CN100372874C - Chlorinated polyethylene with high maximum elongation, and preparation process and application thereof - Google Patents
Chlorinated polyethylene with high maximum elongation, and preparation process and application thereof Download PDFInfo
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- CN100372874C CN100372874C CNB2006100078618A CN200610007861A CN100372874C CN 100372874 C CN100372874 C CN 100372874C CN B2006100078618 A CNB2006100078618 A CN B2006100078618A CN 200610007861 A CN200610007861 A CN 200610007861A CN 100372874 C CN100372874 C CN 100372874C
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- polyethylene
- chlorine
- polyvinyl chloride
- chlorinated polyethylene
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- 239000004709 Chlorinated polyethylene Substances 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 54
- -1 polyethylene Polymers 0.000 claims abstract description 43
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 41
- 239000004698 Polyethylene Substances 0.000 claims abstract description 37
- 229920000573 polyethylene Polymers 0.000 claims abstract description 37
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 64
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 63
- 239000000460 chlorine Substances 0.000 claims description 63
- 238000010792 warming Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 9
- 235000013539 calcium stearate Nutrition 0.000 claims description 9
- 239000008116 calcium stearate Substances 0.000 claims description 9
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000004801 Chlorinated PVC Substances 0.000 claims description 4
- 239000004609 Impact Modifier Substances 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 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 2
- 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
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 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
- 230000035939 shock Effects 0.000 abstract description 35
- 239000011347 resin Substances 0.000 abstract description 32
- 229920005989 resin Polymers 0.000 abstract description 32
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000000806 elastomer Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000012986 modification Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229920001195 polyisoprene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 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
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to chlorinated polyethylene with high maximum elongation, and a preparing method and the application thereof, which belongs to the technical fields of high elastic rubber with weatherability and the preparation thereof. The chlorinated polyethylene is formed by chlorinating polyethylene. The chlorinated polyethylene is characterized in that part of the chlorinated polyethylene is chlorinated below the fusing point of polyethylene; then, the chlorination reaction is carried out when the temperature raises above the fusing point of polyethylene to obtain elastomer of chlorinated polyethylene whose maximum elongation is larger than 800%. the chlorinated polyethylene can be used as a shock resisting modifying agent of polyvinyl chloride. The chlorinated polyethylene has the advantages of high maximum elongation and good shock resisting performance. The chlorinated polyethylene can be used for processing and modifying polyvinyl chloride resin and can have an excellent shock resisting performance under the condition of low dosage. The proportioning of the dosage is about 2 to 25% according to the weight of the polyvinyl chloride resin; a use method is the same with that of the current modifying agent. Because the dosage of the chlorinated polyethylene is low, the problem of the separation of the chlorinated polyethylene in polyvinyl chloride because of excess chlorinated polyethylene is solved; simultaneously, the mechanical performance and the weatherability of the polyvinyl chloride resin are improved.
Description
Technical field
The invention belongs to weathering resistance high elastic rubber and preparing technical field thereof, relate in particular to a kind of impact-resistant modified chlorinatedpolyethylene of polyvinyl chloride (PVC) RESINS that is applied to high maximum elongation, with and its production and application.
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 divinyl one vinylbenzene monomethyl methyl acrylate, 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-No. 28117 communiques) 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, the polyvinyl chloride (PVC) Compound that shock resistance is good and cheap.
The contriver thinks why CPE can improve the resistance to impact shock of PVC, is because CPE has caoutchouc elasticity.The effective means that improves the CPE resistance to impact shock is for improving the caoutchouc elasticity performance of CPE, the caoutchouc elasticity performance is relevant with the tensile yield of rubber, in general, tensile yield is big more, the elastic performance of rubber is good more, then the shock resistance of CPE is just good more, and also nobody thinks that the shock resistance of CPE is directly proportional with the tensile yield of CPE up to now, and also nobody carries out the research of this respect.Find that by studying us the tensile yield of CPE is relevant with the chlorination uniformity coefficient of CPE, even more then its tensile yield that polyethylene is chlorinated is big more, and the chlorating uniformity coefficient has confidential relation with reaction process.
Summary of the invention
The purpose of this invention is to provide a kind of chlorinatedpolyethylene elastomerics and preparation method thereof and as the application of polyvinyl chloride (PVC) RESINS impact modifier with high maximum elongation, this chlorinatedpolyethylene has good powder fluidity, can effectively improve the shock resistance of polyvinyl chloride (PVC) RESINS, solve the problem of the shock resistance difference that exists when using traditional CPE to carry out polyvinyl chloride resin modification.
