CN116003664A - Non-crosslinked vinyl chloride resin particles and method for producing same - Google Patents
Non-crosslinked vinyl chloride resin particles and method for producing same Download PDFInfo
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- CN116003664A CN116003664A CN202211585648.0A CN202211585648A CN116003664A CN 116003664 A CN116003664 A CN 116003664A CN 202211585648 A CN202211585648 A CN 202211585648A CN 116003664 A CN116003664 A CN 116003664A
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- vinyl chloride
- resin particles
- based resin
- monomer
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- 239000002245 particle Substances 0.000 title claims abstract description 85
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- 239000011347 resin Substances 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 16
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims abstract description 13
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000012673 precipitation polymerization Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 49
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 21
- 239000012046 mixed solvent Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- 239000003999 initiator Substances 0.000 claims description 16
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009826 distribution Methods 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 10
- 229940050176 methyl chloride Drugs 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 229940057404 di-(4-tert-butylcyclohexyl)peroxydicarbonate Drugs 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 229920001567 vinyl ester resin Polymers 0.000 claims description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 claims description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 claims description 2
- RAWISQFSQWIXCW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethyloctaneperoxoate Chemical compound CCCCCCC(C)(C)C(=O)OOC(C)(C)CC RAWISQFSQWIXCW-UHFFFAOYSA-N 0.000 claims description 2
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 claims description 2
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OSBFYPMBKGWPHH-UHFFFAOYSA-N C(=O)(OCCCCCCCCCCCCCCCC)OC(=O)OCCCCCCCCCCCCCCCC Chemical compound C(=O)(OCCCCCCCCCCCCCCCC)OC(=O)OCCCCCCCCCCCCCCCC OSBFYPMBKGWPHH-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 claims description 2
- ZGPBOPXFOJBLIV-UHFFFAOYSA-N butoxycarbonyloxy butyl carbonate Chemical compound CCCCOC(=O)OOC(=O)OCCCC ZGPBOPXFOJBLIV-UHFFFAOYSA-N 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940038384 octadecane Drugs 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 claims description 2
- VNJISVYSDHJQFR-UHFFFAOYSA-N tert-butyl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C VNJISVYSDHJQFR-UHFFFAOYSA-N 0.000 claims description 2
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 2
- CSKKAINPUYTTRW-UHFFFAOYSA-N tetradecoxycarbonyloxy tetradecyl carbonate Chemical compound CCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCC CSKKAINPUYTTRW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 13
- 239000004800 polyvinyl chloride Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 7
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YAOJJEJGPZRYJF-UHFFFAOYSA-N 1-ethenoxyhexane Chemical compound CCCCCCOC=C YAOJJEJGPZRYJF-UHFFFAOYSA-N 0.000 description 2
- IOSXLUZXMXORMX-UHFFFAOYSA-N 1-ethenoxypentane Chemical compound CCCCCOC=C IOSXLUZXMXORMX-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- QJNYIFMVIUOUSU-UHFFFAOYSA-N chloroethene;ethenyl acetate;furan-2,5-dione Chemical compound ClC=C.CC(=O)OC=C.O=C1OC(=O)C=C1 QJNYIFMVIUOUSU-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to a non-crosslinked vinyl chloride resin particle and a method for producing the same. The non-crosslinked vinyl chloride-based resin particles of the present invention comprise a vinyl chloride-based unit and at least one unit selected from the group consisting of a maleic anhydride-based unit, an itaconic anhydride-based unit and a citraconic anhydride-based unit, and have a number average molecular weight of 1000 to 20000 and an average particle diameter of less than 1000 nm; the vinyl chloride resin particles are prepared by a free radical precipitation polymerization method, wherein a dispersing aid and a chain transfer agent are not added in the free radical precipitation polymerization process.
Description
Technical Field
The present invention relates to non-crosslinked vinyl chloride resin particles and a method for producing the same.
Background
The low molecular weight polyvinyl chloride copolymer resin, especially the polyvinyl chloride copolymer resin containing the modifiable functional groups (such as carboxyl, hydroxyl, amino and anhydride groups), has the characteristics of low molecular weight polyvinyl chloride resin such as high apparent density, low melting and gelation temperature, good transparency, shorter plasticizing time, good processability and the like, provides further modified and reacted sites, and has wide application in the aspects of paint, printing ink, adhesive and addition auxiliary agents of general resins. In particular, the above resin having a nano-scale has a wide application range in specific technical fields such as electricity, medicine, and optics, in addition to the above fields.
