CN1916046A - Method for preparing impact modifier of polyvinyl chloride in new type structure of hud - Google Patents
Method for preparing impact modifier of polyvinyl chloride in new type structure of hud Download PDFInfo
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- CN1916046A CN1916046A CN 200610112208 CN200610112208A CN1916046A CN 1916046 A CN1916046 A CN 1916046A CN 200610112208 CN200610112208 CN 200610112208 CN 200610112208 A CN200610112208 A CN 200610112208A CN 1916046 A CN1916046 A CN 1916046A
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- Prior art keywords
- polyvinyl chloride
- monomer
- acrylate
- preparation
- emulsion
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- Granted
Links
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 72
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 65
- 239000004609 Impact Modifier Substances 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 238000002360 preparation method Methods 0.000 claims abstract description 58
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 23
- 230000007704 transition Effects 0.000 claims abstract description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 5
- 239000000806 elastomer Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 65
- 239000011246 composite particle Substances 0.000 claims description 43
- 150000002148 esters Chemical class 0.000 claims description 43
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 33
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 26
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- -1 Acrylic ester Chemical class 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 5
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 230000003252 repetitive effect Effects 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 229920000578 graft copolymer Polymers 0.000 claims 1
- 229920000126 latex Polymers 0.000 abstract description 39
- 239000004816 latex Substances 0.000 abstract description 39
- 239000000463 material Substances 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 14
- 229920005989 resin Polymers 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000003607 modifier Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920006037 cross link polymer Polymers 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 2
- 229940070721 polyacrylate Drugs 0.000 description 26
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 26
- 230000008859 change Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000009413 insulation Methods 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 208000014347 autosomal dominant hyaline body myopathy Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- JITOKQVGRJSHHA-UHFFFAOYSA-M monosodium methyl arsenate Chemical compound [Na+].C[As](O)([O-])=O JITOKQVGRJSHHA-UHFFFAOYSA-M 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920005559 polyacrylic rubber Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 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
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
本发明涉及一种核壳结构聚氯乙烯抗冲改性剂的制备方法。该方法采用丙烯酸酯类单体为主要原料，通过半连续加料方式的种子乳液聚合制得具有弹性体内核－过渡层结构的交联聚合物胶乳，然后在上述胶乳存在下，向高压釜中加入氯乙烯单体及其与其它单体共混物进行乳液聚合，制得具有过渡层结构的核壳结构聚氯乙烯抗冲改性剂。该方法制得的改性剂以聚氯乙烯为薄壳，大大改善了共混时改性剂与PVC树脂基体之间的相容性，有效发挥了聚丙烯酸酯类弹性体内核和功能性官能团的特性作用，从而提高聚氯乙烯材料的缺口抗冲性能、耐候、以及耐热稳定性，并且该方法生产成本较纯聚丙烯酸酯改性剂降低，提高了PVC树脂的附加值，拓宽了聚氯乙烯树脂的应用领域与应用地区。The invention relates to a preparation method of a polyvinyl chloride impact modifier with a core-shell structure. The method adopts acrylate monomer as the main raw material, and prepares cross-linked polymer latex with elastomer core-transition layer structure through seed emulsion polymerization in a semi-continuous feeding mode, and then, in the presence of the above-mentioned latex, adds Vinyl chloride monomer and its blend with other monomers are emulsion polymerized to prepare a core-shell structure polyvinyl chloride impact modifier with a transition layer structure. The modifier prepared by this method uses polyvinyl chloride as a thin shell, which greatly improves the compatibility between the modifier and the PVC resin matrix during blending, and effectively utilizes the polyacrylate elastomer core and functional functional groups. The characteristics of the polyvinyl chloride material, thereby improving the notch impact resistance, weather resistance, and heat resistance stability of the polyvinyl chloride material, and the production cost of this method is lower than that of pure polyacrylate modifiers, which increases the added value of PVC resin and broadens the scope of polyvinyl chloride. Application field and application area of vinyl chloride resin.
Description
Divisional original case: impact modifier of polyvinyl chloride in new type structure of hud and its production and application, application number 200510015287.6, September 29 2005 applying date)
Technical field
The invention belongs to the preparation method of general polyvinyl chloride (PVC) RESINS impact modifier, particularly a kind of impact modifier of polyvinyl chloride in new type structure of hud and its production and application.