The technical solution used in the present invention is as follows:
A kind of chlorinatedpolyethylene with high maximum elongation, obtain by the polyethylene chlorination, it is characterized in that this chlorinatedpolyethylene is after poly fusing point is with the lower section chlorination, be warming up to and carry out chlorination reaction more than the poly fusing point, the tensile yield that obtains is greater than the high-elastic gonosome of 800% chlorinatedpolyethylene.
Described chlorinated polyvinyl chloride is that the weight percentage of chlorine is 33～42% chlorinatedpolyethylene.
Described polyethylene is a high density polyethylene(HDPE).
The preparation method of the chlorinated polyvinyl chloride of this high maximum elongation is, in water, add polyethylene, tensio-active agent, dispersion agent and radical initiator, the limit heating edge feeds part chlorine and carry out chlorination reaction below poly melting temperature, make poly surface chlorination hardening, be rapidly heated then more than the poly fusing point, and feeding residue chlorine carries out chlorination reaction, the logical chlorine dose of carrying out chlorination reaction more than the polyethylene fusing point accounts for more than 45% of total chlorine consumption, obtains the high-elastic gonosome of chlorinatedpolyethylene.
The preparation method of the chlorinatedpolyethylene of this high maximum elongation specifically comprises the steps:
(1) water of 500～700 weight parts, the polyethylene of 58～67 weight parts and the tensio-active agent of 0.05～0.15 weight part and the dispersion agent of 0.05～0.3 weight part are put into reactor;
(2) add the radical initiator of 0.07～0.5 weight part and be warming up to 70～80 ℃ sub polyethylene is dispersed in the water under agitation condition, be warming up to 110 ℃ then, the chlorine that feeds 15～30 weight parts in the temperature-rise period carries out chlorination reaction;
(3) be warming up to 130 ℃ again, feed the chlorine of 6～17 weight parts in the temperature-rise period, be warming up to the chlorine that feeds 20～63 weight parts between 130～135 ℃, wherein the chlorine of last stage feeding should account for more than 45% of total chlorine consumption;
(4) chlorination reaction finishes, and obtains the high-elastic gonosome of chlorinatedpolyethylene after neutralization, washing and drying;
(5) calcium stearate of high-elastic gonosome of the chlorinatedpolyethylene of 100 weight parts and 1～5 weight part and/or lime carbonate are joined the homogenizer high speed and mix, promptly obtain tensile yield greater than 800% chlorinatedpolyethylene.
Described polyethylene is a high density polyethylene(HDPE).
Described tensio-active agent comprises Soxylat A 25-7, Sodium dodecylbenzene sulfonate, sodium stearate and potassium stearate.
Described dispersion agent comprises multipolymer, the polyvinylpyrrolidone of methyl methacrylate and methacrylic acid.
Described radical initiator comprises di-isopropylbenzene hydroperoxide, benzoyl peroxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tertbutyl peroxide, hydrogen phosphide cumene.
Described application with chlorinatedpolyethylene of high maximum elongation as The Impact Modifiers for PVC.
