CN114426645A - Preparation method of vinyl chloride copolymer with improved impact resistance - Google Patents
Preparation method of vinyl chloride copolymer with improved impact resistance Download PDFInfo
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- CN114426645A CN114426645A CN202011178282.6A CN202011178282A CN114426645A CN 114426645 A CN114426645 A CN 114426645A CN 202011178282 A CN202011178282 A CN 202011178282A CN 114426645 A CN114426645 A CN 114426645A
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- Prior art keywords
- vinyl chloride
- latex
- acrylate
- weight
- impact resistance
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000004816 latex Substances 0.000 claims abstract description 80
- 229920000126 latex Polymers 0.000 claims abstract description 80
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 239000002245 particle Substances 0.000 claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 41
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 acrylic ester Chemical class 0.000 claims abstract description 35
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 19
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 13
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims abstract description 13
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 150000001447 alkali salts Chemical class 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 235000002639 sodium chloride Nutrition 0.000 claims description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000012874 anionic emulsifier Substances 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 7
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 7
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 7
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical group OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- AQKYLAIZOGOPAW-UHFFFAOYSA-N 2-methylbutan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCC(C)(C)OOC(=O)C(C)(C)C AQKYLAIZOGOPAW-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 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 4
- 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 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003995 emulsifying agent Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 8
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical group CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 229940096992 potassium oleate Drugs 0.000 description 3
- 229940114930 potassium stearate Drugs 0.000 description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 3
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 206010057362 Underdose Diseases 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A preparation method of vinyl chloride copolymer with improved impact resistance belongs to the technical field of vinyl chloride graft copolymerization. The method of the invention comprises the following steps: 1) polymerizing to obtain acrylic ester latex, 2) polymerizing to obtain acrylic ester latex with large particle size, and 3) performing vinyl chloride graft copolymerization to obtain a vinyl chloride graft copolymer. Wherein step 2): adding an inorganic strong acid strong alkali salt aqueous solution into the acrylate latex obtained in the step 1), and standing for 10-20 minutes; adding a first initiator, beginning to add butyl acrylate at 55-70 ℃, and mixing with diallyl phthalate or/and 1, 4-butanediol dimethacrylate by a weight ratio of (15-30): taking 0.2-0.3 of the mixture as a mixed monomer, finishing adding within 30-60 minutes, and polymerizing to obtain acrylate large-particle-size latex with the solid content of 25-35% by mass and the number average particle size of 0.1-0.4 mu m; the vinyl chloride graft copolymer obtained by the method has higher impact resistance.
Description
Technical Field
A preparation method of vinyl chloride copolymer with improved impact resistance belongs to the technical field of vinyl chloride graft copolymerization.
Background
Vinyl chloride copolymers, i.e., polyvinyl chloride resins, PVC resins. For improving and enhancing the mechanical properties of PVC resin, two methods, physical and chemical, are mainly adopted. The physical method mainly comprises means such as blending, for example, the special impact modifier is blended with PVC resin powder, and then operations such as deep plasticizing processing are carried out, so that the impact resistance is effectively improved. The physical method is greatly influenced by factors such as raw materials, processing conditions, formulas and the like, and the impact modifier is easy to have the problems of uneven dispersion, large difference in mechanical property and orientation and the like in PVC resin, so that the quality stability of processed products cannot be fully ensured.
In contrast, the rubber core component with the impact-resistant function is copolymerized with the vinyl chloride monomer in the PVC resin manufacturing process, so that the problems of anisotropy of mechanical properties and stability of products can be effectively solved. The particle size of the latex formed by the rubber core component has an important influence on the modification capability of the resin.
In order to obtain the latex with large particle size, in patent CN103848942B, firstly, inorganic acid, inorganic base or inorganic salt is used as a fluxing agent in advance in the latex, and then, the latex is subjected to high-pressure shearing agglomeration by applying a pressure of 30 to 60MPa, so that the latex with small particle size is coagulated into large particles. However, this process is not suitable for mass production of industrial devices due to the application of high pressure, and the particle size is mainly controlled by pressure and equipment conditions, so that the stability of latex particles is too sensitive to pressure, the particle size control capability is poor, the uniformity of the latex particle size is also poor, and finally, the latex particles are only physically adhered to each other, and the particle size and the distribution can still change in the subsequent process treatment.
