JPH0423656B2 - - Google Patents
Info
- Publication number
- JPH0423656B2 JPH0423656B2 JP6306784A JP6306784A JPH0423656B2 JP H0423656 B2 JPH0423656 B2 JP H0423656B2 JP 6306784 A JP6306784 A JP 6306784A JP 6306784 A JP6306784 A JP 6306784A JP H0423656 B2 JPH0423656 B2 JP H0423656B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- plasticizer
- phthalate
- expandable thermoplastic
- copolymer particles
- 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
- 239000002245 particle Substances 0.000 claims description 36
- 239000004014 plasticizer Substances 0.000 claims description 18
- 229920001169 thermoplastic Polymers 0.000 claims description 17
- 239000004416 thermosoftening plastic Substances 0.000 claims description 15
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims description 10
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical group CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- -1 acrylic ester Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 claims description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical group FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000006260 foam Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000005187 foaming Methods 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FEXXLIKDYGCVGJ-UHFFFAOYSA-N butyl 8-(3-octyloxiran-2-yl)octanoate Chemical compound CCCCCCCCC1OC1CCCCCCCC(=O)OCCCC FEXXLIKDYGCVGJ-UHFFFAOYSA-N 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920006248 expandable polystyrene Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 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
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- GOAHRBQLKIZLKG-UHFFFAOYSA-N 1-tert-butylperoxybutane Chemical compound CCCCOOC(C)(C)C GOAHRBQLKIZLKG-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- YVRDAWCTPKBUPY-UHFFFAOYSA-N 5,5-bis(2-tert-butylperoxypropan-2-yl)cyclohexa-1,3-diene Chemical compound CC(C)(C)OOC(C)(C)C1(C(C)(C)OOC(C)(C)C)CC=CC=C1 YVRDAWCTPKBUPY-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- HAISMSJTPGJFIP-UHFFFAOYSA-N butyl 4-tert-butyl-4,5,5-trimethylhexaneperoxoate Chemical compound CCCCOOC(=O)CCC(C)(C(C)(C)C)C(C)(C)C HAISMSJTPGJFIP-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZICLWBMRDQUIDO-UHFFFAOYSA-N monoisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(O)=O ZICLWBMRDQUIDO-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Description
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The present invention relates to expandable thermoplastic copolymer particles that have excellent heat resistance and solvent resistance, as well as good foamability and moldability. As expandable polymer particles, expandable polystyrene resin particles are well known, and by using these particles, a molded foamed article can be easily obtained at low cost. However, since the monomer constituting the polymer is styrene, this foam molded product has poor heat resistance for use in relatively high-temperature pipe insulation materials, roof insulation materials, automobile parts, solar system insulation materials, etc. There are drawbacks that prevent it from being used for the required purpose. Furthermore, when used in combination with other materials, especially in automobile parts, etc., it also has the disadvantage that it is difficult to select an adhesive because of its poor solvent resistance. The present inventors have determined that in order to obtain expandable thermoplastic polymer particles having sufficient heat resistance and solvent resistance for practical use, the monomer composition constituting the polymer should be 10% or more of alpha methylstyrene. and obtain copolymer particles containing 5% or more of acrylonitrile,
It was thought that it was necessary to incorporate an easily volatile foaming agent into the resin particles. However, after pre-foaming such expandable thermoplastic copolymer particles, molding is performed to obtain a foamed molded product, and if the foamed molded product is left under high temperature, the dimensional change of the foamed molded product will not change. Although there are almost no visible irregularities on the surface of the molded product due to the expansion of the foamed particles forming the surface layer of the molded product (hereinafter referred to as tertiary foaming)