Thereby chlorinatedpolyethylene and the polychloroethylene blended intermolecular forces that can effectively reduce chlorinatedpolyethylene improve its resistance to impact shock.Theoretically, the general synthesizing chlorinated poly reaction of polyethylene chlorination is the heterogeneous high molecular weight reactive that carries out in water, different reaction CONTROL PROCESS will influence polyethylene chlorating uniformity coefficient, and the caoutchouc elasticity of the different chlorinatedpolyethylene of chlorination uniformity coefficient is inevitable different with tensile yield.The contriver discovers that even more its tensile yield of chlorination degree is high more, and resistance to impact shock is high more.When the temperature of reaction of chlorination reaction was low, reaction can only be carried out at poly particle surface, so poly chlorination uniformity coefficient is lower.Chlorination reaction temperature is high more, when particularly more than poly fusing point, carrying out chlorination reaction, because chlorine can enter into the inside of fused polyethylene particle, at this moment chlorination reaction not only carries out also carrying out in poly inside on poly surface, so poly chlorination is just even more, the tensile yield of synthetic chlorinatedpolyethylene and resistance to impact shock are just high more.If but chlorination reaction all more than poly fusing point, carry out, chlorination reaction carry out caking phenomenon can appear in the process, production can't normally be carried out.In order to address this problem, the contriver adopts the chlorine that feeds part under the temperature that is lower than the polyethylene fusing point earlier to make poly surface chlorination hardening, be rapidly heated then to more than the poly fusing point (about 130 ℃), feed remaining chlorine again and carry out chlorination reaction, so just can obtain the uniform chlorinatedpolyethylene of chlorination degree.Experiment showed, for the tensile yield that guarantees chlorinatedpolyethylene greater than 800%, the amount that necessarily requires promptly to feed chlorine under the temperature of reaction more than 130 ℃ at poly fusing point accounts for could realizing more than 45% of total logical chlorine dose.If the logical chlorine dose under the temperature of reaction more than 130 ℃ is less than 45% of total chlorine gas amount, then the tensile yield of chlorinatedpolyethylene is difficult to reach 800%, and its shock strength also can reduce.In addition, when the tensile yield of chlorinatedpolyethylene surpasses 800%, the powder fluidity meeting variation and the apparent density of products obtained therefrom reduce, in order to address this problem, the contriver carries out high-speed stirring with the calcium stearate of the chlorinatedpolyethylene of 100 weight parts and 1-5 weight part and/or lime carbonate with homogenizer and mixes, and improves the apparent density and the powder fluidity of product with this.
When adopting the synthesis technique of traditional chlorinatedpolyethylene, chlorine feeding amount under the temperature of reaction more than 130 ℃ is less than 45% of total chlorine feeding amount, so the tensile yield of the chlorinatedpolyethylene that obtains is generally less than 800%, the resistance to impact shock of the mixture of the polyvinyl chloride of its modification is also undesirable.The contriver finds by changing reaction process, the feeding amount of the chlorine when the temperature of reaction more than 130 ℃ is directly proportional with the tensile yield of resulting chlorinatedpolyethylene, the feeding amount of the chlorine when reducing the temperature of reaction below 130 ℃ and the chlorine feeding amount when increasing temperature of reaction more than 130 ℃, the feeding amount of the chlorine when promptly guaranteeing the temperature of reaction more than 130 ℃ accounts for the ratio of feeding amount of total chlorine greater than 45%, just can obtain a kind of tensile yield greater than 800%, and can increase substantially the novel chlorinatedpolyethylene of the resistance to impact shock of polyvinyl chloride.
This chlorinatedpolyethylene has higher tensile yield and favorable shock resistance, can be used for the processing modified of polyvinyl chloride (PVC) RESINS, and just can play excellent shock resistance under the less situation of consumption.Its consumption proportion is about 2～25% of polyvinyl chloride (PVC) RESINS weight, and using method is identical with existing properties-correcting agent.Because the consumption of chlorinatedpolyethylene is less, has eliminated because of the excessive problem of separating out in polyvinyl chloride of chlorinatedpolyethylene, this has also improved the mechanical property and the weather resistance of polyvinyl chloride (PVC) RESINS simultaneously.
Beneficial effect of the present invention is that this chlorinatedpolyethylene has chlorination uniformity coefficient, tensile yield and characteristic excellent in cushion effect, and has good powder fluidity, and its preparation technology controls simply, is convenient to suitability for industrialized production.This chlorinatedpolyethylene can effectively improve the shock resistance and the weathering resistance of polyvinyl chloride (PVC) RESINS, and has cheap advantage.
Embodiment
The invention will be further elaborated below in conjunction with embodiment, but the present invention is not limited to these embodiment.
Embodiment 1 is with the water of 600 weight parts, the methacrylic acid of the polyethylene of 65 weight parts and 0.1 weight part polyoxyethylene groups ether and 0.2 weight part and the multipolymer of methyl methacrylate are put into reactor, open the benzoyl peroxide that stirs adding 0.15 weight part and be warming up to 75 ℃ simultaneously, after polyethylene is scattered in the water uniformly, the chlorine that begins to feed 20 weight parts carries out chlorination reaction, and be warming up to 110 ℃ gradually, the chlorine that feeds 15 weight parts again is warming up to 130 ℃ simultaneously, temperature is warming up to 135 ℃ by 130 ℃ proceeds reaction, feed the chlorine of remaining 35 weight parts in the temperature-rise period, react completely after neutralize, washing, obtain the chlorinatedpolyethylene of 100 weight parts behind the boiled bed drying, again the chlorinatedpolyethylene of 100 above-mentioned weight parts and the calcium stearate and the 2 weight lime carbonate of 2 weight parts are joined homogenizer after high-speed mixing, promptly obtain tensile yield and be the chlorinatedpolyethylene of 900% good fluidity, the weight percentage of chlorine is 35% in this chlorinatedpolyethylene.