At present, as for the method for obtaining the vinyl chloride resin in the particle form, suspension polymerization and emulsion polymerization in the industrial production mode of polyvinyl chloride are directly utilized to hardly obtain the polyvinyl chloride resin with low molecular weight, and even if a high-temperature polymerization method and a process of adding a chain transfer agent are adopted, the molecular weight of the obtained resin still cannot be very low, and the low molecular weight level (Mn less than or equal to 20000) is hardly reached. In addition, since the dispersing agent/emulsifying agent is used in the above polymerization methods, it is difficult to obtain a pure polyvinyl chloride resin, and the residual dispersing agent/emulsifying agent may affect the usability of the product.
In the field of vinyl chloride copolymer resin synthesis containing modified functional groups, the copolymerization modification of polyvinyl chloride by using various monomers containing anhydride groups is an important technical means for widening the application of polyvinyl chloride resin. However, when conventional suspension or emulsion polymerization is employed, the copolymerization of various monomers containing an acid anhydride group with vinyl chloride is difficult, and the difficulty is that various monomers containing an acid anhydride group are easily hydrolyzed into an acid in an aqueous solution, resulting in a product having a damaged structural content derived from an acid anhydride. In addition, in the polymerization method involving water (in the case where water is contained in the dispersion medium), acid generated by hydrolysis of acid anhydride in water sometimes plays a role in inhibiting polymerization, and the production efficiency is lowered. In particular, these acids are generally more acidic, which results in the stability of the emulsion being greatly negatively affected in emulsion polymerizations (the usual initiators persulfates and emulsifiers are suitable for use in neutral or basic applications). Non-patent document 1 discloses a report of synthesizing a vinyl chloride-maleic anhydride-vinyl acetate terpolymer by emulsion polymerization, in which the adhesive force of the copolymer resin is remarkably improved as the maleic anhydride content increases. However, the molecular weight of the copolymer obtained is high (Mn > 35000) and the maleic anhydride content in the copolymer is very low (4% by weight of the charge, 0.8% by weight in the actual copolymer).
The inventors developed a method for preparing ultra-low molecular weight polyvinyl chloride nanoparticles in previous studies by performing free radical precipitation polymerization of vinyl chloride in an alkane, a mixed solvent of alkane and alkyl ester of organic acid, and a mixed solvent of alkane and ketone, which does not contain any dispersant and stabilizer, to obtain pure polyvinyl chloride nanoparticles (patent document 1). But this only illustrates that this polymerization process is possible for polyvinyl chloride homopolymers. According to the studies of the inventors, the polymerization process is highly selective for the monomers to be used and the polymers to be produced, and the polymerization behavior is fraught with uncertainty in the case of using different units (particularly, large differences in physicochemical properties of monomers, aggregation state).
The object of the invention is therefore: the method for preparing the low-molecular-weight non-crosslinked vinyl chloride resin particles with the modifiable functional groups and the average particle size of less than 1000nm is provided by utilizing free radical precipitation polymerization, so as to overcome the limitations of the existing polymerization method and polymerization technology in preparing the low-molecular-weight vinyl chloride copolymer resin particles.
Patent literature
Patent document 1: CN107602745B
Non-patent literature
Non-patent document 1: xiang Hongwen emulsion copolymerization of vinyl chloride-vinyl acetate-maleic anhydride and copolymer Structure/Property study, in 2014, shuoshi treatise.
Disclosure of Invention
Technical problems to be solved by the invention：
Aiming at the problems that the existing suspending, micro-suspending and emulsion polymerization technology has complex post-treatment process of PVC products and is difficult to obtain vinyl chloride resin particles with low molecular weight, and the prior art only obtains polyvinyl chloride resin particles which are difficult to modify and have limited application fields, the invention aims to provide the non-crosslinked vinyl chloride resin particles with low number average molecular weight and average particle diameter of less than 1000nm, which are obtained by utilizing the pure preparation method of the products, and the preparation method thereof.
