. However, the feed mixture was 18% acrylonitrile, 4 Contains 8% styrene, and 26% ethylbenzene, reactor temperature is 145- 152°C and the prepolymer solution contains 40-65% solids.

Manufacture of bulk ABS3 and 4 The bulk particle component is contained in a mixture of styrene, acrylonitrile, and ethylbenzene. Polybutadiene (BUNHX529C product available from Bayer AG) rubber) and then stir and/or shear these monomers. The rubber particles are produced by polymerization to achieve the desired rubber particle size. Polymerization period In the middle, some of the generated interpolymer is grafted onto the rubber, but some is not. The matrix interpolymer is produced without In the second method, all As in the grafting method, varying amounts of the matrix interpolymer are , depending on the amount of monomers supplied (in addition to the grafted part) Can be done.

Manufacture of blocky ABS5 Repeat the manufacturing method for bulk ABS 3 and 4. However, different polybutadiene (BUNA HX565 product name rubber available from Bayer AG) use. Also, large particles with a bimodal distribution are produced simultaneously in parallel reactors.

Emulsification Production of ABS6.7 and 8 Grafting monomers (styrene and acrylonitrile), mercaptans Aqueous latex containing rubber particles while supplying a persulfate initiator, and an emulsifier. heat the water. SAN-grafted rubber particles as well as some non-grafted SAN The above latex containing was freeze solidified, thawed, centrifuged, and then air dried. to reduce the water content in the resulting powdered polymer composition to less than 1%. This method is Preparation of bimodal emulsion ABS7 and in bimodal emulsion ABS6 and bimodal emulsion ABSg It describes the production of small particles.

Approximately 0.34% by weight based on the total weight of the rubber before addition of grafting monomers By adding the agglomerating agent of AB to the starting aqueous latex of the previous section, the bimodal emulsion AB Manufacture S material. The agglomeration agent consists of a polybutadiene core and an ethyl acrylate-methane core. and a shell of acrylic acid (92/8) copolymer. Some of the particles agglomerate gives a bimodal particle size distribution of large and small particles. Next, add the second latex to the front section. Graft and recover as described.

Further characteristics of these manufacturing methods are shown in the table.

Zero N-phenylmaleimide Example 1 Mixture of 20 parts emulsified ABS6, 20 parts bulk ABS3 and 60 parts MSANI Tri-blend. The resulting blend is then mixed into a homogeneous melt on a mixer; Extruded into strands and then pelletized. These pellets are injection molded Make a standard test bar of the blend composition. Further properties and physical tests of the blend composition The experimental results are shown in Table 1.

Example 2 15 parts emulsified ABS, 6.50 parts bulk ABS 3, and 35 parts MSAN1. The method of Example 1 is repeated using: Further properties and physics of blend compositions The test results are shown in Table 1.

Examples 3-5 and comparative experiments 6-7 The method of Example 1 is repeated using the amounts of blend ingredients specified in Table 2. Bu Further properties and physical property test results of the Lend composition are shown in Table 2.

Table 2 The compositions of Examples 3-5 exhibit high thermal properties as well as unexpectedly high tensile strength. ratio Comparison experiment 6 was outside the desired range of bulk rubber/total rubber ratio and therefore was not acceptable. It has an incredibly low impact value. Comparative experiment 7 did not include bulk ABS and was conducted at the all-rubber level. Ch of 4.2 which is too low despite the fact that it is comparable to that of example 5 It has an arpy value.

Examples 8-■2 and Comparative Experiments 13-14 Blend ingredients in the amounts specified in Table 3 were The method of Example 1 is repeated using: Further properties and physical properties of the blend composition The test results are shown in Table 3.

Examples 8-12 are illustrative of the invention and demonstrate high Vicat softening points and unexpectedly high pull. It shows tensile properties. Comparative experiment 13 contained 14.6% rubber, which is the same as that of the present invention. is above the upper limit of the rubber level specified by . As a result, the impact strength is high Man, Young's modulus is way too low. Comparative experiment 14 included bulk ABS It is outside the scope of the present invention because it contains too much rubber and has a very low modulus. .

Example 15 and comparative experiments 16-18 The method of Example 1 is repeated using the amounts of blend ingredients specified in Table 4. Bu Further properties and physical property test results of the Lend composition are shown in Table 4.

In Table 4, Mw indicates the weight average molecular weight of the MSAN component of the blend.

The data in Table 4 is reasonable for the equal bow 1 tension property (i.e. Charpy > 7) Demonstrates the effect of MSAN molecular weight on impact performance retention. comparative experiment 16. For 17 and 18, the bulk/whole rubber ratio is within the scope of the invention. However, the MSAN molecular weight of 92,000 provides a composition with the desired impact properties. too low.

Examples 20-23 and comparative experiment 19 The method of Example 1 is repeated using the amounts of blend ingredients specified in Table 5. Bu Further properties and physical property test results of the blended compositions are shown in Table 5.