It has become clear that this problem is occurring and the aesthetic appearance is severely damaged. As a result of extensive research in view of these drawbacks, the present inventors have found that by applying a specific plasticizer to the surface of expandable thermoplastic copolymer particles using the above method, tertiary foaming can be achieved even under high temperature conditions. The present inventors have discovered that it is possible to obtain expandable thermoplastic copolymer particles that give a foamed molded article with excellent heat resistance and almost no dimensional change, and have completed the present invention. That is, in the present invention, the monomers constituting the polymer include 10 to 80% by weight of alphamethylstyrene, 5 to 50% by weight of acrylonitrile, and further styrene, chlorostyrene, paramethylstyrene, t-butylstyrene, acrylic ester, and methacrylate. Contains 0 to 70% by weight of at least one compound selected from acid esters, 2 to 15% by weight of an easily volatile blowing agent, and the surface is coated with a plasticizer that is liquid at room temperature with a solubility parameter value of 8.0 to 9.5. The material contains expandable thermoplastic copolymer particles. The amount of alphamethylstyrene used in the present invention is in the range of 10 to 80% by weight, and is determined depending on the desired heat resistance and expansion ratio, but if it is less than 10% by weight, the effect of improving heat resistance is not observed. Gone, 80 again
It is very difficult to produce a copolymer containing alpha methyl styrene in an amount exceeding % by weight at a high polymerization conversion rate. In order to obtain heat resistance of 100â with a 50x foam molded product,
It is necessary to use 20 to 50% by weight of alpha methylstyrene, and in order to obtain heat resistance of 110°C with a 5 to 15 times foamed product, it is necessary to use 50 to 80% by weight of alpha methylstyrene. Furthermore, the acrylonitrile used in the present invention is
It is necessary to make the foam exhibit oil resistance, and conventionally, alpha methylstyrene is used in large quantities.
Although it has been difficult to obtain a high polymerization conversion rate in suspension polymerization, it has been made possible by the combined use of acrylonitrile. If the amount of acrylonitrile used is less than 5% by weight, the polymerization conversion rate of the composition will be low and the oil resistance will not be effective, which is not preferable. Also 50% by weight
Even if it is used in excess of this amount, the polymerization conversion rate will not change and the resin will be colored yellowish brown, which is not preferable. Monomers other than alphamethylstyrene and acrylonitrile include styrene, various substituted styrenes such as chlorostyrene, paramethylstyrene, and t-butylstyrene, acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, methyl methacrylate, and ethyl styrene. One or more types of methacrylic acid esters such as methacrylate and butyl methacrylate can be used as appropriate. Easily volatile blowing agents used in the present invention include:
Aliphatic hydrocarbons such as propane, butane, pentane; cycloaliphatic hydrocarbons such as cyclobutane, cyclopentane, cyclohexane; trichlorofluoromethane, dichlorofluoromethane, dichlorodifluoromethane, methyl chloride, Examples include halogenated hydrocarbons such as chlortetrafluoromethane and ethyl chloride. The amount of these blowing agents to be used varies depending on the desired expansion ratio of the foamed molded product, but by containing 2 to 15% by weight, a foamed molded product that is 2 times to 100 times larger can be obtained. is possible. The present invention is characterized in that, in addition to the above composition, the particle surface is coated with a plasticizer that is liquid at room temperature and has a solubility parameter value of 8.0 to 9.5. Conventional techniques for modifying the surface of expandable thermoplastic resin particles by coating them with a coating agent include coating expandable polystyrene resin particles with various lubricants to improve the surface properties during pre-foaming of the particles. Technologies such as preventing blocking, improving fusion properties during molding, and shortening molding cooling time are known, but the various lubricants used in these technologies can be replaced with the copolymer of the present invention. Even when used in a combined composition, it does not have any significant effect on the molding process and the resulting foam. This is because the copolymer in the present invention has oil resistance due to the monomer used. However, if conventionally expandable styrene resin particles were coated with a plasticizer that is liquid at room temperature, cracks would occur on the particle surface and the foaming agent in the particles would quickly dissipate, causing problems in use. It was hot. However, in the present invention, when the above composition is coated with a plasticizer that is liquid at room temperature and has a solubility parameter value of 8.0 to 9.5, cracks occur on the particle surface and the blowing agent in the particles quickly evaporates. There were no such problems, and a remarkable effect was obtained in suppressing tertiary foaming of the foam molded product obtained using the particles. Plasticizer solubility parameter value less than 8.0 and 9.5