(2) modified PVC resin
Above-mentioned chlorinatedpolyethylene (CPE) and polyvinyl chloride (PVC) RESINS are pressed column weight amount ratio prescription batching:
92.5 parts of polyvinyl chloride (PVC) RESINS
7.5 parts of CPE
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 sheet material.The test of resistance to impact shock is undertaken by the method shown in the GB/T8814 standard.
Among this chlorinatedpolyethylene preparation technology, the logical chlorine dose in differing temps zone promptly sees Table 1 with the tensile yield of this chlorinatedpolyethylene and the resistance to impact shock data of the polyvinyl chloride (PVC) RESINS after the modification.
Embodiment 2-5 adopts the method identical with embodiment 1 to prepare chlorinatedpolyethylene, but wherein 75 ℃ to 110 ℃, the amount of chlorine that feeds between 110 ℃ to 130 ℃ and 130 ℃ to 135 ℃ (leading to chlorine dose) accounts for the weight percent difference of total chlorine gas amount.Preparation modified PVC resin mixture process is with embodiment 1.Each experimental data sees Table 1.
Comparative Examples 1-3 adopts the method identical with embodiment 1 to prepare chlorinatedpolyethylene, but wherein 75 ℃ to 110 ℃, the amount of chlorine that feeds between 110 ℃ to 130 ℃ and 130 ℃ to 135 ℃ (leading to chlorine dose) accounts for the weight percent difference of total chlorine gas amount.Preparation modified PVC resin mixture process is with embodiment 1.Each experimental data sees Table 1.
The resistance to impact shock of polyvinyl chloride (PVC) RESINS is pressed the method test shown in the GB/T8814 standard.
The tensile yield of chlorinatedpolyethylene is tested by the method shown in the GB/T528-1998 standard.
The tensile yield data of the logical chlorine dose in differing temps zone and chlorinatedpolyethylene in table 1 embodiment and the comparative example
Be the data of resistance to impact shock of the polyvinyl chloride (PVC) Compound of modification
The tensile yield of chlorinatedpolyethylene CPE is relevant with the synthetic reaction process condition as can be seen from Table 1, special relevant with the logical chlorine dose of differential responses temperature province, 130 ℃ to 135 ℃ logical chlorine dose is high more, the tensile yield of resulting CPE is high more, and the resistance to impact shock of the PVC after the CPE modification that tensile yield is high is also high more simultaneously.130 ℃ to 135 ℃ logical chlorine dose will be lower than embodiment in the comparative example, so its tensile yield just is lower than embodiment.Like this by increasing in the polyethylene chlorination process the i.e. logical chlorine dose between 130 ℃ to 135 ℃ of high temperature section, we just can obtain tensile yield greater than 800% CPE, and the resistance to impact shock of the PVC of the CPE modification that the while tensile yield is high more is high more.
Synthesizing of embodiment 6 chlorinatedpolyethylenees
Water with 700 weight parts, the polyvinylpyrrolidone of the Soxylat A 25-7 of the polyethylene of 60 weight parts and 0.15 weight part and 0.2 weight part is put into reactor, open the hydrogen phosphide cumene that stirs adding 0.35 weight part and be warming up to 75 ℃ simultaneously, after polyethylene is scattered in the water uniformly, the chlorine that begins to feed 20 weight parts is warming up to 110 ℃ of chlorine that feed 15 weight parts more simultaneously and is warming up to 130～135 ℃ of chlorine that feed remaining 45 weight parts more simultaneously, react completely after neutralize, washing, obtain the snappiness chlorinatedpolyethylene behind the boiled bed drying, again the calcium stearate of the chlorinatedpolyethylene of 100 above-mentioned weight parts and 2 weight parts and 2 weight lime carbonate are joined homogenizer and after high-speed mixing, promptly obtain the chlorinatedpolyethylene that tensile yield is 930% good fluidity.