The method for adjusting the pH value of an acrylate latex system by using a diluted water-soluble strong acid solution, which is proposed in the patent application No. CN109467646A, can prepare a latex with a large particle size, but the pH value change range in the diameter expansion process is narrow, the final particle size is greatly influenced by the stirring condition, the temperature, the acid solution diffusion condition and the like, and the particle size is not easy to control.
Currently, there is an urgent need for a vinyl chloride graft copolymer having excellent impact resistance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides a preparation method of vinyl chloride copolymer with improved impact resistance, and the vinyl chloride graft copolymer obtained by the method has higher impact resistance.
The technical scheme of the method for solving the technical problems is as follows: the preparation method of the vinyl chloride copolymer with improved impact resistance comprises the following steps: 1) polymerizing to obtain acrylic ester latex, 2) polymerizing to obtain acrylic ester latex with large particle size, and 3) vinyl chloride graft copolymerization;
wherein, step 1): uniformly mixing water, an anionic emulsifier, a first dispersant, a first initiator, an acrylate monomer and a cross-linking agent; polymerizing under inert atmosphere to obtain acrylic ester latex;
step 2): adding an aqueous solution of an inorganic strong acid strong alkali salt into the acrylate latex obtained in the step 1) by stirring, and standing for 10-20 minutes; adding a first initiator, heating to 55-70 ℃, starting adding an acrylate mixed monomer, finishing adding within 30-60 minutes, and carrying out polymerization reaction to obtain acrylate large-particle-size latex with the solid content of 25-35% by mass and the number average particle size of 0.1-0.4 mu m;
the acrylate mixed monomer in the step 2) is butyl acrylate, and is mixed with diallyl phthalate or/and 1, 4-butanediol dimethacrylate according to a weight ratio of 15-30: 0.2 to 0.3 of a mixture;
step 3): and (3) mixing water, a second dispersing agent, a pH regulator and a second initiator with a vinyl chloride monomer and the acrylic ester large-particle-size latex obtained in the step 2) uniformly under the conditions of inert atmosphere and vacuum pumping, and carrying out suspension graft polymerization to obtain the vinyl chloride graft copolymer.
The specific operation of the step 1) is as follows: uniformly mixing 160-220 parts by weight of desalted water, 0.5-5.0 parts by weight of anionic emulsifier, 0.08-0.1 part by weight of first dispersant, 0.10-1.0 part by weight of first initiator, 100 parts by weight of acrylate monomer and 0.75-2 parts by weight of cross-linking agent; and carrying out polymerization reaction at 55-70 ℃ in an inert atmosphere to obtain the acrylate latex with the solid content of 30-40% by mass and the number average particle size of 0.050-0.100 mu m.
The specific operation of the step 2) is as follows: stirring and adding 50-90 parts by mass of an aqueous solution of 5-10% inorganic strong acid strong base salt to the acrylate latex obtained in the step 1) at 20-50 ℃, and standing for 10-20 minutes; adding 0.06-0.11 part of first initiator by weight, heating to 55-70 ℃, starting to add 10-50 parts of acrylate mixed monomer, and finishing adding within 30-60 minutes to obtain the acrylate large-particle-size latex with the solid content of 27-33% by mass and the number average particle size of 0.1-0.3 mu m.
The specific operation of the step 3) is as follows: adding 150-200 parts by weight of desalted water, 0.1-0.2 part by weight of second dispersing agent, 0.05-0.20 part by weight of pH regulator and 0.01-0.2 part by weight of second initiator, adding 100 parts by weight of vinyl chloride monomer and 18-45 parts by weight of the acrylic ester large-particle-size latex obtained in the step 2) under the protection of inert atmosphere and after vacuum pumping, uniformly mixing, carrying out suspension graft polymerization at the temperature of 45-65 ℃, and carrying out termination, degassing, dehydration, drying and screening to obtain the vinyl chloride graft copolymer.
