JPS6326763B2 - - Google Patents
Info
- Publication number
- JPS6326763B2 JPS6326763B2 JP16237681A JP16237681A JPS6326763B2 JP S6326763 B2 JPS6326763 B2 JP S6326763B2 JP 16237681 A JP16237681 A JP 16237681A JP 16237681 A JP16237681 A JP 16237681A JP S6326763 B2 JPS6326763 B2 JP S6326763B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomer
- parts
- acid
- latex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000178 monomer Substances 0.000 claims description 49
- 229920000126 latex Polymers 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 31
- 229920001971 elastomer Polymers 0.000 claims description 30
- 239000005060 rubber Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 239000004816 latex Substances 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 230000000379 polymerizing effect Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920000578 graft copolymer Polymers 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229940096992 potassium oleate Drugs 0.000 description 4
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 2
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- GGSRTHRSSCWGGK-UHFFFAOYSA-L 2,2-dibutyl-5-hydroxy-1,3,2-dioxastannepane-4,7-dione Chemical compound CCCC[Sn]1(CCCC)OC(=O)CC(O)C(=O)O1 GGSRTHRSSCWGGK-UHFFFAOYSA-L 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- GXBDYVJMWRTUNT-UHFFFAOYSA-N buta-1,3-diene;2-methylprop-2-enoic acid Chemical compound C=CC=C.CC(=C)C(O)=O GXBDYVJMWRTUNT-UHFFFAOYSA-N 0.000 description 1
- YIEXROAWVNRRMJ-UHFFFAOYSA-N buta-1,3-diene;butyl prop-2-enoate Chemical compound C=CC=C.CCCCOC(=O)C=C YIEXROAWVNRRMJ-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- SMUVTFSHWISULV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C(C)=C SMUVTFSHWISULV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KUKFKAPJCRZILJ-UHFFFAOYSA-N prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C KUKFKAPJCRZILJ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
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The present invention relates to a new thermoplastic resin having excellent impact resistance. Impact-resistant resins such as ABS resin and high-impact polystyrene are usually obtained by graft polymerizing styrene, acrylonitrile, methyl methacrylate, and other monomers to rubber components.
The composition and structure of the graft copolymer, the rubber content, the polymerization method, etc. greatly influence the physical properties of the final composition. In particular, when graft polymerizing rubber components using emulsion polymerization, it is a widely known fact that the particle size of the base rubber component controls the impact resistance and processability of the final composition. The larger the size, the better the impact resistance and processability of the resulting resin. Therefore, attempts have been made to make the rubber particle size as large as possible, and various proposals have been made so far. The present applicant also previously swelled a diene rubber with a copolymer latex consisting of an unsaturated acid monomer and an alkyl acrylate in the presence of a large particle size rubber latex. Both are a type of monomer and CH 2 = which can be copolymerized with this monomer.
We proposed a resin composition with good impact resistance obtained by polymerizing a mixture consisting of a monomer having a C Proceeds in a short time,
The present invention was completed based on the discovery that a resin composition with even better impact resistance could be obtained by graft polymerizing the obtained large particle diameter rubber. The present invention is directed to (a) a rubber having a pH of 7 or higher (A )
For 100 parts by weight of latex (as solid content),
(b) 3 to 30% by weight of at least one unsaturated acid selected from the group of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and at least one alkyl acrylate whose alkyl group has 1 to 12 carbon atoms 97 Of the monomer (b) consisting of ~35% by weight and 0-48% by weight of other copolymerizable monomers, first polymerize the portion that is 5-90% by weight and does not contain the unsaturated acid. After that, 0.1 to 5 parts by weight (as solid content) of an acid group-containing copolymer (B) latex obtained by polymerizing the remaining 95 to 10% by weight of the monomer (b) containing the unsaturated acid.