The effect of suppressing tertiary foaming becomes smaller when the temperature exceeds 100. Plasticizers used in the present invention for this purpose include phthalate esters such as dibutyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, and butylbenzyl phthalate; Various plasticizers include aliphatic dibasic acid esters such as 2-ethylhexyl, dioctyl azelaate, and dibutyl sebacate; aliphatic esters such as butyl stearate and butyl oleate; in particular, di-2-phthalate; -Ethylhexyl, isodecyl phthalate, butylbenzyl phthalate, di-2 adipate
- Ethylhexyne, dibutyl sebacate are preferred. The amount of these plasticizers used varies depending on the type of plasticizer used, but is preferably 0.01 to 1.0% by weight based on the expandable thermoplastic copolymer particles. If it is less than 0.01% by weight, the effect of suppressing tertiary foaming will be small;
If it is used in excess of 1% by weight, the moldability will deteriorate when the particles are pre-foamed and then molded, and the condition range for obtaining a molded product having the shape of the mold and a smooth surface will be extremely narrow. , or disappear altogether, which is not desirable. As a method for obtaining the expandable thermoplastic copolymer particles of the present invention, a copolymer of the above composition is obtained by an emulsion polymerization method, and then pelletized and impregnated with an easily volatile blowing agent in an autoclave. A method of coating expandable thermoplastic polymer particles with a plasticizer. A copolymer of the above composition is obtained by a copolymerization method, and then pelletized and impregnated with an easily volatile blowing agent in an autoclave. A method of coating expandable thermoplastic copolymer particles with a plasticizer, in which copolymer particles of the above composition are obtained by suspension polymerization, and then impregnated with an easily volatile blowing agent. Examples include a method of coating the combined particles with a plasticizer. However, in the emulsion polymerization method, there is an increase in cost due to the complexity of the process and a decrease in quality due to the contamination of emulsifiers and coagulants. It is inferior to the suspension polymerization method in terms of the complexity of the process, which requires subsequent impregnation with a blowing agent. Conventionally, it has been extremely difficult to obtain a copolymer with a high molecular weight that can be put to practical use by using a large amount of alphamethylstyrene as described above and carrying out suspension polymerization or polymerization. In the present invention, what makes it possible to polymerize an alphamethylstyrene-acrylonitrile copolymer with a high molecular weight that can be put to practical use through suspension polymerization and polymerization is the use of a specific initiator. The choice is the use and polymerization temperature conditions.
Initiators to be used from this point of view include:
A difunctional organic peroxide that generates t-butoxy radicals is used, and those having a 10-hour half-life temperature of 60 to 120°C are particularly suitable. Initiators that meet these conditions and can be used in practice include di-t-butylperoxyhexahydroterephthalate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, and di-t-butylperoxyhexahydroterephthalate. -butyl peroxyazelate, 2,
5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,1-di-t-butylperoxycyclohexane, 1,3-bis(t-butylperoxyisopropyl)benzene, 2,2-di(t-butylperoxyisopropyl)benzene Examples include (t-butylperoxy)butane, 4,4-di-t-butylperoxyvaleric acid n-butyl ester, di-t-butylperoxytrimethyl adipate, and the like. The amount of these initiators used is 0.1 to 2.0% by weight based on the total amount of monomers. 0.1
If the amount is less than % by weight, an industrially practical polymerization conversion rate may not be obtained at all, or it may take a long time, resulting in extremely poor productivity. If it is used in an amount exceeding 2.0% by weight, the molecular weight will drop significantly and satisfactory foam molding will not be possible, or even if foam molding can be carried out, only a foam molded product with significantly inferior strength will be obtained. In addition, the polymerization temperature when using these initiators is
The temperature is preferably 80 to 130°C. If the temperature is less than 80°C, the polymerization conversion rate will be extremely low, and if it exceeds 130°C, the molecular weight will decrease, making it difficult to obtain a satisfactory foam molded product. The thus obtained expandable thermoplastic copolymer particles of the present invention are heated by a heating medium such as water vapor or hot air.