The acrylate monomer in the step 1) is butyl acrylate.
The cross-linking agent in the step 1) is at least one of diallyl phthalate and 1, 4-butanediol dimethacrylate.
The inorganic strong acid strong base salt in the step 2) is sodium chloride, potassium chloride or sodium sulfate.
The first initiator in the steps 1) and 2) is potassium persulfate, sodium persulfate or ammonium persulfate, and the first dispersant in the step 1) is potassium chloride or sodium pyrophosphate.
The second initiator in the step 3) is any two of tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, cumyl peroxyneodecanoate and di (2-ethylhexyl) peroxydicarbonate.
And 3) the second dispersing agent is hydroxypropyl methyl cellulose, and the pH regulator is ammonium bicarbonate or sodium hydroxide.
The invention is described below:
the anionic emulsifier in the step 1) is potassium laurate, potassium oleate or potassium stearate.
The amount of the inorganic strong acid strong base salt in the aqueous solution of the inorganic strong acid strong base salt in the step 2) is 0.1-5.0% by mass based on the dry weight of the acrylate latex in the step 2).
Preferably, the addition in the step 2) is completed within 30-60 minutes, and preferably, the addition is performed at a constant speed.
0.01 part of terminator used for terminating in the step 3), and the terminator is diethylhydroxylamine.
Preferably, the acrylate latex obtained in the step 1) has a solid content of 33-38.5% by mass and a number average particle size of 0.06-0.09 μm. When the solid content is too low, the use amount of the inorganic salt used for the salinity of the latex is increased, and when the solid content is too high, the problem of local over-concentration of the salinity is easily generated in the process of adding the inorganic salt solution, and the latex is unstable to generate rubber lumps or rubber residues. Thus, the concentration of the acrylate latex obtained in step 1) is higher than 35%, step 1) further comprising: and (3) adding desalted water to dilute the obtained acrylate latex to a solid content of 33-35%, and using the diluted acrylate latex as the raw material in the step 2).
Preferably, the acrylic ester large-particle-size latex obtained in the step 2) has the solid content of 27-33% in percentage by weight and the number average particle size of 0.19-0.30.
Researches show that the main factors influencing the impact modification effect of the impact modifier with the core-shell structure on the polyvinyl chloride resin comprise the composition, the dosage, the particle size, the core-shell ratio and the like of the core polymer. The invention adopts acrylate latex polymerized by polyacrylate with low glass transition temperature, and the alkyl chain in the acrylate molecule contains C2-C4 acrylate monomer.
The butyl acrylate is used in the steps 1) and 2), the molecular weight of the butyl acrylate is relatively high, only one double bond structure capable of participating in copolymerization exists in the monomer molecules, and after the double bonds are opened and polymerized to form a polymer, no redundant double bonds exist, so that the sensitivity to environmental influence factors such as ultraviolet light, heat and the like is relatively low, and the structural stability is relatively high.
In order to form the acrylate rubber phase latex having a crosslinked structure, the crosslinking agent should have a molecular structure containing two or more non-conjugated copolymerizable double bonds, and diallyl phthalate or/and 1, 4-butylene glycol dimethacrylate is preferably used in the present invention in view of polymerization reactivity with the acrylate monomer and monomer compatibility.
The step 1) mainly considers the stability of a polymerization system, and the emulsifier used for polymerization mainly takes an anionic emulsifier with stronger emulsifying and dispersing performances. In the invention, strong acid and strong base inorganic salts are used as the latex salinity regulator, but emulsifiers with poor sensitivity to inorganic salt concentration and over-strong protection capability such as sodium dodecyl sulfate, sodium dodecyl basic sulfonate and the like are not suitable to be used, and in addition, polymer emulsifiers with higher hydrophilicity are not suitable to be used. The invention discovers that in order to agglomerate the small-particle-size latex particles into large-particle-size particles by a chemical method, the emulsifier is preferably a strongly alkaline saponified substance of fatty acid with 12 to 18 carbon atoms in the linear alkyl (C12-C18), wherein the emulsifier is preferably a water-soluble saponified metal salt at normal temperature, and is mainly potassium salt, so that potassium laurate, potassium oleate and potassium stearate are preferably used. The reasonable dosage of the anionic emulsifier plays an important role, when the dosage of the anionic emulsifier is too small, the stability of an emulsion polymerization system in the polymerization process of the acrylic ester is poor, and when the dosage of the emulsifier is too high, the particle size of acrylic ester latex particles is smaller, so that the dosage of inorganic salt used in salinity regulation is increased.