Background technology
Polyvinyl chloride (PVC) is as Application and Development large general-purpose plastics kind the earliest, have over-all propertieies such as good rigidity, erosion resistance, electric insulating quality and cheap price because of it and be widely used in every field, its output occupies second in macromolecular material.Yet PVC exists shortcomings such as thermostability and poor in processability, notched Izod impact strength be low.For overcoming these shortcomings, people do not have interruption all the time to the research of PVC modification for a long time.Present employed method of modifying mainly is (grafting) copolymerization chemical modification and the modification of mechanical blending physics, and blending method is because of its easy extremely people favor.Wherein acrylic modifier (ACR) is with fastest developing speed best with application in the various properties-correcting agent of PVC.
Generally speaking, synthetic ACR stratum nucleare is made up of butyl polyacrylate (PBA) usually at present, and shell mainly is polymethylmethacrylate (PMMA).Its PMMA shell mainly is to play the effect that increases consistency between ACR and the PVC, and very little to the toughening effect of PVC.Result of study shows: the toughening effect of ACR depends primarily on the content of rubber phase.Under the identical rubber content, pure nuclear PBA has higher toughening efficiency than nuclear-shell ACR.Therefore, nuclear-shell ACR makes corresponding the reducing of effective volume of its rubber phase because of the existence of transition layer, and toughening modifying efficient reduces, and production cost increases.Simultaneously low by the PVC material at low temperature notched Izod impact strength of nuclear-shell ACR modification, this material is restricted in the use of the open air of cold district.
Disclosed among the Chinese patent CN 1418898A is a kind of preparation method of high-impact polyacrylate composite particles grafting vinyl chloride emulsion resin.What it adopted is the method that directly obtains the modified emulsion polyvinyl chloride (PVC) RESINS by ACR situ-formed graft vinylchlorid, and its ACR is not more than 20: 80 with the nucleocapsid of vinylchlorid than all, and for PVC, the production cost of compound resin is higher.
Disclosed among the Chinese patent CN 1488657A is that nucleocapsid structure polyvinyl chloride impact hits properties-correcting agent and its production and application.It adopts the homopolymer of divinyl or multipolymer to be nuclear, and polymethylmethacrylate is a shell, and the nucleocapsid ratio is 50～93: 7～50, is applicable to polycarbonate, polybutylene terephthalate and Styrene-Acrylnitrile Copolymer system.But owing to contain two keys in the polyhutadiene molecule, be the stratum nucleare polymkeric substance with it, the easy variable color of properties-correcting agent, weathering resistance is not good, and properties-correcting agent adding umber is more in the blend process, and cost is increased.
Summary of the invention
With regard to the above-mentioned problem of mentioning, the granulating difficulty was prone to caking and coalescence phenomenon problem when the prepared polyacrylate/polyvinyl chloride impact modifier of the present invention was attempted to solve by the direct breakdown of emulsion of pure polyacrylic rubber latex; Particle dispersive non-uniformity problem in matrix resin in the blend course of processing; The not good problem of consistency and interfacial adhesion between properties-correcting agent and the modified matrix; General polyvinyl chloride (PVC) RESINS weathering resistance and poor impact toughness, thermotolerance and poor heat stability problem, and problem such as traditional ACR properties-correcting agent production cost height.
Technical scheme:
Impact modifier of polyvinyl chloride in new type structure of hud, it is characterized in that this properties-correcting agent composite particles is made of rubber elastomer kernel and plastics shell, the properties-correcting agent particle core is mainly cross-linking type polyacrylate(s) elastomerics, account for 20～80% of composite particles gross weight, shell plastics phase component be ryuron or with vinylchlorid be main component with other monomeric multipolymer, account for 20～80% of composite particles gross weight.
