CN100408605C - Graft copolymer of chlorinated polyethylene-alkyl-acrylates, and preparing method and use - Google Patents
Graft copolymer of chlorinated polyethylene-alkyl-acrylates, and preparing method and use Download PDFInfo
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- CN100408605C CN100408605C CNB2006100018956A CN200610001895A CN100408605C CN 100408605 C CN100408605 C CN 100408605C CN B2006100018956 A CNB2006100018956 A CN B2006100018956A CN 200610001895 A CN200610001895 A CN 200610001895A CN 100408605 C CN100408605 C CN 100408605C
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920000578 graft copolymer Polymers 0.000 title abstract description 46
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 56
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- -1 acrylic acid alkyl ester compound Chemical class 0.000 claims description 23
- 239000003607 modifier Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 229940114930 potassium stearate Drugs 0.000 claims description 3
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 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 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 229940080350 sodium stearate Drugs 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 64
- 239000011347 resin Substances 0.000 abstract description 30
- 229920005989 resin Polymers 0.000 abstract description 30
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract description 17
- 239000000843 powder Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000035939 shock Effects 0.000 description 31
- 239000000203 mixture Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 14
- 239000004609 Impact Modifier Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000004135 Bone phosphate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a graft copolymer of chlorinated polyethylene-alkyl-acrylate, a preparing method and an application thereof, which belongs to the technical field of macromolecular graft copolymers and a preparation technique thereof. The graft copolymer of chlorinated polyethylene-alkyl-acrylate is prepared by alkyl-acrylate compounds on chlorinated polyethylene via graft copolymerization, wherein chlorinated polyethylene takes 75 to 95% of raw materials by weight, the alkyl-acrylate compounds take 5 to 25% of raw materials by weight, and the carbon number of alkyl in the alkyl-acrylate compounds is from 2 to 8. The present invention also provides an application of the graft copolymer of chlorinated polyethylene-alkyl-acrylate as a modifying agent. The graft copolymer of chlorinated polyethylene-alkyl-acrylate having favorable powder flowability can be used as the modifying agent for processing polyvinyl chloride resin in order to effectively improve the weather resistance, the impact resistance and the processing performance of the polyvinyl chloride resin, and has the advantages of low cost and simple preparing method.
Description
Technical field
The invention belongs to polymer quasi-graft copolymer and preparing technical field thereof, relate in particular to a kind of impact processing modifier graft copolymer of chlorinated polyethylene-alkyl-acrylates that is applied to polyvinyl chloride (PVC) RESINS and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is a kind of universal thermoplastics of excellent property, is one of plastics variety of China's output maximum.Polyvinyl chloride to shape performance very poor, must add various processing aids, to improve its processing characteristics; The resistance to impact shock of the goods after polyvinyl chloride shapes is poor, and people have invented several different methods to improve the resistance to impact shock of polrvinyl chloride product.One of them method is exactly to add the terpolymer of butadiene-styrene-methyl methacrylate, and just the MBS resin improves the shock strength of polrvinyl chloride product.Although but the resistance to impact shock of resultant goods was than higher after the MBS resin was processed with the mixture of PVC, weathering resistance is poor, and after outdoor application for some time, the resistance to impact shock of goods can descend rapidly.So, can only be in indoor use through the polyvinyl chloride of MBS modification.
The reason of MBS resin weathering resistance difference is that the UV resistant performance of main component polyhutadiene wherein is poor.In order to improve the weathering resistance of MBS, people have invented not double bond containing anti-impact modifier-acrylic ester impact-resisting modifier again.Acrylic ester impact-resisting modifier is the acrylate nucleoid-shell graft copolymer (special public clear 51-28117 communique) that obtains by monomeric mixtures such as grafting alkyl methacrylate, vinylbenzene, vinyl cyanide on lightly crosslinked acrylic ester elastomer.The nuclear of acrylate nucleoid-shell graft copolymer partly is acrylic ester elastomer, polrvinyl chloride product with this acrylate nucleoid-shell graft copolymer impact modifier modification has good weathering resistance, but, be difficult to be promoted the use of widely because it costs an arm and a leg.