After pre-foaming to a desired magnification, it is filled into a mold that can be closed but cannot be sealed, and heated again with a heating medium such as steam to form a heat-resistant foam having a desired shape. obtain. The present invention will be explained below with reference to Examples. Example 1 110 parts by weight of pure water in an autoclave equipped with a stirrer,
After adding 0.08 parts by weight of tricalcium phosphate and 0.003 parts by weight of sodium dodecylbenzenesulfonate, 30 parts by weight of alphamethylstyrene was added under stirring.
Monomers consisting of 20 parts by weight of acrylonitrile, 50 parts by weight of styrene, 1.0 parts by weight of toluene, and
Butyl peroxyhexahydroterephthalate
Mix 0.5 parts by weight and add into the autoclave.
After the temperature was raised to 95°C, 0.3 parts by weight of tribasic calcium phosphate was added 3 hours later, and polymerization was continued for an additional 5 hours. The polymerization conversion rate of the obtained composition was 99.4%. Next, 10 parts by weight of butane was added, and impregnation with a blowing agent was carried out at 100° C. for 8 hours. The obtained expandable thermoplastic copolymer particles were used as resin (A), and the following experiments were conducted using this resin (A). Example 2 0.1 part by weight of di-2-ethylhexyl phthalate (SP value: 8.9) and 0.1 part by weight of calcium stearate powder as an antiblocking agent were added to the resin (A) obtained in Example 1 in a blender equipped with a stirrer. coated. Next, the resin is heated with steam to preliminarily lighten to an apparent magnification of 50 times, then filled into a mold that can be closed but cannot be sealed, and heated with steam to form a plate-shaped foam of 45 cm x 30 cm x 2 cm. A molded body was obtained. The above foamed molded product was left in a hot air soaking dryer at 100° C. for one week, and then the state of tertiary foaming on the surface of the molded product was examined, and the results are shown in Table 1. Examples 3 to 5 Examples were carried out in the same manner as in Example 2, except that di-2-ethylhexyl phthalate was changed to dibutyl phthalate, butylbenzyl phthalate, or di-2-ethylhexyl adipate. The results are shown in Table-1. Comparative Examples 1 to 4 In Example 2, a blank without di-2-ethylhexyl phthalate (Comparative Example 1), a paraffinic oil (Comparative Example 2), butyl epoxy stearate ( Comparative Example 3) and diethylene glycol dibenzoate (Comparative Example 4) were used, but the results were shown in Table 1.
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Î: Considerably present Examples 6 and 7 Table 2 shows the results of carrying out the same procedure as in Example 2 except that the amount of di-2-ethylhexyl phthalate was changed to 0.05 parts by weight and 0.5 parts by weight.
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ããçµæãè¡šâïŒã«ç€ºããã[Table] Example 8 110 parts by weight of pure water in an autoclave equipped with a stirrer,
After adding 0.08 parts by weight of tricalcium phosphate and 0.003 parts by weight of sodium dodecylbenzenesulfonate, 70 parts by weight of alphamethylstyrene was added under stirring.
A monomer consisting of 30 parts by weight of acrylonitrile,
1,1-di-t-butylperoxy-3,3,5
- Mixing 1.0 part of trimethylcyclohexane,
After adding it to the autoclave and raising the temperature to 100â,
After 3 hours, 0.3 parts by weight of tribasic calcium phosphate was added, and polymerization was continued for an additional 5 hours. The polymerization conversion rate of the obtained composition was 99.3%. Then 4 parts of butane was added and impregnated with a blowing agent for 15 hours at 100°C. The obtained expandable thermoplastic copolymer particles were used as resin (B), and the following experiments were conducted using this resin (B). Example 9 Di-2-ethylhexyl phthalate was added to the resin (B) obtained in Example 8 in a blender equipped with a stirrer.