Polyvinyl chloride (PVC) RESINS is carried out the modification experiment, above-mentioned chlorinatedpolyethylene (CPE) and polyvinyl chloride (PVC) RESINS is 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.After tested, this polyvinyl chloride (PVC) RESINS mixture has good resistance to impact shock, can reach 20.6KJ/M
2
Embodiment 7 is with the water of 550 weight parts, the Soxylat A 25-7 of the polyethylene of 63 weight parts and 0.1 weight part, 0.04 the polyvinylpyrrolidone of the sodium stearate of weight part and 0.2 weight part is put into reactor, open the tertbutyl peroxide that stirs adding 0.3 weight part and be warming up to 75 ℃ simultaneously, after polyethylene is scattered in the water uniformly, the chlorine that begins to feed 20 weight parts is warming up to 110 ℃ of chlorine that feed 13 weight parts more simultaneously and is warming up to 130～135 ℃ of chlorine that feed remaining 41 weight parts more simultaneously, react completely after neutralize, washing, obtain the chlorinatedpolyethylene of 100 weight parts behind the boiled bed drying, again the calcium stearate of the chlorinatedpolyethylene of 100 above-mentioned weight parts and 2 weight parts and 2 weight lime carbonate are joined homogenizer and after high-speed mixing, promptly obtain the chlorinatedpolyethylene that tensile yield is 1000% good fluidity.
Adopt the method identical to be used for the modification of polyvinyl chloride (PVC) RESINS, but wherein CPE adopt the product 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 and higher resistance to impact shock.
Embodiment 8 is with the water of 500 weight parts, the polyvinylpyrrolidone of the sodium stearate of the polyethylene of 58 weight parts and 0.05 weight part and 0.05 weight part is put into reactor, open the tertbutyl peroxide that stirs adding 0.5 weight part and be warming up to 70 ℃ simultaneously, after polyethylene is scattered in the water uniformly, the chlorine that begins to feed 15 weight parts is warming up to 110 ℃ of chlorine that feed 6 weight parts more simultaneously and is warming up to 130～135 ℃ of chlorine that feed remaining 20 weight parts more simultaneously, react completely after neutralize, washing, obtain the chlorinatedpolyethylene of 100 weight parts behind the boiled bed drying, again the calcium stearate of the chlorinatedpolyethylene of 100 above-mentioned weight parts and 5 weight parts is joined homogenizer and after high-speed mixing, promptly obtain the chlorinatedpolyethylene that tensile yield is 800% good fluidity.
Adopt the method identical to be used for the modification of polyvinyl chloride (PVC) RESINS, but wherein CPE adopt the product 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 and higher resistance to impact shock.
Embodiment 9 is with the water of 700 weight parts, the polyvinylpyrrolidone of the Soxylat A 25-7 of the polyethylene of 67 weight parts and 0.15 weight part and 0.3 weight part is put into reactor, open the hydrogen phosphide cumene that stirs adding 0.07 weight part and be warming up to 80 ℃ simultaneously, after polyethylene is scattered in the water uniformly, the chlorine that begins to feed 30 weight parts is warming up to 110 ℃ of chlorine that feed 17 weight parts more simultaneously and is warming up to 130～135 ℃ of chlorine that feed remaining 63 weight parts more simultaneously, react completely after neutralize, washing, obtain the snappiness chlorinatedpolyethylene behind the boiled bed drying, again the chlorinatedpolyethylene of 100 above-mentioned weight parts and 2 weight lime carbonate are joined homogenizer and after high-speed mixing, promptly obtain the chlorinatedpolyethylene that tensile yield is 1200% good fluidity.
Claims (10)
1. chlorinatedpolyethylene with high maximum elongation, obtain by the polyethylene chlorination, it is characterized in that this chlorinatedpolyethylene is after poly fusing point is with the lower section chlorination, be warming up to and carry out chlorination reaction more than the poly fusing point, the tensile yield that obtains is greater than the high-elastic gonosome of 800% chlorinatedpolyethylene; Described chlorinatedpolyethylene is prepared by following method: add polyethylene, tensio-active agent, dispersion agent and radical initiator in water, heat temperature raising limit, limit feeds part chlorine and carry out chlorination reaction below poly melting temperature, make poly surface chlorination hardening, be rapidly heated then more than the poly fusing point, and feeding residue chlorine carries out chlorination reaction in temperature-rise period, the logical chlorine dose of carrying out chlorination reaction more than the polyethylene fusing point accounts for more than 45% of total chlorine consumption, obtains the high-elastic gonosome of chlorinatedpolyethylene.