Do not contain two keys in the chlorinatedpolyethylene (CPE), and cheap so be widely used in the impact modification of no plasticized PVC goods.But because the shock resistance weak effect of chlorinatedpolyethylene need the amount of adding bigger, but this has destroyed the mechanical property of PVC goods again largely.Simultaneously owing to contain the chlorine atom in the chlorinatedpolyethylene, and the easy decomposes of chlorinatedpolyethylene, when large usage quantity, the consumption of CPE will above CPE in PVC saturation solubility and separate out, form independent CPE phase, can only dissolve in the PVC phase mutually because the thermo-stabilizer in the polyvinyl chloride (PVC) Compound can not dissolve in CPE, so CPE very easily decomposes mutually and produces hydrogenchloride, and hydrogenchloride has quickened the decomposition of PVC greatly the weather resistance of goods is declined to a great extent.Therefore the mechanical property of collateral security PVC goods and the angle of weather resistance are set out, if reduce the usage quantity of CPE in polyvinyl chloride (PVC) Compound when can significantly improve the shock resistance of CPE, we just can obtain a kind of weathering resistance, shock resistance, excellent processability and cheap polyvinyl chloride (PVC) Compound.
The effective means that improves the CPE resistance to impact shock improves the rubber performance of CPE for reducing the second-order transition temperature of CPE.In general, the rubber that second-order transition temperature is lower, weathering resistance is good is the polymkeric substance of alkyl-acrylates class, therefore as long as being carried out graft polymerization, CPE and alkyl-acrylates class monomer just can achieve the goal, but the mixture of the CPE-alkyl-acrylates that obtains by simple mixing lumps easily, powder fluidity is poor, can't mix with PVC, can not use as the properties-correcting agent of PVC.
Summary of the invention
The purpose of this invention is to provide a kind of graft copolymer of chlorinated polyethylene-alkyl-acrylates with good powder fluidity, with and preparation method thereof and as the application of polyvinyl chloride (PVC) RESINS modifier, solved the problem that traditional use CPE carries out the processing characteristics, shock resistance and the weathering resistance difference that exist in the polyvinyl chloride resin modification.
The technical solution used in the present invention is as follows:
Graft copolymer of chlorinated polyethylene-alkyl-acrylates, it is characterized in that it is to be prepared from by the graft copolymerization on chlorinatedpolyethylene of alkyl-acrylates compound, wherein to account for the weight percent of raw material be 75～95% to chlorinatedpolyethylene, the weight percent that the alkyl-acrylates compound accounts for raw material is 5～25%, and the carbonatoms of the alkyl in the described alkyl-acrylates compound is 2～8.
Described chlorinatedpolyethylene is 33～37% chlorinatedpolyethylene for the chlorine weight percentage.
The weight percent that described preferred chlorinatedpolyethylene accounts for raw material is 85～90%, and the weight percent that the alkyl-acrylates compound accounts for raw material is 10～15%.
The method for making of above-mentioned graft copolymer of chlorinated polyethylene-alkyl-acrylates, the chlorinatedpolyethylene that it is characterized in that accounting for the alkyl-acrylates compound of raw material gross weight 5～25% and account for raw material gross weight 75～95% is put into reactor, and add entry and account for the tensio-active agent of raw material gross weight 0.1～2%, under nitrogen atmosphere, stir and be warming up to 70～90 ℃, kept 0.5～2 hour, add the radical initiator that accounts for raw material gross weight 0.1～2% then and cause copolyreaction, and under 50～500 rev/mins stirring velocity, reacted 3～5 hours, obtain graft copolymer of chlorinated polyethylene-alkyl-acrylates.
Described tensio-active agent comprises Soxylat A 25-7, Sodium dodecylbenzene sulfonate, sodium stearate, potassium stearate.
Described radical initiator comprises di-isopropylbenzene hydroperoxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tertbutyl peroxide or hydrogen phosphide cumene.
The preferred add-on of described water is 4～6 times of raw material gross weight.
This graft copolymer of chlorinated polyethylene-alkyl-acrylates is as the application of polychloroethylene processing modifier.