The technical scheme for realizing the invention is as follows:
to solve the problems of the prior art, the present inventors found that: the desired vinyl chloride-based resin particles of the present invention can be prepared by conducting precipitation polymerization by selecting an appropriate polymerization medium. In the whole process of the precipitation polymerization formed by the method, all monomers and polymerization aids such as an initiator and the like can be dissolved in a solvent at first, and the reaction system is a clear and transparent homogeneous solution; the initiator is decomposed to generate free radicals and initiate the polymerization of monomers when heated in the solution; because the solubility parameter of the obtained vinyl chloride resin in the solvent is greatly different from the solubility parameter of each monomer and the solubility parameter of the solvent, the polymer molecular chain can not be dissolved in the monomer or the solvent medium, and the polymer molecular chain can be precipitated, aggregated and nucleated from the reaction system to form nano particles; when the particle size and concentration reach a certain value, the system becomes turbid and becomes a heterogeneous polymerization system. Since each monomer cannot be absorbed by the particles to be swelled, each monomer can only be polymerized in solution in the subsequent polymerization process, and the generated molecular chain is partially deposited on the surface of the original particles to enable the original particles to grow, and part of the molecular chain is self-nucleated to form new particles; since these particles are linked without a macromolecular surfactant and the monomers cannot be swelled to polymerize within the particles, the polymer particles formed by the final polymerization will be very small (less than 1 μm, generally, there is no limitation on the lower limit of the particle size, but preferably 20nm to 900nm, more preferably 100nm to 800 nm). Because of the small particle size and large surface area, the particles can exist stably in a polymerization medium under static and dynamic (such as stirring) conditions, cannot be deposited on the bottom of a reactor to form a block, cannot be adhered to the wall of the reactor, and therefore, belongs to self-stable precipitation polymerization. The polymer precipitation depends mainly on two factors, critical concentration and critical molecular weight. The polymerization will proceed such that the concentration and molecular weight of the resulting polymer in the solvent will increase simultaneously. Therefore, once the polymerization degree of the molecular chain free radical of the polymer exceeds a critical value during polymerization, the molecular chain free radical can be precipitated from the solution to become solid particles or be deposited on the surfaces of the solid particles; the monomers are still in solution, which severely inhibits or stops chain radical growth. The vinyl chloride-based resin obtained by such heterogeneous polymerization can have a very low molecular weight and can cause the vinyl chloride-based resin particles to be copolymerized with a structural unit having a modifiable functional group (acid anhydride group) (further, the structural unit can be copolymerized into the vinyl chloride-based resin particles with high efficiency, which is also very preferable because vinyl chloride is a gaseous monomer).
Therefore, the invention adopts the following technical scheme:
non-crosslinked vinyl chloride resin particles: the vinyl chloride-based resin particles contain a vinyl chloride-based unit and at least one unit selected from the group consisting of a maleic anhydride-based unit, an itaconic anhydride-based unit and a citraconic anhydride-based unit, and have a number average molecular weight of 1000 to 20000 (preferably, 1500 to 18000, more preferably, 2000 to 15000) and an average particle diameter of less than 1000nm (preferably, 20 to 900nm, more preferably, 50 to 880 nm, still more preferably, 100 to 800 nm); the vinyl chloride resin particles are prepared by a free radical precipitation polymerization method, wherein a dispersing aid and a chain transfer agent are not added in the free radical precipitation polymerization process.
Preferably, the vinyl chloride-based resin particles have a molecular weight distribution of 1.05 to 2.40 (more preferably, 1.20 to 2.20, still more preferably, 1.50 to 2.00), and a particle size distribution of 1.00 to 1.50 (more preferably, 1.02 to 1.45, still more preferably, 1.05 to 1.40).
In the present invention, the microscopic morphology (average particle diameter and particle diameter distribution, specifically, 100 particles arbitrarily selected in the visual field are measured to obtain particle diameter distribution, and the average of the particle diameters is taken as average particle diameter) of the produced vinyl chloride resin is observed by a scanning electron microscope, and the number average molecular weight and molecular weight distribution of the produced vinyl chloride resin are measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard.