The first initiator in the steps 1) and 2) belongs to a water-soluble persulfate initiator, preferably potassium sulfate, sodium persulfate or ammonium persulfate. If the amount of the first initiator is too low, the polymerization time is prolonged, the monomer reaction is incomplete, and the conversion rate is low. When the amount of the first initiator is too high, too many free radicals are generated in polymerization, the average particle size of the latex is reduced, problems of concentrated release of heat in polymerization reaction and the like occur, glue residue is generated, and the yield and the quality of the acrylate latex are affected.
The polymerization reaction efficiency and the polymerization stability can be ensured at the polymerization temperature of 55-70 ℃ in the step 1) and the step 2).
The applicant found that: in the polymerization reaction process, when the consumption of persulfate is too large, the pH value of a polymerization emulsion system is reduced, the stability of the system is influenced, and the polymerization reaction is accelerated due to the increase of acidity, so that the pH value of the system is sometimes required to be ensured to be stable. A small amount of basic salt can be used to neutralize the hydrogen ions released by the decomposition of persulfate. Alkaline salts that may be used include sodium bicarbonate, sodium pyrophosphate, sodium carbonate.
In step 2), the concentration of the salt (salinity) of the acrylate latex should first be adjusted using an inorganic strong acid strong base salt. Optional inorganic salts include sodium chloride, potassium chloride, sodium sulfate. By adjusting the salt concentration appropriately, the protective effect of the emulsifier on the polymer latex particles can be kept short of the critical point, and the stability is good. When a small amount of oil phase monomer is added, the protection effect provided by the emulsifier on the surface of the latex particle is reduced, the stability approaches to a critical point along with the addition of the monomer, and local instability occurs, so that adjacent latex particles are adhered and agglomerated with each other to form the latex with large particle size. At this time, if the monomer on the surface of the latex particle is caused to react to form a polymer, the agglomeration effect due to the influence of the salt concentration is solidified, and finally, a large-particle-size latex is formed.
In the invention, the monomer dosage used in the step 2) is obviously lower than that in the step 1), so that the system is prevented from generating micelle or glue residue due to insufficient dosage of the emulsifier in the latex, and generating large glue blocks in severe cases.
Adding hydroxypropyl methyl cellulose in the step 3), preferably, the hydroxypropyl methyl cellulose has a methoxyl content of 28-29%, a hydroxypropyl content of 6.0-12.0% and a viscosity of 40-60 mPa & s.
In the suspension graft copolymerization of vinyl chloride, some water-soluble inorganic salts can be used to participate in the polymerization reaction, such as ammonium bicarbonate or sodium hydroxide as pH regulator, to ensure the stability of the suspension polymerization system.
The research result of the invention shows that for the acrylic ester latex-vinyl chloride graft copolymer, when the latex content is lower than 4 weight percent, the impact resistance of the vinyl chloride copolymer resin is not obviously increased, but when the latex content is higher than 20 weight percent, the impact resistance effect is not further obviously improved, and the latex particles are agglomerated in the polyvinyl chloride graft copolymer and are difficult to disperse, so that the impact resistance is reduced.