Alkyl-acrylates polymkeric substance in the graft copolymer of chlorinated polyethylene-alkyl-acrylates can effectively reduce the second-order transition temperature of chlorinatedpolyethylene and improve the rubber performance that it has.Theoretically, the shock resistance of the high more then multipolymer of the content of alkyl-acrylates polymkeric substance is high more in the graft copolymer of chlorinated polyethylene-alkyl-acrylates, but when the weight percent content of alkyl-acrylates polymkeric substance in the graft copolymer of chlorinated polyethylene-alkyl-acrylates surpasses 25%, the powder fluidity variation of graft copolymer is difficult to produce normally and use.When the weight percent content of alkyl-acrylates base polymer in the graft copolymer was lower than 5%, its shock strength was too low, and usage quantity can not descend, and can not obtain weathering resistance, the polyvinyl chloride (PVC) Compound that shock resistance and processibility are good.
In order to improve the powder fluidity energy of graft copolymer of chlorinated polyethylene-alkyl-acrylates, the contriver has taked elder generation that the alkyl-acrylates compound is dissolved in the CPE particle, and then the method for carrying out graft copolymerization, make the interior polymeric of alkyl-acrylates compound at CPE, contain the polyvinyl chloride of alkyl-acrylates polymkeric substance and good fluidity-alkyl acrylate by graft copolymerization thing and obtain inside, wherein the second-order transition temperature of grafted alkyl-acrylates polymkeric substance is less than-20 ℃.Because the second-order transition temperature of alkyl-acrylates polymkeric substance is far below CPE, so the resistance to impact shock of chlorinated polyethylene-alkyl-acrylates multipolymer will be higher than CPE, the usage quantity of CPE-alkyl-acrylates analog copolymer in polyvinyl chloride (PVC) Compound can be lower than CPE like this, simultaneously because the alkyl-acrylates base polymer has good processing properties, we have just obtained a kind of weathering resistance, the polyvinyl chloride (PVC) Compound that shock resistance and processibility are good with CPE-alkyl-acrylates multipolymer and PVC blend like this.
The carbonatoms of the alkyl in the aforesaid propylene acid alkyl ester compounds is 2～8, for example vinylformic acid ethyl ester, vinylformic acid propyl diester, butyl acrylate cores, the different zinc ester of vinylformic acid, vinylformic acid heptyl ester or the like.
This graft copolymer of chlorinated polyethylene-alkyl-acrylates can be used for the modification of polyvinyl chloride with the same method of existing properties-correcting agent, and its add-on is 2～25% of polyvinyl chloride and this two gross weight of graft copolymer.
Beneficial effect of the present invention is, this graft copolymer of chlorinated polyethylene-alkyl-acrylates has good powder fluidity, can be used as the impact processing modifier of polyvinyl chloride (PVC) RESINS, can effectively improve weathering resistance, shock resistance and the processing characteristics of polyvinyl chloride (PVC) RESINS, and have that cost is low, the simple advantage of preparation method.
Embodiment
Embodiment 1
(1) graft copolymer of chlorinated polyethylene-alkyl-acrylates is synthetic
The chlorine weight percent content that adds water, 85 weight parts of 500 weight parts in the four-hole boiling flask that agitator, thermometer and nitrogen pipeline are housed is the sodium lauryl sulphate of 35% chlorinatedpolyethylene, the different monooctyl ester of 15 parts by weight of acrylic and 2 weight parts, under nitrogen atmosphere, be warming up to 80 ℃ while stirring, stirred 1 hour, the di-isopropylbenzene hydroperoxide that adds 1 weight part then reacted 3 hours, reached 98% through detecting the polymeric transformation efficiency.Obtain desired graft copolymer of chlorinated polyethylene-alkyl-acrylates through after centrifugal, the drying.
(2) modified PVC resin
Above-mentioned graft copolymer of chlorinated polyethylene-alkyl-acrylates and polyvinyl chloride (PVC) RESINS are prepared burden by following prescription:
92.5 parts of polyvinyl chloride
7.5 parts of CPE-alkyl-acrylates graft copolymers
2 parts of tribasic lead sulfates
1 part of dibasic Lead Phosphite
1 part of lead stearate
0.5 part of calcium stearate
0.15 part of polyethylene wax
Various raw materials are dropped into the homogenizer high speed by above-mentioned formula rate mix, reach 120 ℃ after the discharging cooling, obtain the polyvinyl chloride (PVC) RESINS mixture.Open with two roller mills then and be smelt the test that sheet material carries out thermostability and light stability.The test of resistance to impact shock is undertaken by the method shown in the GB/T8814 standard.