Preferably, the proportion of the units based on vinyl chloride is 20 to 95mol% (more preferably, 30 to 95mol%, still more preferably, 40 to 90mol%, particularly preferably, 45 to 90 mol%) and the proportion of at least one unit selected from the group consisting of the units based on maleic anhydride, the units based on itaconic anhydride and the units based on citraconic anhydride is 5 to 80mol% (more preferably, 5 to 70mol%, still more preferably, 6 to 60mol%, particularly preferably, 10 to 50 mol%) with respect to the entire units of the vinyl chloride-based resin particles. When at least one unit selected from the group consisting of a unit based on maleic anhydride, a unit based on itaconic anhydride and a unit based on citraconic anhydride is only a unit based on maleic anhydride, the proportion of the unit based on maleic anhydride is not more than 50mol%.
Preferably, the vinyl chloride-based resin particles further comprise units based on other monomers (i.e., units other than the vinyl chloride-based unit and at least one unit selected from the group consisting of a maleic anhydride-based unit, an itaconic anhydride-based unit, and a citraconic anhydride-based unit), the other monomers being selected from monofunctional styrene-based monomers such as styrene, α -methylstyrene, o-methylstyrene, and the like; monofunctional (meth) acrylates such as C1-13 alkyl (meth) acrylate, C1-13 hydroxyalkyl (meth) acrylate, glycidyl (meth) acrylate; monofunctional vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, and the like; monofunctional vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, and the like.
In some embodiments, more preferably, the proportion of the units based on the other monomer in the vinyl chloride-based resin particles is smaller than the proportion of the units based on vinyl chloride in terms of mol.
In other specific embodiments, more preferably, the proportion of the units based on other monomers is 40mol% or less (further preferably 20mol% or less, particularly preferably 10mol% or less, most preferably 5mol% or less) with respect to the entire units of the vinyl chloride-based resin particles.
A method for producing vinyl chloride resin particles comprises: the method comprises the following steps: adding vinyl chloride, at least one monomer selected from maleic anhydride, itaconic anhydride and citraconic anhydride, a solvent, and a radical initiator to a polymerization reactor, and performing polymerization under dynamic (e.g., stirring, ultrasonic wave, shaking, etc. dynamic action conventional in the art) or static (i.e., without applying any dynamic action) conditions without using a dispersing aid and a chain transfer agent; the solvent is a poor solvent for the vinyl chloride resin particles.
Preferably, the temperature of the polymerization reaction is 30 to 60 ℃ (more preferably 35 to 55 ℃). Preferably, the polymerization time is 4 to 24 hours (more preferably, 5 to 20 hours).
Preferably, the concentration of all monomers including vinyl chloride and at least one monomer selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride in the polymerization reaction system is 10wt% to 40wt% (more preferably, 15wt% to 35 wt%). In the invention, as the reaction system is a precipitation polymerization system, which is a process that the generated polymer gradually precipitates from the precipitant, when the monomer concentration is too high, the pressure in the kettle is easily caused to be too high, the stacking density of particles in the system is increased, and two results are caused: firstly, the particle size distribution of the product is easy to be uneven, and secondly, the molecular weight distribution of the product is easy to be widened; when the monomer concentration is too low, because the chloroethylene is gas, a certain amount of monomer remains above the liquid level of the reaction kettle, and the chloroethylene is not easy to enter a precipitant phase due to low pressure in the kettle, so that the product conversion rate is lower.
Preferably, the proportion of vinyl chloride is 20 to 95mol% (more preferably, 30 to 95mol%, further preferably, 40 to 90mol%, particularly preferably, 45 to 90 mol%) and the proportion of at least one monomer selected from maleic anhydride, itaconic anhydride and citraconic anhydride is 5 to 80mol% (more preferably, 5 to 70mol%, further preferably, 6 to 60mol%, particularly preferably, 10 to 50 mol%) with respect to the whole units.
Preferably, other monomers are also involved in the polymerization reaction, said other monomers being selected from monofunctional styrenic monomers such as styrene, alpha-methylstyrene, o-methylstyrene, etc.; monofunctional (meth) acrylates such as C1-13 alkyl (meth) acrylate, C1-13 hydroxyalkyl (meth) acrylate, glycidyl (meth) acrylate; monofunctional vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, and the like; monofunctional vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, and the like.
More preferably, the proportion of the other monomer is 40mol% or less (further preferably 20mol% or less, particularly preferably 10mol% or less, most preferably 5mol% or less) with respect to the whole unit.
The ratio of the other monomer to vinyl chloride in all the units is not limited, and may be set depending on the copolymerization ability of the system.