Compared with the prior art, the invention has the beneficial effects that: the vinyl chloride graft copolymer obtained by the invention has shorter plasticizing time and excellent processing performance. Firstly, in the step 2), firstly, stirring and adding an aqueous solution of an inorganic strong acid strong base salt, standing for 10-20 minutes, and then adding a first initiator to heat and polymerize. Secondly, the acrylate mixed monomer used in the step 2) is butyl acrylate, and the butyl acrylate and diallyl phthalate or/and 1, 4-butanediol dimethacrylate are mixed according to the weight ratio of 15-30: 0.2 to 0.3 of a mixture. Thirdly, the temperature is raised to 55-70 ℃ in the step 2), 10-50 parts of acrylate mixed monomer is added, and the addition is completed within 30-60 minutes, so that the instability of a latex polymerization system caused by the centralized addition of the monomer is avoided. The impact resistance of the vinyl chloride graft copolymer can be obviously improved through the design.
Detailed Description
The present invention is further illustrated by the following specific examples, of which example 1 is the most preferred.
Example 1
1) Polymerizing to obtain acrylic ester latex
Adding 180 parts of desalted water, 1 part of potassium stearate, 0.08 part of sodium pyrophosphate and a monomer mixture consisting of 100 parts of butyl acrylate and 0.75 part of diallyl phthalate into a four-neck flask provided with a nitrogen inlet, a stirrer, a reflux condenser tube and a temperature raising and reducing device, blowing the air in the flask clean by nitrogen, starting stirring, raising the temperature to 70 ℃, and adding 0.30 part of ammonium persulfate to initiate polymerization; after the conversion rate reaches more than 99 percent, obtaining the acrylate latex with the solid content of 35.0 percent and the arithmetic mean grain diameter of 0.078 mu m;
2) polymerizing to obtain the acrylic ester large-particle-size latex
Cooling the acrylic ester latex obtained in the step 1) to 45 ℃, dropwise adding 80 parts of potassium chloride aqueous solution with the concentration of 5.0 mass percent under the stirring state, stabilizing for 10 minutes, adding 0.11 part of ammonium persulfate initiator, heating to 70 ℃, dropwise adding a mixed monomer consisting of 30 parts of butyl acrylate and 0.23 part of 1, 4-butanediol dimethacrylate at a constant speed for 30 minutes, and continuously reacting until the monomer conversion rate is more than 98% to obtain acrylic ester large-particle-size latex with the solid content of 32.5% and the average particle size of 0.233 mu m;
3) vinyl chloride graft copolymerization
Adding 100 parts of desalted water, 0.18 part of hydroxypropyl methyl cellulose E50 (product of Dow chemical company), 0.05 part of ammonium bicarbonate, 0.06 part of tert-butyl peroxyneodecanoate and 0.06 part of tert-amyl peroxypivalate into a clean stainless steel pressure polymerization kettle, sealing the polymerization kettle, replacing the air in the kettle with nitrogen, vacuumizing to below-0.080 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing at normal temperature for 15 minutes, adding 40 parts of the acrylate large-particle-size latex obtained in the step 2), heating to 52 ℃ for reaction, and adding 0.01 part of termination agent diethyl hydroxylamine when the pressure drops to 0.27 MPa. And (3) discharging unreacted monomers, dehydrating the obtained resin slurry to obtain a wet material, drying at 60 ℃, and sieving to obtain the chloroethylene graft copolymer.
Example 2
1) Polymerizing to obtain acrylic ester latex
220 parts of desalted water, 1.5 parts of potassium oleate, 0.10 part of sodium pyrophosphate and a monomer mixture consisting of 100 parts of butyl acrylate and 2 parts of 1, 4-butanediol dimethacrylate are added into a four-neck flask provided with a nitrogen inlet, a stirrer, a reflux condenser tube and a temperature raising and reducing device, the air in the flask is completely blown by nitrogen, the stirring is started, the temperature is raised to 55 ℃, and 0.75 part of sodium persulfate is added to initiate polymerization reaction; after the conversion rate reaches more than 98 percent, obtaining the acrylic ester large-particle-size latex with the solid content of 33.3 percent and the arithmetic mean particle size of 0.075 mu m;
2) polymerizing to obtain the acrylic ester large-particle-size latex
Cooling the acrylic ester latex obtained in the step 1) to 30 ℃, dropwise adding 90 parts of sodium sulfate aqueous solution with the concentration of 6.0 mass percent under the stirring state, stabilizing for 10 minutes, adding 0.11 part of sodium persulfate initiator, heating to 65 ℃, dropwise adding a mixed monomer consisting of 15 parts of butyl acrylate and 0.3 part of 1, 4-butanediol dimethacrylate at a constant speed for 60 minutes, and continuously reacting until the monomer conversion rate is more than 95%, thereby obtaining the acrylic ester latex with the solid content of 27.0 percent and the average particle size of 0.211 mu m.