(c) at least one selected from the group of styrene, acrylonitrile and methyl methacrylate in the presence of 7 to 70 parts by weight (as solids) of an enlarged rubber latex having a particle size of at least 0.2Ό obtained by adding It is characterized by polymerizing 93 to 30 parts by weight of a monomer mixture consisting of 30% by weight or more of one type of monomer and 30% by weight or less of a monomer having a CH 2 =C< group copolymerizable with the monomer. This is a method for producing a thermoplastic resin with excellent impact resistance. The rubber component (A) is 1.3-polybutadiene or a copolymer containing 50% or more of 1.3-butadiene,
For example, butadiene-styrene, butadiene-
Butadiene-aromatic vinyl compound copolymers such as vinyltoluene copolymers, butadiene-acrylonitrile copolymers, butadiene-methacrylonitrile copolymers, butadiene-methyl acrylate, butadiene-ethyl acrylate, butadiene-butyl acrylate, butadiene-2-
Butadiene-acrylic acid ester copolymers such as ethylhexyl acrylate copolymers, butadiene-methyl methacrylate, butadiene-
It includes butadiene-methacrylic acid ester copolymers such as ethyl methacrylate copolymers, and also terpolymers containing 50% or more of butadiene. These can be easily obtained by commonly known emulsion polymerization. There are no particular restrictions on the catalyst, emulsifier, etc., and the particle size thereof is 0.04 to 0.2Ό. A copolymer (B) containing acrylic acid, methacrylic acid, itaconic acid and crotonic acid is then used to thicken the rubber latex. It is essential that this copolymer (B) contains an acid group-containing monomer and an acrylate, and at least one type of alkyl acrylate whose alkyl group has 1 to 12 carbon atoms is selected as the acrylate. It can be done. Even if a monomer such as methacrylate, styrene, or acrylonitrile is used instead of acrylate, no effect is observed. However, it is possible to replace up to half of the acrylate with other monomers. The acid group-containing monomer is used in an amount of 3 to 30% by weight, but if it is less than 3%, the enlargement ability is small;
Also, if it exceeds 30%, the enlargement ability is too strong,
This is not preferable because it generates particles that are larger than 1Ό. In addition, the optimal content of the acid group-containing monomer varies depending on the degree of hydrophilicity of the acrylate used. If the acrylate has a high hydrophilicity, the enlargement effect will be reduced in the region where the amount of the acid group-containing monomer is small. On the other hand, if the amount of acid group-containing monomer increases, the latex will be destroyed, which is undesirable.On the other hand, if the hydrophilicity of acrylate is low, areas with a low amount of acid group-containing monomer will have the effect of thickening. is small, and the effect will not be seen unless the amount of the acid group-containing monomer exceeds a certain level.
For example, in the case of highly hydrophilic acrylates such as methyl acrylate and ethyl acrylate, it is optimal when the amount of acid group-containing monomer is 5 to 10%, whereas hydrophobic In the case of butyl acrylate and 2-ethylhexyl acrylate, which are alkyl acrylates, the optimum amount is 13 to 20% of the acid group-containing monomer. However, when a highly hydrophilic acrylate is used, even if the amount of acid group-containing monomer is 5 to 10%, the system tends to become unstable, which leads to the formation of cullets (coarse particles). On the other hand, when hydrophobic acrylates such as those described above are used, the system does not become unstable and uniform enlarged particles can often be obtained. In addition to the above, examples of acid group-containing monomers or similar monomers include cinnamic acid, maleic anhydride,
There are butenetricarboxylic acids and the like, but their use is not practical due to their low enlargement ability. Acid group-containing copolymer (B) used in the present invention
The latex contains 3 to 30% by weight of at least one unsaturated acid selected from the group of acrylic acid, methacrylic acid, itaconic acid and crotonic acid, and at least one alkyl acrylate whose alkyl group has 1 to 12 carbon atoms. Of the monomer (b) consisting of ~35% by weight and 0-48% by weight of other copolymerizable monomers, first polymerize the portion that is 5-90% by weight and does not contain the unsaturated acid. After that, the remaining 95 to 10% by weight of the monomer (b) containing the unsaturated acid must be continuously polymerized without forming new particles, resulting in a latex with a two-layer structure. . This acid group-containing polymer (B) latex is the base rubber (A).
By adding an inorganic electrolyte, preferably an inorganic salt, particularly a neutral inorganic salt, to the latex, the particle size of the base rubber can be enlarged very efficiently and stably. The amount of the acid group-containing polymer (B) latex added is 0.1 to 5 parts by weight, particularly preferably 0.5 to 3 parts by weight, per 100 parts by weight of the base rubber (A). In addition, the inorganic electrolyte is added per 100 parts by weight of the base rubber (A).