The selection principle of the solvent in the invention is as follows: (1) The solvent has good dissolving capacity to the monomer and the initiator, so that a homogeneous system is ensured before the reaction; (2) The selected solvent is insoluble in the vinyl chloride resin formed, and the polymer precipitates from the solvent when the molecular weight reaches a certain critical length; (3) The polymerization product does not deposit on the reactor walls and paddles and does not deposit on the bottom of the reactor in a lump, so that relatively stable particles can be formed in the polymerization medium.
In view of good operability of the polymerization system, it is preferable that the poor solvent is selected from alkyl esters of organic acids, or mixed solvents of alkanes and ketones, or mixed solvents of alkanes and alkyl esters of organic acids, or mixed solvents of alkanes and methyl chloride. For the mixed solvent, the ratio between the solvents can be appropriately adjusted depending on the requirements for the product and the kind of monomer used without limitation.
More preferably, the volume fraction of ketone in the mixed solution of alkane and ketone is 10% to 60% (further preferably, 12% to 58%, particularly preferably, 15% to 55%), the volume fraction of alkyl ester of organic acid in the mixed solution of alkane and alkyl ester of organic acid is 20% to 99% (further preferably, 35% to 90%, particularly preferably, 45% to 85%), and the volume fraction of methyl chloride in the mixed solution of alkane and methyl chloride is 5% to 40% (further preferably, 10% to 35%, particularly preferably, 15% to 30%).
Still more preferably, the alkane is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane, pentane, n-octane, undecane, dodecane, tridecane, tetradecane, pentadecane, and octadecane; the ketone is at least one selected from acetone, butanone and cyclohexanone; the organic acid alkyl ester is at least one selected from ethyl acetate, butyl acetate, dimethyl carbonate and isoamyl acetate; the methyl chloride is at least one selected from methyl chloride and chloroform.
Further, it is preferable that the poor solvent is selected from a mixed solvent of an alkane and a ketone, or a mixed solvent of an alkane and an alkyl ester of an organic acid, or a mixed solvent of an alkane and methyl chloride.
Preferably, the free radical initiator is an azo-type initiator or an organic peroxide-type initiator. Preferably, the initiator is used in the reaction system in an amount of 0.1 to 4wt% (more preferably, 0.5 to 3 wt%) based on the total monomer mass.
More preferably, the azo initiator is at least one selected from azodiisobutyronitrile and azodiisoheptonitrile; the organic peroxide initiator is at least one selected from tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, di (hexadecyl) dicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxypivalate, di- (4-tert-butylcyclohexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxy2-ethylhexanoate, ditetradecyl peroxydicarbonate, tert-butyl peroxyacetate, cumyl peroxyneodecanoate, di-tert-butyl peroxide, cyclohexyl sulfonyl acetyl peroxide, diisobutyryl peroxide, 1, 3-tetramethylbutyl peroxyneodecanoate, di-3-methoxybutyl peroxydicarbonate and 1, 3-tetramethylbutyl peroxypivalate.
The production method of the present invention may further include other steps conventional in the art, for example, a step of separating the obtained vinyl chloride resin particles from the polymerization system by centrifugation, ultrafiltration or the like, a step of washing the obtained vinyl chloride resin particles, a step of drying the obtained vinyl chloride resin particles, a step of recovering various monomers remaining in the reaction system after the completion of the reaction, and the like.
The beneficial effects of the invention are that：
The present invention provides a vinyl chloride resin particle having a non-crosslinked, low number average molecular weight and a modifiable functional group, and a method for producing the same. According to the present invention, a series of vinyl chloride resin particles having a modified functional group and having a non-crosslinked, low number average molecular weight, and a composition which can be adjusted in a wide range can be prepared according to the process conditions and the requirements of the product properties. In addition, the obtained vinyl chloride resin particles have the size with the average particle diameter of less than 1000nm (further, the uniformity of the size is high, for example, the particle size distribution can reach 1.00-1.50), the preparation method is simple and easy to implement, the conversion rate is high, the post-treatment is simple and convenient, the product is pure, and the possibility is provided for various application scenes in the later period.
Detailed Description
In order that the above-recited features and advantages of the present invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof. As can be appreciated, the scope of the present invention is not limited by the following examples.