0.1 part by weight and 0.1 part by weight of calcium stearate powder as an antiblocking agent. Next, the resin is heated with steam to pre-foam to an apparent magnification of 5 times, and then filled into a mold that can be closed but cannot be sealed, and heated with steam to form a mold of 45 cm x 30 cm.
A plate-shaped foamed molded product with a size of 0.7 cm was obtained. After this plate-shaped foam molded product was left in a hot air soaking dryer at 110° C. for 24 hours, the state of tertiary foaming on the surface of the molded product was examined, and the results are shown in Table 3. Examples 10 to 12 The same procedure as in Example 9 was carried out except that dibutyl phthalate was changed to butyl benzyl phthalate and dioctyl adipate instead of di-2-ethylhexyl phthalate. The results are shown in Table-3. Comparative Example 5 The same procedure as Example 9 was carried out except that di-2-ethylhexyl phthalate was not used.
The results are shown in Table-3. Comparative Examples 6 to 8 The same procedure as Example 9 was carried out except that paraffin oil, butyl epoxy stearate, and diethylene glycol dibenzoate were used in place of di-2-ethylhexyl phthalate. The results are shown in Table-3.
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Claims (1)
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ç¯å²ç¬¬ïŒé èšèŒã®çºæ³¡æ§ç±å¯å¡æ§å ±éåäœç²åã ïŒ å¯å¡å€ãèèªæäºå¡©åºé žãšã¹ãã«ã§ããç¹èš±
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çºæ³¡æ§ç±å¯å¡æ§å ±éåäœç²åã[Scope of Claims] 1 The monomers constituting the polymer are 10 to 80% by weight of alphamethylstyrene and 5 to 50% by weight of acrylonitrile.
% by weight, and 0 to 70% by weight of at least one compound selected from styrene, chlorostyrene, paramethylstyrene, t-butylstyrene, acrylic ester, and methacrylic ester, and 2 to 15% by weight of an easily volatile blowing agent. % by weight, the surface of which is coated with a plasticizer that is liquid at room temperature and has a solubility parameter value of 8.0 to 9.5. 2. The expandable thermoplastic copolymer particles according to claim 1, wherein the plasticizer is a phthalate ester. 3. The expandable thermoplastic copolymer particles according to claim 1, wherein the plasticizer is an aliphatic dibasic acid ester. 4 The plasticizer is di-2-ethylhexyl phthalate,
The expandable thermoplastic copolymer particles according to claim 1, which are diisodecyl phthalate or butylbenzyl phthalate. 5. The expandable thermoplastic copolymer particles according to claim 1, wherein the plasticizer is dioctyl adipate or dibutyl sebacate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6306784A JPS60206850A (en) | 1984-03-29 | 1984-03-29 | Expandable thermoplastic copolymer particle |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6306784A JPS60206850A (en) | 1984-03-29 | 1984-03-29 | Expandable thermoplastic copolymer particle |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60206850A JPS60206850A (en) | 1985-10-18 |
JPH0423656B2 true JPH0423656B2 (en) | 1992-04-22 |
Family
ID=13218621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6306784A Granted JPS60206850A (en) | 1984-03-29 | 1984-03-29 | Expandable thermoplastic copolymer particle |
Country Status (1)
Country | Link |
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JP (1) | JPS60206850A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2565225B1 (en) | 2011-08-31 | 2014-04-16 | Basf Se | Coated expandable polymer particle |
DE102012217659A1 (en) | 2012-09-27 | 2014-03-27 | Basf Se | Expandable polymer particle useful for producing foam molded part or block of foam which is useful in e.g. furniture, construction and stand construction automotive industry, comprises polymerized styrene and/or alpha-methyl styrene |
-
1984
- 1984-03-29 JP JP6306784A patent/JPS60206850A/en active Granted
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JPS60206850A (en) | 1985-10-18 |
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