Addition of 0.05 to 4 parts by weight, particularly 0.1 to 1 part by weight, will increase the size of the base rubber more efficiently and will greatly improve the stability of the resulting large particle size rubber latex. As the inorganic electrolyte, commonly known inorganic salts such as KCl, NaCl, Na 2 SO 4 etc. can be used. Further, this inorganic electrolyte can be added in advance during polymerization of the base rubber latex, and has the same effect as when added during enlargement. When carrying out the enlargement treatment of the present invention, it is necessary to maintain the pH of the base rubber (A) latex at 7 or higher. When the PH value is on the acidic side, even if the acid group-containing copolymer (B) latex is added, the enlargement efficiency is low, and the composition targeted by the present invention cannot be advantageously produced. The pH of the base rubber (A) latex may be adjusted to 7 or higher during the polymerization of the base rubber, or may be adjusted separately before the enlargement treatment. In the presence of 7 to 70 parts by weight of the rubber latex that has been enlarged in this way, the desired impact-resistant resin can be obtained by polymerizing monomers mainly consisting of styrene, acrylonitrile, and methyl methacrylate. . Examples of monomers to be grafted onto the rubber latex include styrene alone, methyl methacrylate alone, styrene-acrylonitrile monomer mixture, styrene-acrylic acid ester monomer mixture, methyl methacrylate-acrylonitrile monomer mixture, and methyl methacrylate-acrylic. Examples include acid ester monomer mixtures, acrylonitrile-acrylic acid ester monomer mixtures, and monomer mixtures of three or more of these monomers. In this emulsion graft polymerization, commonly known emulsifiers and catalysts are used, and there are no particular restrictions on the type and amount added. If the rubber content is less than 7% by weight, the impact resistance is low and there is no practical value, and if it exceeds 70% by weight, fluidity and processability deteriorate, which is not preferable. The preferred rubber content is 10-25% by weight. Further, by blending a resin not containing rubber with the above graft polymer, a resin composition with good impact resistance can be obtained. In this case, the rubber content in the base graft polymer may not be in the range of 7 to 70% by weight, but the final content after blending may be in the range of 7 to 70% by weight. preferable. Examples of rubber-free resins used at this time include polystyrene, polymethyl methacrylate, AS resin, polyvinyl chloride, and polycarbonate. When graft polymerizing the enlarged rubber, the graft monomer may be added all at once, added in portions, added continuously, or each monomer may be graft polymerized individually in stages. Also good. Known antioxidants, lubricants, colorants, fillers, etc. can be added to the resulting graft or graft-blend polymer. The composition obtained by the production method of the present invention has the following advantages compared to conventionally known thermoplastic resin compositions. 1. It is possible to manufacture continuously from the polymerization of the rubber to the polymerization of the final composition. 2 No special equipment is required. 3. Rubber polymerization can be carried out in a short time, resulting in extremely high productivity. 4. Since no specific dispersant or emulsifier is required during rubber enlargement treatment, it is economical and the final composition has good thermal stability. 5. Very little formation of excessive coagulum (coagulum) after rubber enlargement treatment and graft polymerization. 6. Rubber with a large particle diameter (0.4 to 1 ÎŒm), which is extremely difficult to obtain using conventional enlargement methods, can be easily obtained, so a composition with extremely high impact strength can be obtained. In the following examples, "parts" and "%" mean "parts by weight" and "% by weight," respectively. Example 1 Synthesis of base rubber (A-1) 1.3-Butadiene 66 parts Butyl acrylate 9ã Styrene 25ã Diisopropylbenzene hydroperoxide 0.2 parts Potassium oleate 1.0ã Potassium rosinate 1.0ã Sodium pyrophosphate 0.5ã Ferrous sulfate 0.005 ã Dextrose 0.3ã Water 200ã According to the above composition, autoclave 100 at 50â
Polymerized with Polymerization was almost completed in 9 hours, and the conversion rate was
A rubber latex with a particle size of 97% and a particle size of 0.08Ό was obtained. Acid group-containing copolymer latex for enlargement (B-1)
Synthesis of n-butyl acrylate 25 parts Potassium oleate 2ã Sodium dioctyl sulfosuccinate 1ã Cumene hydroperoxide 0.1ã Sodium formaldehyde sulfoxylate 0.3ã Water 200ã After polymerizing the mixture of the above composition at 70°C for 1.5 hours, continue At 70°C, a mixture consisting of 60 parts of n-butyl acrylate, 15 parts of methacrylic acid, and 0.3 parts of cumene hydroperoxide was added dropwise over 1 hour, and then 1
Stirring was continued for hours to obtain a copolymer latex with a conversion rate of 98%. Adjustment of enlarged latex Base rubber latex (A-1) 100 parts (solid content)