The preparation method that impact modifier of polyvinyl chloride in new type structure of hud adopted is that to adopt acrylic ester monomer be main raw material, and the seeded emulsion polymerization by the semi-continuous charging mode makes the cross-linked polymer latex with pure nuclear or nucleocapsid structure.In the presence of above-mentioned latex, in autoclave, add vinyl chloride monomer and carry out letex polymerization then, make polyacrylate/polyvinyl chloride composite particles properties-correcting agent with nucleocapsid structure.Its preparation method may further comprise the steps:
(1) preparation of poly acrylate composite emulsion
A. the preparation of seed emulsion
Get rid of oxygen to reaction system drum nitrogen, carry out emulsion polymerization by following composition and consumption:
The composition parts by weight
Deionized water 200
The mixed solution 17.7～20.3 of seed comonomer and linking agent
Emulsifying agent 0.1～1.2
Initiator 0.2～0.4
Heated up in the above-mentioned reaction mixture back that stirs, in 60～90 ℃ of reactions 1～4 hour down;
Described emulsifying agent is a sodium lauryl sulphate, and initiator is a Potassium Persulphate, and the seed comonomer is an acrylate co-monomers in the mixed solution of seed comonomer and linking agent, and acrylate co-monomers is 17.5: 0.2～2.8 with the ratio of cross-linked dosage
B. the preparation of stratum nucleare emulsion
The composition parts by weight
Nuclear layer monomer and linking agent mixed solution 75.8～87.0
Emulsifying agent 0.1～1.2
Initiator 0.2～0.4
Stablizer 0～9.5
Disposable adding to guarantee the stable of emulsion system, continues the disposable initiator solution of adding or drip the stratum nucleare formula ratio in this system according to the emulsifier solution of stratum nucleare formula rate amount after 15～20 minutes in the seed emulsion that is obtained by a. step; The mode that adopts one-time continuous to drip simultaneously or drip in two steps drips the acrylate co-monomers and the mixed solution of linking agent of stratum nucleare prescription, and the dropping time is 0.5～3 hour, after dropwising, with the same temperature of a step under continuation polyreaction 1～4 hour;
Described emulsifying agent is a sodium lauryl sulphate, and initiator is a Potassium Persulphate, and wherein nuclear layer monomer is an acrylate co-monomers in nuclear layer monomer and the linking agent mixed solution, and acrylate co-monomers is 75: 0.8～12 with the dosage of crosslinking agent ratio
C. the preparation of shell emulsion
The composition parts by weight
Esters of acrylic acid cross-linkable monomer 0～37.0
Initiator 0.1～0.4
Emulsifying agent 0.4～1.2
After above-mentioned b. reaction finishes, thermal reacting for two hours, wherein after 1.5 hours, to the disposable aqueous solution of adding shell formula rate amount emulsifying agent of this system, the disposable aqueous solution of adding initiator in the shell prescription drips the monomer that shell is filled a prescription simultaneously after 15～20 minutes, and the dropping time is 0.5～3 hour, after dropwising, continue with a. step uniform temp under reacted 1～4 hour;
Described emulsifying agent is a sodium lauryl sulphate, and initiator is a Potassium Persulphate,
(2) has the preparation of middle layer or transition layer poly acrylate composite emulsion
Preparation with middle layer or transition layer poly acrylate composite emulsion is at above-mentioned a, on the b reaction basis, after promptly obtaining the seed emulsion of step a., when preparation stratum nucleare emulsion, in system, drip most nuclear layer monomer earlier, after treating that monomer dropping finishes, in residue small portion nuclear layer monomer, add and carry out copolyreaction according to selected monomer, linking agent, the stablizer that has functional groups of experimental design;
(3) the vinyl chloride monomer graft polymerization on polyacrylic ester composite particles surface
1. the polyacrylic ester composite particles emulsion with step (1) a.b. or step (2) gained joins in the autoclave, adds other component simultaneously, and the compositing formula of graft polymerization reaction mixed solution is as follows:
The composition parts by weight
Deionized water 300～800
Emulsifying agent 0～1.2
Initiator 0.5～1.2
Composite particles emulsion 350～500
PH regulator agent 9～25