3) Vinyl chloride graft copolymerization
Adding 200 parts of desalted water, 0.10 part of hydroxypropyl methyl cellulose E50 (product of Dow chemical company), 0.05 part of ammonium bicarbonate and an initiator consisting of 0.03 part of tert-butyl peroxyneodecanoate and 0.06 part of tert-amyl peroxypivalate into a clean stainless steel pressure polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen, vacuumizing to be below-0.080 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing for 15 minutes at normal temperature, adding 18.5 parts of the acrylic ester large-particle-size latex obtained in the step 2), heating to 63.5 ℃ for reaction, and adding 0.01 part of termination agent diethylhydroxylamine when the pressure drops to 0.35 MPa; and (3) discharging unreacted monomers, dehydrating the obtained resin slurry to obtain a wet material, drying at 60 ℃, and sieving to obtain the chloroethylene graft copolymer.
Example 3
1) Polymerizing to obtain acrylic ester latex
160 parts of desalted water, 100 parts of butyl acrylate, 1 part of diallyl phthalate, 2 parts of potassium laurate and 0.08 part of potassium chloride are added into a four-neck flask provided with a nitrogen inlet, a stirrer, a reflux condenser tube and a temperature raising and reducing device; blowing the air in the bottle clean by using nitrogen, starting stirring, heating to 65 ℃, and adding 0.25 part of potassium persulfate to initiate polymerization; when the conversion rate reaches more than 97 percent, finishing the polymerization reaction to obtain acrylic ester latex with the solid content of 38.2 percent and the arithmetic mean particle size of 0.063 mu m;
2) polymerizing to obtain the acrylic ester large-particle-size latex
Cooling the acrylic ester latex obtained in the step 1) to 40 ℃, adding 40 parts of desalted water to dilute the solid content to 33%, dropwise adding 50 parts of sodium chloride aqueous solution with the concentration of 5.0 mass percent under the stirring state, keeping for 10 minutes, adding 0.06 part of potassium persulfate, heating to 65 ℃, dropwise adding a mixed monomer consisting of 20 parts of butyl acrylate and 0.2 part of diallyl phthalate at a constant speed within 45 minutes, and continuously reacting until the monomer conversion rate is more than 96% to obtain acrylic ester large-particle-size latex with the solid content of 32.0% and the average particle size of 0.177 mu m;
3) vinyl chloride graft copolymerization
Adding 130 parts of desalted water, 0.12 part of hydroxypropyl methyl cellulose E50 (product of Dow chemical company), 0.06 part of ammonium bicarbonate and an initiator consisting of 0.04 part of cumyl peroxyneodecanoate and 0.09 part of di (2-ethylhexyl) peroxydicarbonate into a clean stainless steel pressure polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen, pumping vacuum to be below-0.080 MPa, adding 100 parts of vinyl chloride monomer, stirring and mixing at normal temperature for 15 minutes, adding 31.2 parts of the acrylic ester large-particle-size latex obtained in the step 2), heating to 57 ℃ for reaction, and adding 0.01 part of termination agent diethylhydroxylamine when the pressure drops to 0.15 MPa; and (3) discharging unreacted monomers, dehydrating the obtained resin slurry to obtain a wet material, drying at 60 ℃, and sieving to obtain the chloroethylene graft copolymer.
Example 4
This example is the same as example 1, except that: different from the mixed monomers, the mixed monomers used in this example are: a mixed monomer consisting of 30 parts of butyl acrylate, 0.08 part of diallyl phthalate and 0.15 part of 1, 4-butylene glycol dimethacrylate.