Embodiment 2-5 adopts the method identical with embodiment 1 to prepare graft copolymer of chlorinated polyethylene-alkyl-acrylates, and still wherein the weight ratio of chlorinatedpolyethylene and Isooctyl acrylate monomer is different.Preparation modified chlorinated polyethylene resin technology is with embodiment 1.Wherein the weight ratio data of chlorinatedpolyethylene and Isooctyl acrylate monomer see Table 1.
Comparative Examples 1-3 adopts the method identical with embodiment 1 to prepare graft copolymer of chlorinated polyethylene-alkyl-acrylates, but wherein the weight ratio of chlorinatedpolyethylene and Isooctyl acrylate monomer is different, wherein Comparative Examples 1 adopts conventional modifier CPE to contrast, and preparation modified chlorinated polyethylene resin technology is with embodiment 1.Wherein the weight ratio data of chlorinatedpolyethylene and Isooctyl acrylate monomer see Table 1.
Carry out the resistance to impact shock test by the polyvinyl chloride (PVC) RESINS that the method shown in the GB/T8814 standard obtains embodiment 1-5 and Comparative Examples 1-3.The resistance to impact shock data of the polyvinyl chloride (PVC) RESINS of the graft copolymer of chlorinated polyethylene-alkyl-acrylates modification that different ratios is formed see Table 1.
The resistance to impact shock data of the polyvinyl chloride (PVC) RESINS of graft copolymerization raw material composition and modification among table 1 embodiment 1-5 and the Comparative Examples 1-3
"
*" expression impact modifier caking, can not mix with polyvinyl chloride.
CPE-alkyl-acrylates graft copolymer plays good modification performance to polyvinyl chloride (PVC) RESINS as can be seen from Table 1, can effectively improve the shock resistance of polyvinyl chloride (PVC) RESINS.The ratio of alkyl-acrylates polymkeric substance is high more in the graft copolymer, and the shock strength of polyvinyl chloride (PVC) Compound is high more, can be found out by Comparative Examples 2, and when the ratio of alkyl-acrylates polymkeric substance was lower than 5%, the shock strength of polyvinyl chloride (PVC) Compound can be very low; By Comparative Examples 3 as can be known, when the ratio of alkyl-acrylates polymkeric substance in the CPE-alkyl-acrylates graft copolymer is higher than 25%, the powder fluidity variation of anti-impact modifier, can lump and can not with the PVC uniform mixing.By Comparative Examples 1 as can be seen, adopting at present, the shock strength of the polyvinyl chloride (PVC) RESINS of the conventional CPE impact modifier that uses is significantly less than CPE-alkyl-acrylates graft copolymer properties-correcting agent provided by the invention.
Resistance to impact shock when 0 ℃ of polyvinyl chloride (PVC) Compound is 21.6KJ/m
2The time, the ratio of weight and number of institute's synthetic impact modifier and polyvinyl chloride and the thermostability of corresponding polyvinyl chloride (PVC) Compound and the contrast of light stability see Table 2 among embodiment 1-5 and the comparative example 1-2.The test condition of thermostability is: the test condition of 180 ℃ of 60 minutes light stability is: irradiation is 48 hours in the ultraviolet lamp baking oven of 60W.
The composition of the polyvinyl chloride (PVC) RESINS of the identical resistance to impact shock of table 2 and its thermally-stabilised and light stability
"
*" represent that intensity of variation is poor, thermostability and good light stability; And "
* * * *" expression intensity of variation height, thermostability and light stability are poor.
Ratio along with alkyl-acrylates polymkeric substance in the impact modifier is high more as can be seen by table 1 and table 2, when reaching identical resistance to impact shock, the weight ratio of impact modifier and PVC is come lowly more in polyvinyl chloride (PVC) Compound, that is to say that the consumption of impact modifier is fewer and feweri.Its thermostability and light stability are become better and better simultaneously.In an embodiment because so the few weathering resistance of consumption (thermostability and light stability) of impact modifier is all right, and in the Comparative Examples since the add-on of impact modifier how so weathering resistance is poor.Adopt graft copolymer of chlorinated polyethylene-alkyl-acrylates of the present invention, can obtain a kind of weathering resistance, the polyvinyl chloride (PVC) Compound that shock resistance is all good.