Acrylic ester copolymerization monomer 0～84
Vinyl chloride monomer 90～300
Reaction system is airtight, vacuumize, fill nitrogen, exhaust, after the repetitive operation three times, add vinyl chloride monomer, in 40～70 ℃ of following polymerizations 4～30 hours, polymerization pressure is at 0.4～1.2MPa, after 0.2～0.6MPa has fallen in question response pressure, the fast cooling termination reaction, remove unreacted vinyl chloride monomer, the discharging sampling obtains hud typed polyacrylate/polyvinyl chloride composite particles properties-correcting agent with the freezing breakdown of emulsion of prepared vinylchlorid graftomer emulsion, filtration, washing, drying, and the nucleocapsid ratio is 20: 80～80: 20;
Emulsifying agent described in the above-mentioned preparation process is a sodium lauryl sulphate, initiator is a Potassium Persulphate, and seed a and the described acrylate monomer of stratum nucleare b refer to other acrylate of butyl acrylate (BA), 2-EHA (EHA) or second-order transition temperature Tg＜-10 ℃ and their blend; Particularly butyl acrylate and 2-EHA copolymerized monomer mixture, its weight ratio is 100～0: 0～100, and related acrylate monomer refers to other (methyl) acrylate of methyl methacrylate, ethyl propenoate, vinylformic acid double cyclopentenyl ester or second-order transition temperature Tg＞-10 ℃ in the shell; In the vinylchlorid graft polymerization reaction, the polyacrylic ester stratum nucleare is 20～80: 80～20 with the nucleocapsid ratio of polyvinyl chloride shell; Used pH regulator agent is ten water Sodium Tetraboratees, sodium bicarbonate, sodium hydroxide, yellow soda ash, and the concentration of sodium hydroxide solution is 0.5～10%, and the pH scope is 6～12;
Or 2. above-mentioned composite particles emulsion in is 1. changed into the composite particles emulsion of step (1) c. gained, and all the other are operated with 1. identical, and gained is a three-layer nuclear shell type polyacrylate/polyvinyl chloride composite particles properties-correcting agent;
In above-mentioned 1 (3) preparation process the grafting vinyl chloride shell consist of ryuron and based on the vinylchlorid composition with other monomeric multipolymer, and nucleocapsid is than more than or equal to 50: 50;
Seed a and the described acrylate monomer of stratum nucleare b refer to other acrylate of butyl acrylate (BA), 2-EHA (EHA) or second-order transition temperature Tg＜-10 ℃ and their blend in above-mentioned preparation method;
Selected linking agent is the acrylic ester cross-linking agent that has two or more active identical or inequality pair keys in operation steps among the above-mentioned preparation method (1) and (2), be 1,4 butanediol diacrylate (BDDA), allyl methacrylate(AMA) (ALMA), Viscoat 295 (TMPTA), trimethylolpropane trimethacrylate (TMPTMA) or vinylformic acid double cyclopentenyl ester (DCPA);
The monomer that has functional groups of middle layer or transition layer is to have sterically hindered (methyl) vinylformic acid double cyclopentenyl ester, allyl methacrylate(AMA) (ALMA) than macoradical, have the terminal hydroxy group organic block, have the acrylate of soft segment side group or have heat-resisting group in above-mentioned preparation method, and the acrylate that has terminal hydroxy group organic block or soft segment side group is the organo-siloxane of acrylated, methacrylic acid (3-trimethoxy silicon) propyl ester (MSMA), vinyltriethoxysilane (VTES); The N-substituted maleimide amine or the Phthalic acid, diallyl ester that have heat-resisting group;
The middle layer in step in above-mentioned preparation method (1) b and (2) or the stablizer that has functional groups of transition layer are the esters of acrylic acid organotin stabilizer that contains the organotin atom: dimercapto 2-ethyl hexyl ethanoate dioctyltin or maleic acid ester butyl tin (ZT-203);
The vinyl chloride monomer feed way comprises with the continuous charging and the disposable gap of certain speed reinforced in the present invention.In the process of this properties-correcting agent of preparation, preferentially select the continuous charging mode for use.
Novel The Impact Modifiers for PVC involved in the present invention, it is applicable to the polyvinyl chloride (PVC) RESINS blending modification system, during blend in per 100 parts of polyvinyl chloride (PVC) RESINS add-on be 3～12 parts anti-impact modifier.