Example 5
This example is the same as example 1, except that: replacing 0.75 part of diallyl phthalate in step 1) with 0.3 part of diallyl phthalate and 0.45 part of 1, 4-butanediol dimethacrylate.
Comparative example 1
The comparative preparation method differs from example 1 in that: this comparative example employed only steps 1) and 3), without operating step 2).
Comparative example 2
The comparative preparation method differs from example 1 in that: step 2) no potassium chloride aqueous solution is added, and step 2) the potassium chloride aqueous solution is replaced by desalted water with equal weight.
Performance testing
The vinyl chloride graft copolymers obtained in examples and comparative examples were subjected to the following performance tests, and the test results are shown in Table 1.
1. The particle size of the copolymer latex and the particle size of the graft copolymer resin are measured by a Mastersizer 2000 laser particle size analyzer manufactured by Malvern company;
2. vinyl chloride polymerization conversion: gravimetric method;
3. apparent density: testing according to GB/T20022-2005;
4. impact strength of the simply supported beam notch: testing at 23 ℃ according to the conditions specified in GB/T1043.1-2008;
4.1) sample strip formula, which comprises the following components in parts by weight: 100 parts of vinyl chloride graft copolymer resin, 88311.5 parts of organic tin, 600.5 parts of lubricant ZB, 740.4 parts of lubricant ZB;
4.2) sample preparation method of sample strips: weighing and mixing the materials according to the formula, kneading in a high-speed mixer, mixing (175 +/-5 ℃ for 5 minutes) by an SK-160B double-roll mixing mill to prepare a mixed sheet, pressing the mixed sheet on a hot press to obtain a sheet with the thickness of 4mm (180 +/-2 ℃ for 3 minutes), and preparing a simply supported beam impact sample strip according to standard requirements;
5. and (3) determining the processability of the vinyl chloride graft copolymer resin: preparing sample strips from the mixture in the step 4.1) to the step 4.2), and carrying out plasticizing performance test on a torque rheometer of HAAKE company in Germany under the test conditions of 160 ℃ of temperature, 40r/min of rotor speed and 68g of feeding amount.
Table 1 results of performance testing
As can be seen from table 1:
examples 1 to 5 have high impact strength. Among them, example 1 is superior in impact resistance and shortest in plasticizing time, and comparative example 1 is the most preferable example without the operation of step 2), and the obtained vinyl chloride graft copolymer is low in impact resistance.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing a vinyl chloride copolymer having improved impact resistance, comprising the steps of: 1) polymerizing to obtain acrylic ester latex, 2) polymerizing to obtain acrylic ester latex with large particle size, and 3) vinyl chloride graft copolymerization;
wherein, step 1): uniformly mixing water, an anionic emulsifier, a first dispersant, a first initiator, an acrylate monomer and a cross-linking agent; polymerizing under inert atmosphere to obtain acrylic ester latex;
step 2): adding an aqueous solution of an inorganic strong acid strong alkali salt into the acrylate latex obtained in the step 1) by stirring, and standing for 10-20 minutes; adding a first initiator, heating to 55-70 ℃, starting adding an acrylate mixed monomer, finishing adding within 30-60 minutes, and carrying out polymerization reaction to obtain acrylate large-particle-size latex with the solid content of 25-35% by mass and the number average particle size of 0.1-0.4 mu m;
the acrylate mixed monomer in the step 2) is butyl acrylate, and is mixed with diallyl phthalate or/and 1, 4-butanediol dimethacrylate according to a weight ratio of 15-30: 0.2 to 0.3 of a mixture;
step 3): and (3) mixing water, a second dispersing agent, a pH regulator and a second initiator with a vinyl chloride monomer and the acrylic ester large-particle-size latex obtained in the step 2) uniformly under the conditions of inert atmosphere and vacuum pumping, and carrying out suspension graft polymerization to obtain the vinyl chloride graft copolymer.