1.5 parts (solid content) of latex (B-1) was added to the mixture over 5 seconds while stirring. Table 1 shows the results of measuring particle diameters using an electron microscope for samples taken immediately after stirring this latex for 30 minutes and for samples taken after being left for 5 days. Next, using the enlarged latex obtained by stirring for 30 minutes, graft polymerization was immediately carried out according to the following composition to synthesize a graft polymer. Synthesis of graft polymer (G-1) Enlarged rubber (solid content) 60 parts Styrene 21ã Methyl methacrylate 19ã Cumene hydroperoxide 0.16ã Sodium formaldehyde sulfoxylate 0.1ã Potassium oleate 1.0ã Water 200ã (Polymerization conditions 70 â4 hours) 2 parts of butylated hydroxytoluene and 0.5 parts of dilaurylthiopropionate were added as antioxidants to the obtained polymer latex, which was coagulated with a 5% aqueous sulfuric acid solution, washed, and dried to obtain a white powder. . To 10 parts of this powdered resin (G-1) were added 100 parts of polyvinyl chloride (PVC) with a degree of polymerization of 700, 3.0 parts of dibutyl tin malate, 1.0 parts of butyl stearate, 0.3 parts of stearyl alcohol, and 0.2 parts of Hoechstwax OP. , mixed on a mixing roll at 165â, then
Pressure molded at 180â-150Kg/ cm2 for 15 minutes
When Charpy Impact was measured, the results shown in Table 1 were obtained. For comparison, a similar evaluation was conducted using a latex (B-2) obtained by polymerizing a mixture having the following composition in one step. n-Butyl acrylate 85 parts Methacrylic acid 15 Potassium oleate 2 Sodium dioctyl sulfosuccinate 1 Cumene hydroperoxide 0.4 Sodium formaldehyde sulfoxylate 0.3 Water 200
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瀺ããã[Table] As is clear from Table 1, by forming the enlargement agent into a two-layer structure, the particle size can be enlarged more efficiently, and the stability of the obtained enlarged latex can also be improved. Furthermore, it can be seen that when the graft polymer is blended with PVC, the development of impact strength becomes better. Example 2 1 as acid group-containing copolymer latex for enlargement
A latex (B-3) in which the first stage consisted of 20 parts of butyl acrylate and 5 parts of methyl methacrylate and the second stage consisted of 60 parts of butyl acrylate and 15 parts of methacrylic acid was prepared in the same manner as (B-1) in Example 1. Synthesized with. Table 2 shows the impact strength of various synthetic rubbers which were enlarged using this compound and the monomers shown in Table 2 were graft-polymerized in the presence of 20 parts of these enlarged rubbers.
Claims (1)
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æ¹æ³ã1 (a) 100 to 50% by weight of 1,3-butadiene and a monomer having a CH 2 =C< group that can be copolymerized therewith from 0 to
Rubber (A) latex with a pH of 7 or higher consisting of 50% by weight
3 to 30% by weight of at least one unsaturated acid selected from the group of (b) acrylic acid, methacrylic acid, itaconic acid, and crotonic acid, based on 100 parts by weight (as solid content), Of the monomer (b) consisting of 97 to 35% by weight of at least one kind of alkyl acrylate of 1 to 12 and 0 to 48% by weight of other copolymerizable monomers, first, 5 to 90% by weight of the monomer (b) is An acid group-containing copolymer (B) obtained by polymerizing the portion not containing the unsaturated acid and then polymerizing the remaining 95 to 10% by weight of the monomer (b) containing the unsaturated acid. 7 to 70 parts by weight (as solid content) of enlarged rubber latex with a particle size of at least 0.2 Ό obtained by adding 0.1 to 5 parts by weight (as solid content) of latex
(iii) copolymerizable with at least 30% by weight of at least one monomer selected from the group of styrene acrylonitrile and methyl methacrylate;
A method for producing a thermoplastic resin having excellent impact resistance, comprising polymerizing 93 to 30 parts by weight of a monomer mixture comprising 30% by weight or less of a monomer having a CH 2 =C< group.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16237681A JPS5863713A (en) | 1981-10-12 | 1981-10-12 | Thermoplastic resin having excellent impact strength |
CA000412311A CA1193036A (en) | 1981-10-09 | 1982-09-27 | Process for producing impact resistant graft resins including an agglomerated rubber |
DE8282109304T DE3276755D1 (en) | 1981-10-09 | 1982-10-07 | Process for producing impact resistant resins |
EP82109304A EP0077038B2 (en) | 1981-10-09 | 1982-10-07 | Process for producing impact resistant resins |
US06/433,507 US4487890A (en) | 1981-10-09 | 1982-10-08 | Process for producing impact resistant resins |
KR8204554A KR860000302B1 (en) | 1981-10-09 | 1982-10-08 | Process for producing impact resistant resins |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16237681A JPS5863713A (en) | 1981-10-12 | 1981-10-12 | Thermoplastic resin having excellent impact strength |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5863713A JPS5863713A (en) | 1983-04-15 |
JPS6326763B2 true JPS6326763B2 (en) | 1988-05-31 |
Family
ID=15753392
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16237681A Granted JPS5863713A (en) | 1981-10-09 | 1981-10-12 | Thermoplastic resin having excellent impact strength |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5863713A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0870799A4 (en) * | 1995-12-13 | 2000-05-24 | Kanegafuchi Chemical Ind | Rubber latex, graft copolymer, and thermoplastic resin composition |
-
1981
- 1981-10-12 JP JP16237681A patent/JPS5863713A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5863713A (en) | 1983-04-15 |
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