Embodiment 6
(1) impact modifier is synthetic
The weight percentage of the chlorine of the water of adding 600 weight parts, 75 weight parts is 33% CPE in the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed, the Sodium dodecylbenzene sulfonate of 25 parts by weight of acrylic butyl esters, 0.1 weight part is warming up to 90 ℃ while stirring under nitrogen atmosphere, stirred 0.5 hour after, add the Potassium Persulphate afterreaction 5 hours of 0.1 weight part, the polymeric transformation efficiency reaches 97%.Through centrifugal, obtain desired CPE-alkyl-acrylates graft copolymer after the drying.
(2) modified PVC resin
Above-mentioned graft copolymer of chlorinated polyethylene-alkyl-acrylates and polyvinyl chloride (PVC) RESINS are prepared burden by following prescription:
85 parts of polyvinyl chloride
15 parts of CPE-alkyl-acrylates graft copolymers
2 parts of tribasic lead sulfates
1 part of dibasic Lead Phosphite
1 part of lead stearate
0.5 part of calcium stearate
0.15 part of polyethylene wax
Various raw materials are dropped into the homogenizer high speed by above-mentioned formula rate mix, reach 120 ℃ after the discharging cooling, obtain the polyvinyl chloride (PVC) RESINS mixture.After tested, this polyvinyl chloride (PVC) RESINS mixture has good weathering resistance, resistance to impact shock and processing characteristics.
Embodiment 7
(1) impact modifier is synthetic
The weight percentage of the chlorine of the water of adding 400 weight parts, 95 weight parts is 37% CPE in the four-hole boiling flask that agitator, thermometer and nitrogen pipeline are housed, the potassium stearate of 5 parts by weight of acrylic ethyl esters, 1 weight part is warming up to 70 ℃ while stirring under nitrogen atmosphere, stirred 2 hours after, add the tertbutyl peroxide afterreaction 4 hours of 0.5 weight part, the polymeric transformation efficiency reaches 98%.Through centrifugal, obtain desired CPE-alkyl-acrylates graft copolymer after the drying.
(2) polyvinyl chloride (PVC) Compound
Adopt the method identical to be used for the modification of polyvinyl chloride (PVC) RESINS, but wherein CPE-alkyl-acrylates graft copolymer adopt the multipolymer that present embodiment prepares, and obtains the polyvinyl chloride (PVC) RESINS mixture with embodiment 6.After tested, this polyvinyl chloride (PVC) RESINS mixture has good weathering resistance, resistance to impact shock and processing characteristics.
Embodiment 8
(1) impact modifier is synthetic
In the four-hole boiling flask that agitator, mercurythermometer and nitrogen pipeline are housed, add the water of 300 weight parts, 90 parts the weight percentage of chlorine and be 34 CPE, 10 parts vinylformic acid pentyl ester, 0.5 Soxylat A 25-7 be warming up to 80 ℃ while stirring, stirred 1 hour after, the ammonium persulphate that adds 0.5 weight part, keep mixing speed at 200 rev/mins, reacted 4 hours down at 80 ℃, the polymeric transformation efficiency reaches 98%.Through centrifugal, obtain desired CPE-alkyl-acrylates graft copolymer after the drying.
(2) polyvinyl chloride (PVC) Compound
Above-mentioned graft copolymer of chlorinated polyethylene-alkyl-acrylates and polyvinyl chloride (PVC) RESINS are prepared burden by following prescription:
80 parts of polyvinyl chloride
20 parts of CPE-alkyl-acrylates graft copolymers
20 parts in lime carbonate
3 parts of titanium dioxides
2 parts of tribasic lead sulfates
1 part of dibasic Lead Phosphite
1 part of lead stearate
0.5 part of calcium stearate
0.15 part of polyethylene wax
Various raw materials are dropped into the homogenizer high speed by above-mentioned formula rate mix, reach 120 ℃ after the discharging cooling, obtain the polyvinyl chloride (PVC) RESINS mixture.After tested, this polyvinyl chloride (PVC) RESINS mixture has good weathering resistance, resistance to impact shock and processing characteristics.