Beneficial effect:
Our polyacrylic ester that adopts butyl acrylate (BA), Isooctyl acrylate monomer (EHA) or both multipolymers etc. to have lower glass transition temperatures (Tg≤-50 ℃) is a kernel in the present invention, being the shell composition with PVC prepares the impact modifier of polyvinyl chloride of novel big nucleocapsid ratio by seeded emulsion polymerization, again the performance by the blend method modified polyvinyl chloride.This novel properties-correcting agent, owing to directly form as shell with polyvinyl chloride, its shell (PVC) can be compatible fully with matrix polyvinyl chloride resin on the one hand, therefore properties-correcting agent disperses uneven problem in the time of can effectively solving mechanical blending in matrix resin, because the existence of stratum nucleare polyacrylic ester and shell vinylchlorid chemical graft multipolymer can obviously increase the alternate interface binding power of rubber phase and matrix PVC two, improve the consistency between rubber phase and the PVC, on the other hand, different with PBA/PMMA (ACR) is: new modified dose transition layer is thin, form a functionalized polypropylene acid esters composite emulsion with thin middle layer unimolecular layer, for providing more active grafting site at its surface grafting vinyl chloride copolymer shell, the grafting of PVC directly occurs on the rubbery kernel rather than on the PMMA.After PVC and the new modified dose of blend, properties-correcting agent shell and matrix PVC are compatible fully, and intermingling material rubber core under extraneous impact force action at first becomes the stress concentration center, and shear deformation even " cavitation " take place in advance, dissipation striking energy effective, the toughening efficiency height of properties-correcting agent.Thereby this material has good low-temperature impact toughness.In addition, can select appropriate functional monomer or material composition as required as unimolecular layer or transition layer, again by the characteristic of functional polymer being directly applied to the modification of polyvinyl chloride with the vinylchlorid grafting, improve the performance such as anti-notch shock toughness, thermotolerance, thermostability, weathering resistance of general polyvinyl chloride (PVC) RESINS, thereby reach the purpose of modified polyvinyl chloride over-all properties.And because this properties-correcting agent is made shell with polyvinyl chloride, production cost is obviously reduced, the preparation of impact modifier of polyvinyl chloride in new type structure of hud can be from microcosmic particle structure design angle, reach the modified effect of expection, for Application Areas and the application area of expanding polyvinyl chloride provides the theory and technology support.Experimental result shows that when properties-correcting agent added umber 3～12 parts of scopes, properties-correcting agent can play toughening effect in the blend process, and the purer polyvinyl chloride of intermingling material notched Izod impact strength is the highest to improve 30 times.
Embodiment
Embodiment 1:
(1) preparation of polyacrylic ester compounded latex
The mixed solution (14g BA, 3.5g EHA, 0.2g BDDA) that in the four-hole reaction flask that reflux exchanger and stirring are housed, adds 200ml deionized water, 0.50g emulsifier sodium lauryl sulfate (SDS) and seed comonomer and linking agent, stir and logical nitrogen under the room temperature, make it fully emulsified.Begin warming-in-water then, simultaneously to the logical water coolant of reflux exchanger.When system temperature reaches 64 ℃, begin to add the required 0.2g initiator potassium persulfate of seed stage (K
2S
2O
8), during the reaction beginning, the system heat release heats up.The question response liquid temp is constant during to 75 ℃, insulation reaction 1 hour.Finish the synthetic of seed emulsion.
Insulation reaction finishes the back to the required emulsifying agent 0.5g of the disposable adding stratum nucleare of system SDS, after 15～20 minutes in this system the disposable initiator 0.4g K that adds or drip the stratum nucleare formula ratio
2S
2O
8, dripping the mixed solution (60g BA, 15g EHA, 0.8g BDDA) of nuclear layer monomer and linking agent simultaneously, the dropping time is 0.5～3 hour.After waiting to dropwise, continue insulation reaction 2 hours, finish the stratum nucleare reaction.Finish reaction, cooling discharge.Obtain the polyacrylic ester compounded latex.
(2) the polyacrylate grafting vinyl chloride composite particles is synthetic
In the stainless steel autoclave that has stirring, charging opening, nitrogen inlet and pump drainage mouth, add 340ml deionized water, 1.0g emulsifying agent SDS, 0.8g initiator potassium persulfate K
2S
2O
8And above-mentioned synthetic contains the polyacrylic ester composite particles latex 500g (calculating according to the solid content of compounded latex (1)) of the about 24g of amount of solid, regulates the pH value of mixed reaction solution 9.5～10.5 with 9g 1%NaOH solution.Vacuumize, inflated with nitrogen, emptying, after the repetitive operation three times, adopt the mode of continuous charging to add the 120g vinyl chloride monomer and under room temperature, stir.Temperature reaction, the controlled polymerization temperature is at 50 ± 0.5 ℃.Reaction pressure is 0.5MPa, when question response still pressure reduces 0.2MPa, and fast cooling, decompression removes unreacted vinyl chloride monomer, discharging, sampling, are drying to obtain polyacrylate/polyvinyl chloride composite particles properties-correcting agent at the freezing breakdown of emulsion of all the other emulsions, and actual nucleocapsid ratio is 50: 50.