Example 1
MAH 1.36g, bis- (4-tert-butylcyclohexyl) peroxydicarbonate 0.1g, a mixed solvent of 60g of n-hexane and ethyl acetate (v: v=3:7) were added into a 100ml reaction kettle, VCM 13.64g was added after vacuum pumping, and after reaction for 8 hours at 45 ℃, the sample was centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 2
5.15g of MAH, 0.1g of bis- (4-tert-butylcyclohexyl) peroxydicarbonate and 60g of a mixed solvent of n-hexane and ethyl acetate (v: v=3:7) are added into a 100ml reaction kettle, after vacuum pumping, 9.85g of VCM is added, after reaction for 8 hours at 45 ℃, the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 3
MAH 7.67g, bis- (4-t-butylcyclohexyl) peroxydicarbonate 0.1g, a mixed solvent of 60g of n-hexane and ethyl acetate (v: v=3:7) were added to a 100ml reaction vessel, VCM 7.33g was added after vacuum pumping, and after reaction at 45℃for 8 hours, the sample was centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 4
5.15g of MAH, 0.1g of bis- (4-tert-butylcyclohexyl) peroxydicarbonate and 60g of a mixed solvent of n-hexane and ethyl acetate (v: v=5:5) are added into a 100ml reaction kettle, after vacuum pumping, 9.85g of VCM is added, after reaction for 8 hours at 45 ℃, the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 5
5.15g of MAH, 0.1g of di- (4-tert-butylcyclohexyl) peroxydicarbonate and 60g of a mixed solvent of n-hexane and isoamyl acetate (v: v=3:7) are added to a 100ml reaction kettle, the mixture is vacuumized, 9.85g of VCM is added, the mixture is reacted at 45 ℃ for 8 hours, and after the reaction, the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 6
5.15g of MAH, 0.1g of di- (4-tert-butylcyclohexyl) peroxydicarbonate and 60g of a mixed solvent of n-hexane and dimethyl carbonate (v: v=3:7) are added into a 100ml reaction kettle, the mixture is vacuumized, 9.85g of VCM is added, the mixture is reacted for 8 hours at 45 ℃, and the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 7
5.15g of MAH, 0.1g of bis- (4-tert-butylcyclohexyl) peroxydicarbonate and 60g of n-hexane are added into a 100ml reaction kettle, and after vacuumizing, 9.85g of VCM is added, and after reacting for 8 hours at 45 ℃, the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
Example 8
5.15g of MAH, 0.1g of bis- (4-tert-butylcyclohexyl) peroxydicarbonate and 60g of ethyl acetate are added into a 100ml reaction kettle, and after vacuumizing, 9.85g of VCM is added, and after reacting for 8 hours at 45 ℃, the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
Comparative example 1
5.15g of MAH, 0.1g of bis- (4-tert-butylcyclohexyl) peroxydicarbonate, 0.15g of Span-60, 60g of a mixed solvent of n-hexane and ethyl acetate (v: v=3:7) are added into a 100ml reaction kettle, after vacuum pumping, 9.85g of VCM is added, after reaction for 8 hours at 45 ℃, the sample is centrifugally washed and dried in a vacuum oven at 30 ℃.
In the present invention, the vinyl chloride resin particles having a low molecular weight and modified functional groups as desired in the present invention can be easily obtained in each example. In example 7, since only n-hexane was used as an alkane, the morphology of the obtained particles was irregular. In example 8, the resulting particles exhibited partial dissolution and blocking phenomena due to the use of ethyl acetate alone, and dimensional uniformity was negatively affected.
Since the dispersant Span-60 was added to comparative example 1, the average particle diameter of the obtained resin particles could not meet the expectations of the present invention, and further, even after a large amount of washing, the obtained resin particles had the dispersant adsorbed thereon.
Claims (10)
1. A non-crosslinked vinyl chloride-based resin particle characterized in that: the vinyl chloride-based resin particles comprise a unit based on vinyl chloride and at least one unit selected from the group consisting of a unit based on maleic anhydride, a unit based on itaconic anhydride and a unit based on citraconic anhydride, and have a number average molecular weight of 1000 to 20000 and an average particle diameter of less than 1000 nm; the vinyl chloride resin particles are prepared by a free radical precipitation polymerization method, wherein a dispersing aid and a chain transfer agent are not added in the free radical precipitation polymerization process.