Claims (8)
1. chlorinatedpolyethylene-alkyl acrylate by graft copolymerization thing, it is characterized in that it is to be prepared from by acrylic acid alkyl ester compound graft copolymerization on chlorinatedpolyethylene, wherein to account for the weight percent of raw material be 75～95% to chlorinatedpolyethylene, the weight percent that acrylic acid alkyl ester compound accounts for raw material is 5～25%, and the carbonatoms of the alkyl in the described acrylic acid alkyl ester compound is 2～8.
2. chlorinatedpolyethylene according to claim 1-alkyl acrylate by graft copolymerization thing is characterized in that described chlorinatedpolyethylene is 33～37% chlorinatedpolyethylene for the chlorine weight percentage.
3. chlorinatedpolyethylene according to claim 1-alkyl acrylate by graft copolymerization thing is characterized in that the weight percent that described chlorinatedpolyethylene accounts for raw material is 85～90%, and the weight percent that acrylic acid alkyl ester compound accounts for raw material is 10～15%.
4. the method for making of the described chlorinatedpolyethylene of claim 1-alkyl acrylate by graft copolymerization thing, the chlorinatedpolyethylene that it is characterized in that accounting for the acrylic acid alkyl ester compound of raw material gross weight 5～25% and account for raw material gross weight 75～95% is put into reactor, and add entry and account for the tensio-active agent of raw material gross weight 0.1～2%, under nitrogen atmosphere, stir and be warming up to 70～90 ℃, kept 0.5～2 hour, add the radical initiator that accounts for raw material gross weight 0.1～2% then and cause copolyreaction, and under 50～500 rev/mins stirring velocity, reacted 3～5 hours, obtain chlorinatedpolyethylene-alkyl acrylate by graft copolymerization thing.
5. the method for making of chlorinatedpolyethylene according to claim 4-alkyl acrylate by graft copolymerization thing is characterized in that described tensio-active agent comprises Soxylat A 25-7, Sodium dodecylbenzene sulfonate, sodium stearate or potassium stearate.
6. the method for making of chlorinatedpolyethylene according to claim 4-alkyl acrylate by graft copolymerization thing is characterized in that described radical initiator comprises di-isopropylbenzene hydroperoxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tertbutyl peroxide or hydrogen phosphide cumene.
7. the method for making of chlorinatedpolyethylene according to claim 4-alkyl acrylate by graft copolymerization thing, the add-on that it is characterized in that described water are 4～6 times of raw material gross weight.
8. the described chlorinatedpolyethylene of claim 1-alkyl acrylate by graft copolymerization thing is as the application of polychloroethylene processing modifier.
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| CN103113687B (en) * | 2012-05-02 | 2013-12-04 | 江苏天腾化工有限公司 | PVC (Polyvinyl Chloride) impact modifier and preparation method thereof |
| CN103130962B (en) * | 2013-03-06 | 2016-12-28 | 曹广文 | Chlorinated polyethylene rubber, butyl acrylate, acrylonitrile, N phenyl maleimide graft copolymer and preparation method thereof |
| CN103755877B (en) * | 2013-12-21 | 2015-12-09 | 山东日科橡塑科技有限公司 | A kind of ACM production technique with high maximum elongation |
| KR101754470B1 (en) * | 2015-06-26 | 2017-07-06 | 주식회사 케이씨씨 | Copolymer of acrylate modified chlorinated polyolefin and primer coat composition for plastic substrate comprising the same |
| CN105504172B (en) * | 2015-12-23 | 2020-08-07 | 河北雄发新材料科技发展有限公司 | Preparation process of modified chlorinated polyethylene for rubber and plastic material |
| CN105693891A (en) * | 2016-04-23 | 2016-06-22 | 山东日科橡塑科技有限公司 | Polyvinyl chloride low temperature toughening modifier and polyvinyl chloride mixture containing same |
| CN112920413B (en) * | 2021-01-29 | 2022-02-22 | 常州爱特恩新材料科技有限公司 | Ionomer type grafted multifunctional material, preparation method thereof and application thereof in PVC (polyvinyl chloride) |
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