The preparation of Mechanics Performance Testing sample: press table 1 prescription, after composite particles properties-correcting agent that embodiment is made and suspension PVC and various auxiliary agent prepare, be placed on and mix 10min. in the high-speed mixer.Then mixed material is placed on the twin-roll machine mixing, 170～175 ℃ of control roller temperature, the thin-pass number of times is 12 times, the about 0.9mm of slice thickness.With going out sheet material on request thickness overlay in the mould, preheating 12min in 180 ℃ of following hydropress is forced into 15MPa pressurize 4min., then is chilled to the room temperature slice under 12MPa, impacts and tensile bars usefulness for tailoring.
Table 1 composite particles properties-correcting agent and PVC processing experiment composition of raw materials
| Component | SLK-1000PVC | The embodiment composite particles | Organotin | Calcium stearate | Stearyl alcohol |
| Mass ratio | 100 | 6 | 2.0 | 0.8 | 0.8 |
Shock strength test: above-mentioned sheet coupon is cut into the notch shock batten by the GB/T1043-93 standard with omnipotent sampling machine, at least after placing 24h, newly think carefully on the ZBC-4 type charpy impact test machine that company limited produces in Shenzhen and to carry out shock test, probe temperature is 23 ℃.
The tensile property test: institute's panel is cut into the dumbbell shape tensile bars by the GB/T1040-92 standard, tests its tensile strength with RGT-10A type microcomputer control electronics universal testing machine down at 23 ℃, draw speed is 20mm/min..
According to the test method of GB-1633-79 softening temperature (dimension card), measure thermoplastics in liquid heat-transfer medium, under certain load and certain constant heatingrate's condition, the temperature when sample is pressed into 1 millimeter by 1 millimeter 2 indentor point.Determining instrument is the thermal distortion of XWB-300F type, vicat softening point temperature determinator.
Concrete test result sees Table 12.
Embodiment 2:
In compounded latex (1) preparation process, change linking agent into allyl methacrylate(AMA) (ALMA), all the other prescriptions and operation are with embodiment 1.
Embodiment 3:
In compounded latex (1) preparation process, change linking agent into vinylformic acid double cyclopentenyl ester (DCPA), all the other prescriptions and operation are with embodiment 1.
Embodiment 4:
(1) preparation of polyacrylic ester compounded latex
The prescription of seed preparatory phase and step are with embodiment 1 (1), but at the stratum nucleare synthesis phase, at first drip 90% (54g BA, 13.5g EHA, 0.7g BDDA) of nuclear layer monomer and linking agent total mass, dropwise the back and mend dropping residue 10% nuclear layer monomer and linking agent mixed solution (6g BA, 1.5g EHA, 2.8g BDDA), dropwise follow-up continuation of insurance temperature reaction 2 hours, finish reaction, cooling discharge.In this example, the cross-linked dosage that the cross-linked dosage of seed and 90% nuclear layer monomer is 1%, 10% nuclear layer monomer is the cross-linked dosage that total dosage of crosslinking agent deducts seed and 90% nuclear layer monomer.
(2) the polyacrylate grafting vinyl chloride composite particles is synthetic
The about 24g composite particles of the solid content that adds in this process latex is the compounded latex (calculating according to the solid content in this routine compounded latex (1)) for preparing in the top step, and other operation steps is with embodiment 1.
Embodiment 5:
Change the linking agent among the embodiment 4 (1) into ALMA, all the other prescriptions and operation are with embodiment 4.
Embodiment 6:
Change the linking agent among the embodiment 4 (1) into DCPA, all the other prescriptions and operation are with embodiment 4.
Embodiment 7:
Change the linking agent among the embodiment 4 (1) into TMPTMA, all the other prescriptions and operation are with embodiment 4.
Embodiment 8
(1) preparation of polyacrylic ester compounded latex
The mixed solution (11.2g BA, 2.8g EHA, 0.2g ALMA) that in the four-hole reaction flask, adds 100ml deionized water, 0.2g emulsifier sodium lauryl sulfate (SDS) and seed comonomer and linking agent, logical nitrogen and stirring under the room temperature.During heating systems temperature to 75 ℃, add 0.2g initiator K
2S
2O
8, the system heat release heats up during the reaction beginning.The question response liquid temp is constant during to 75 ℃, insulation reaction 1 hour.Finish the seed stage polyreaction.