2. The vinyl chloride-based resin particles according to claim 1, wherein the vinyl chloride-based resin particles have a molecular weight distribution of 1.05 to 2.40, have an average particle diameter of 20 to 900nm, and have a particle diameter distribution of 1.00 to 1.50.
3. The vinyl chloride-based resin particle according to claim 1 or 2, wherein the proportion of units based on vinyl chloride is 20 to 95mol% and the proportion of at least one unit selected from the group consisting of units based on maleic anhydride, units based on itaconic anhydride and units based on citraconic anhydride is 5 to 80mol% with respect to the total units of the vinyl chloride-based resin particle.
4. The vinyl chloride-based resin particle according to any one of claims 1 to 3, wherein the vinyl chloride-based resin particle further comprises a unit based on another monomer, and the other monomer is at least one selected from the group consisting of a monofunctional styrene-based monomer, a monofunctional (meth) acrylate, a monofunctional vinyl ester-based monomer, and a monofunctional vinyl ether-based monomer.
5. A method for producing the vinyl chloride-based resin particles according to any one of claims 1 to 4, comprising: adding chloroethylene, at least one monomer selected from maleic anhydride, itaconic anhydride and citraconic anhydride, a solvent and a free radical initiator into a polymerization reactor, and carrying out polymerization under the condition of dynamic action or static action without using a dispersing auxiliary agent and a chain transfer agent; the solvent is a poor solvent for the vinyl chloride resin particles.
6. The method for producing vinyl chloride-based resin particles according to claim 5, wherein the polymerization reaction temperature is 30 to 60℃and the polymerization reaction time is 4 to 24 hours; the concentration of all monomers including vinyl chloride and at least one monomer selected from maleic anhydride, itaconic anhydride and citraconic anhydride in the polymerization reaction system is 10wt% to 40wt%.
7. The method for producing vinyl chloride-based resin particles according to claim 5 or 6, wherein the proportion of vinyl chloride is 20 to 95mol% relative to the total units, and the proportion of at least one monomer selected from the group consisting of maleic anhydride, itaconic anhydride and citraconic anhydride is 5 to 80mol%.
8. The method for producing vinyl chloride resin particles according to any one of claims 5 to 7, wherein the poor solvent is selected from the group consisting of an alkyl ester of an organic acid, a mixed solvent of an alkane and a ketone, a mixed solvent of an alkane and an alkyl ester of an organic acid, and a mixed solvent of an alkane and methyl chloride. Preferably, the volume fraction of ketone in the mixed solution of alkane and ketone is 10% -60%, the volume fraction of organic acid alkyl ester in the mixed solution of alkane and organic acid alkyl ester is 20% -99%, and the volume fraction of chloromethane in the mixed solution of alkane and chloromethane is 5% -40%.
9. The method for producing vinyl chloride-based resin particles according to claim 8, wherein the alkane is at least one selected from the group consisting of n-hexane, n-heptane, cyclohexane, pentane, n-octane, undecane, dodecane, tridecane, tetradecane, pentadecane, and octadecane; the ketone is at least one selected from acetone, butanone and cyclohexanone; the organic acid alkyl ester is at least one selected from ethyl acetate, butyl acetate, dimethyl carbonate and isoamyl acetate; the methyl chloride is at least one selected from methyl chloride and chloroform.
10. The method for producing vinyl chloride-based resin particles according to any one of claims 5 to 9, wherein the radical initiator is an azo-based initiator or an organic peroxide-based initiator, and the amount of the initiator used in the reaction system is 0.1 to 4% by weight based on the total monomer mass; preferably, the azo initiator is at least one selected from azodiisobutyronitrile and azodiisoheptonitrile; the organic peroxide initiator is at least one selected from tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, di (hexadecyl) dicarbonate, tert-amyl peroxyneodecanoate, tert-butyl peroxypivalate, di- (4-tert-butylcyclohexyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxy2-ethylhexanoate, ditetradecyl peroxydicarbonate, tert-butyl peroxyacetate, cumyl peroxyneodecanoate, di-tert-butyl peroxide, cyclohexyl sulfonyl acetyl peroxide, diisobutyryl peroxide, 1, 3-tetramethylbutyl peroxyneodecanoate, di-3-methoxybutyl peroxydicarbonate and 1, 3-tetramethylbutyl peroxypivalate.
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