2. A method of preparing a vinyl chloride copolymer with improved impact resistance according to claim 1, wherein: the specific operation of the step 1) is as follows: uniformly mixing 160-220 parts by weight of desalted water, 0.5-5.0 parts by weight of anionic emulsifier, 0.08-0.1 part by weight of first dispersant, 0.10-1.0 part by weight of first initiator, 100 parts by weight of acrylate monomer and 0.75-2 parts by weight of cross-linking agent; and carrying out polymerization reaction at 55-70 ℃ in an inert atmosphere to obtain the acrylate latex with the solid content of 30-40% by mass and the number average particle size of 0.050-0.100 mu m.
3. A method of preparing a vinyl chloride copolymer with improved impact resistance according to claim 1, wherein: the specific operation of the step 2) is as follows: stirring and adding 50-90 parts by mass of an aqueous solution of 5-10% inorganic strong acid strong base salt to the acrylate latex obtained in the step 1) at 20-50 ℃, and standing for 10-20 minutes; adding 0.06-0.11 part of first initiator by weight, heating to 55-70 ℃, starting to add 10-50 parts of acrylate mixed monomer, and finishing adding within 30-60 minutes to obtain the acrylate large-particle-size latex with the solid content of 27-33% by mass and the number average particle size of 0.1-0.3 mu m.
4. A method of preparing a vinyl chloride copolymer with improved impact resistance according to claim 1, wherein: the specific operation of the step 3) is as follows: adding 150-200 parts by weight of desalted water, 0.1-0.2 part by weight of second dispersing agent, 0.05-0.20 part by weight of pH regulator and 0.01-0.2 part by weight of second initiator, adding 100 parts by weight of vinyl chloride monomer and 18-45 parts by weight of the acrylic ester large-particle-size latex obtained in the step 2) under the protection of inert atmosphere and after vacuum pumping, uniformly mixing, carrying out suspension graft polymerization at the temperature of 45-65 ℃, and carrying out termination, degassing, dehydration, drying and screening to obtain the vinyl chloride graft copolymer.
5. A method for preparing a vinyl chloride copolymer with improved impact resistance according to claim 1 or 2, characterized in that: the acrylate monomer in the step 1) is butyl acrylate.
6. A method for preparing a vinyl chloride copolymer with improved impact resistance according to claim 1 or 2, characterized in that: the cross-linking agent in the step 1) is at least one of diallyl phthalate and 1, 4-butanediol dimethacrylate.
7. A method for preparing a vinyl chloride copolymer with improved impact resistance according to claim 1 or 3, characterized in that: the inorganic strong acid strong base salt in the step 2) is sodium chloride, potassium chloride or sodium sulfate.
8. A method for preparing a vinyl chloride copolymer with improved impact resistance according to claim 1 or 2, characterized in that: the first initiator in the steps 1) and 2) is potassium persulfate, sodium persulfate or ammonium persulfate; the first dispersant in the step 1) is potassium chloride or sodium pyrophosphate.
9. A method for preparing vinyl chloride copolymer with improved impact resistance according to claim 1 or 4, wherein: the second initiator in the step 3) is any two of tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, cumyl peroxyneodecanoate and di (2-ethylhexyl) peroxydicarbonate.
10. A process for preparing a vinyl chloride copolymer with improved impact resistance according to claim 1 or 4, characterized in that: and 3) the second dispersing agent is hydroxypropyl methyl cellulose, and the pH regulator is ammonium bicarbonate or sodium hydroxide.
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| CN109467646A (en) * | 2018-10-10 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of preparation method of vinyl chloride graft copolymer |
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| US3959408A (en) * | 1973-04-09 | 1976-05-25 | Kureha Kagaku Kogyo Kabushiki Kaisha | Vinyl chloride resins blended with two step graft resins |
| KR19990069231A (en) * | 1998-02-05 | 1999-09-06 | 성재갑 | Manufacturing Method of Vinyl Chloride Resin for Straight Processing with Excellent Impact Resistance |
| CN1743371A (en) * | 2005-09-29 | 2006-03-08 | 河北工业大学 | Nucleocapsid structure polyvinyl chloride impact modifier, and its preparing method and use |
| CN104558428A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | High-toughened chloroethylene grafted copolymer and preparation method thereof |
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