2. the chlorinatedpolyethylene with high maximum elongation according to claim 1 is characterized in that described chlorinated polyvinyl chloride is that the weight percentage of chlorine is 33～42% chlorinatedpolyethylene.
3. the chlorinatedpolyethylene with high maximum elongation according to claim 1 is characterized in that described polyethylene is a high density polyethylene(HDPE).
4. the preparation method of the chlorinated polyvinyl chloride of the described high maximum elongation of claim 1, it is characterized in that in water, adding polyethylene, tensio-active agent, dispersion agent and radical initiator, heat temperature raising limit, limit feeds part chlorine and carry out chlorination reaction below poly melting temperature, make poly surface chlorination hardening, be rapidly heated then more than the poly fusing point, and feeding residue chlorine carries out chlorination reaction in temperature-rise period, the logical chlorine dose of carrying out chlorination reaction more than the polyethylene fusing point accounts for more than 45% of total chlorine consumption, obtains the high-elastic gonosome of chlorinatedpolyethylene.
5. the preparation method of the chlorinatedpolyethylene of high maximum elongation according to claim 4 is characterized in that specifically comprising being prepared as follows step:
(1) water of 500～700 weight parts, the polyethylene of 58～67 weight parts and the tensio-active agent of 0.05～0.15 weight part and the dispersion agent of 0.05～0.3 weight part are put into reactor;
(2) add the radical initiator of 0.07～0.5 weight part and be warming up to 70～80 ℃ sub polyethylene is dispersed in the water under agitation condition, be warming up to 110 ℃ then, the chlorine that feeds 15～30 weight parts in the temperature-rise period carries out chlorination reaction;
(3) be warming up to 130 ℃ again, feed the chlorine of 6～17 weight parts in the temperature-rise period, be warming up to the chlorine that feeds 20～63 weight parts between 130～135 ℃, wherein the chlorine of last stage feeding should account for more than 45% of total chlorine consumption;
(4) chlorination reaction finishes, and obtains the high-elastic gonosome of chlorinatedpolyethylene after neutralization, washing and drying;
(5) calcium stearate of high-elastic gonosome of the chlorinatedpolyethylene of 100 weight parts and 1～5 weight part and/or lime carbonate are joined the homogenizer high speed and mix, promptly obtain tensile yield greater than 800% chlorinatedpolyethylene.
6. according to the preparation method of the chlorinatedpolyethylene of claim 4 or 5 described high maximum elongations, it is characterized in that described polyethylene is a high density polyethylene(HDPE).
7. according to the preparation method of the chlorinatedpolyethylene of claim 4 or 5 described high maximum elongations, it is characterized in that described tensio-active agent comprises Soxylat A 25-7, Sodium dodecylbenzene sulfonate, sodium stearate and potassium stearate.
8. according to the preparation method of the chlorinatedpolyethylene of claim 4 or 5 described high maximum elongations, it is characterized in that described dispersion agent comprises multipolymer, the polyvinylpyrrolidone of methyl methacrylate and methacrylic acid.
9. according to the preparation method of the chlorinatedpolyethylene of claim 4 or 5 described high maximum elongations, it is characterized in that described radical initiator comprises di-isopropylbenzene hydroperoxide, benzoyl peroxide, Potassium Persulphate, ammonium persulphate, Sodium Persulfate, tertbutyl peroxide, hydrogen phosphide cumene.
10. the described application of claim 1 with chlorinatedpolyethylene of high maximum elongation as The Impact Modifiers for PVC.
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| CN104193856B (en) * | 2014-09-04 | 2015-05-27 | 江苏科利新材料有限公司 | Preparation method for chlorinated polyethylene rubber |
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| CN107200943A (en) * | 2017-07-24 | 2017-09-26 | 河北泰纳新材料科技有限公司 | A kind of preparation method of haloflex |
| CN107602742A (en) * | 2017-09-26 | 2018-01-19 | 山东三义实业股份有限公司 | A kind of superpower super elongation haloflex and preparation method thereof |
| CN112375326B (en) * | 2021-01-12 | 2021-03-16 | 潍坊硕邑化学有限公司 | Preparation method of chlorinated polyethylene with high elongation at break |
| CN118459902B (en) * | 2024-07-15 | 2024-09-27 | 山东三义集团股份有限公司 | Preparation method of high-elongation-at-break chlorinated polyethylene |
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