The methacrylate-butadiene styrene used (referred to as "rMBS" in Table 5) b) The rubber grade is Paraplex from Rohm and Haas Company. 3607). (Paraplex is a Rohm & Haas Company. is a trademark of

In the examples summarized in Tables 1-4, the emulsifying component of the blend system is substantially 100% % of rubber particles made from butadiene. However, Examples 20 and 2 Milk consisting of 93% butadiene and 7% styrene as shown by 2 Rubber particles are within the scope of this invention. The use of unimodal ABS is also shown in Example 20. ing. The use of bimodal block ABS is shown in Example 21. Another impact degeneration capsule For example, a mixture of emulsified ABS and MBS is shown in Example 23 and provides the desired It provides blends with a range of physical properties. However, since the monomodal lumpy ABS component For a rubber particle size of 1.11 microns, as shown by comparative experiment I9, was found to be above the upper limit for maintaining good tensile properties.

Summary book (a) Monovinylidene aromatic monomer, maleimide monomer and ethylenically unsaturated Interpolymer near (b) emulsification method containing nitrile monomer in a polymerized form The first graft copolymer thus prepared comprises 10 to 60% by weight of ethylene. polyunsaturated nitrile monomer and copolymerizable monovinylidene aromatic compound of 40 to 901j196 30 to 70% by weight of a copolymer (A) containing an aromatic monomer in polymerized form; and the copolymer (A) has 30 to 70% of rubbery groups in the graft copolymer. material polymer (B) at least partially grafted to 0.05~O,SS 7 to 25% by weight of rubber particle size distribution with an average particle size of microns: and (C ) Produced by bulk polymerization method, containing 15-36% by weight of ethylenically unsaturated nitrile monomer. - and 64 to 85% by weight of a copolymerizable monovinylidene aromatic monomer. and having an average particle size of less than 1 micron. A second graft copolymer comprising a copolymer (C) obtained by partially grafting -17 to 85% by weight, and the total rubber content of the composition is 8.5 to 13.5% by weight. rubber modification in which the ratio of bulk rubber to total rubber weight in weight % is from 0.09 to 0.4; Rigid, heat resistant, impact resistant polymer composition. This composition is used as a modified material for sound .

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Claims (12)

[Claims] 1. (1) 7 to 76% by weight of monovinylidene aromatic composition based on the rubber-modified composition. Incorporation of group monomers, maleimide monomers, and ethylenically unsaturated nitrile monomers Terpolymer; (2) 7 to 25% by weight based on the rubber modified composition, produced by an emulsification method. a first graft copolymer composition; and (3) 1 based on the rubber modified composition. 7 to 85% by weight of the second graft copolymer composition prepared by the bulk method. (a) the weight average molecular weight of the interpolymer is at least is also 120,000, (b) the first graft copolymer composition has average particles of 0.05 to 0.65 microns; from 30 to 70% by weight of the emulsified rubbery base polymer having the diameter 30 to 70% by weight of the fluffed copolymer (A), (c) said copolymer ( A) is 10-60% by weight of ethylenically unsaturated nitrile monomer and 40-90% by weight % of copolymerizable monovinylidene aromatic monomer in polymerized form; (d) the second graft copolymer composition is in bulk having an average particle size of less than 1 micron; comprising a copolymer (B) at least partially grafted onto a rubbery base polymer; fruit, (e) the copolymer (B) is an ethylenically unsaturated nitrile monomer containing 15 to 36% by weight; A form obtained by polymerizing 64 to 85% by weight of copolymerizable monovinylidene aromatic monomer with Contain in the body, (f) the total rubber content of the rubber modified composition has from 8.5 to 13.5% by weight; and (g) Rubber produced by bulk polymerization relative to the total rubber content of the rubber modified composition. A rubber modified composition characterized in that the weight ratio of particles is 0.09 to 0.4. 2. The emulsified rubber-like base polymer has a bimodal rubber particle size distribution, with the peak particle size value being small. 0.05-0.25μ for particles and 0.35-0.7 for large particles A composition according to claim 1, which has a particle diameter of 5μ. 3. Any of claims 1 to 2, wherein the maleimide monomer comprises N-phenylmaleimide. The composition of item 1. 4. The MSAN type interpolymer must have a molecular weight of at least 150,000. The composition according to any one of claims 1 to 3. 5. The set according to any one of claims 1 to 4, wherein the total rubber content is 10 to 13.5% by weight. A product. 6. Any one of claims 1 to 5 having a chirpy impact value of at least 7 KJ/m2. Composition of item 1. 7. Any one of claims 1 to 6 having a Vicat heat distortion temperature of at least 104°C. composition of the term. 8. Any one of claims 1 to 7 having a tensile yield of at least 50 N/mm2. Composition of. 9. Any one of claims 1 to 8 having an elastic modulus of at least 2400 MPa. Composition of item 1. 10. The interpolymer is an ethylenically unsaturated nitrile monomer containing 15 to 43% by weight. 8-50% by weight of N-arylmaleimide monomer and 14-75% by weight of N-arylmaleimide monomer. A composition according to any one of claims 1 to 9, comprising a monovinylidene aromatic monomer. 11. Claim 1 wherein said second graft copolymer comprises 0.75 to 15% by weight rubber. The composition according to any one of items 1 to 10. 12. Any of claims 1 to 11, wherein the Vicat heat distortion temperature is at least 112°C. The composition of item 1.