Be incubated after 1 hour to the required emulsifying agent 0.4g of the disposable adding stratum nucleare of system SDS, after 15～20 minutes in this system the disposable initiator 0.1g K that adds or drip the stratum nucleare formula ratio
2S
2O
8, drip the mixed solution (45.0g BA, 11.3g EHA, 0.6g ALMA) of nuclear layer monomer and linking agent simultaneously, after waiting to dropwise, continued insulation reaction 2 hours, finish the stratum nucleare polyreaction.
Wherein after carrying out 1.5 hours, above-mentioned insulation reaction adds required emulsifying agent in the shell prescription to this system is disposable.The disposable aqueous solution of adding initiator in the shell prescription after 15～20 minutes.Drip shell monomers (3.7g DCPA) simultaneously.The dropping time is 0.5～3 hour, dropwises the back insulation reaction 2 hours, cooling discharge.Obtain the polyacrylic ester compounded latex.
(2) polyacrylic ester/PVC's is synthetic
In stainless steel autoclave, add 353ml deionized water, 1.2g initiator K
2S
2O
8And above-mentioned synthetic contains the polyacrylic ester composite particles latex 400g (calculating according to the solid content of compounded latex in this example (1)) of the about 24g of amount of solid, regulates the pH value of mixed reaction solution 9.5～10.5 with 15g1%NaOH solution.After filling nitrogen deoxygenation three times, adopt the mode of continuous charging to add the 120g vinyl chloride monomer and under room temperature, stir.Temperature reaction, the controlled polymerization temperature is at 50 ± 0.5 ℃.Reaction pressure is 0.5MPa, when question response still pressure reduces 0.2MPa, and fast cooling, decompression removes unreacted vinylchlorid, and discharging, sampling, are drying to obtain polyacrylate/polyvinyl chloride composite particles properties-correcting agent at all the other emulsion breakings, and the nucleocapsid ratio is 50: 50.
Embodiment 9:
Present embodiment is promptly adding 0.9g stablizer maleic acid ester butyl tin (ZT-203) in the nuclear layer monomer mixed solution on the basis of embodiment 2.All the other prescriptions and operation are with embodiment 2.
Embodiment 10:
Change the BA in the nuclear layer monomer mixed solution into ethyl propenoate (EA) on the basis of embodiment 9, all the other prescriptions and operation are with embodiment 9.
Illustrate: in following examples, except that special indicating, seed and stratum nucleare emulsifying agent are 0.5g among the embodiment; Seed and stratum nucleare initiator are respectively 0.2g, 0.4g; Changing factor add-on (%) is the percentage ratio that accounts for the monomer total amount.
Embodiment 11～15:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 2 among the embodiment 11～15, and synthetic (2) of operation steps and polyacrylate/polyvinyl chloride composite particles are with embodiment 1.
The preparation embodiment of table 2 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | Stratum nucleare (g) | Changing factor |
| BA∶EHA∶BDDA | BA∶EHA∶BDDA | BDDA(％) | |
| 11 12 13 14 | 14∶3.5∶0.4 14∶3.5∶0.7 14∶3.5∶1.1 14∶3.5∶1.4 | 60∶15∶1.5 60∶15∶3.0 60∶15∶4.5 60∶15∶6.0 | 2 4 6 8 |
| 15 | 14∶3.5∶1.8 | 60∶15∶7.5 | 10 |
Embodiment 16～22:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 3 among the embodiment 16～22, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 2.
The preparation embodiment of table 3 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | Stratum nucleare (g) | Changing factor |
| BA∶EHA∶ALMA | BA∶EHA∶ALMA | ALMA(％) | |
| 16 17 18 19 20 21 22 | 14∶3.5∶0.3 14∶3.5∶0.4 14∶3.5∶0.7 14∶3.5∶1.1 14∶3.5∶1.4 14∶3.5∶2.1 14∶3.5∶2.8 | 60∶15∶1.1 60∶15∶1.5 60∶15∶3.0 60∶15∶4.5 60∶15∶6.0 60∶15∶9.0 60∶15∶12.0 | 1.5 2 4 6 8 12 16 |
Embodiment 23～27:
Embodiment 23～27th, the polyacrylic ester compounded latex of operation steps (1) preparation among the embodiment 18～22 do not carried out the grafting vinyl chloride reaction of step (2), but direct freezing breakdown of emulsion, obtain the polyacrylic ester composite particles, all the other operation stepss are with embodiment 18～22.
Embodiment 28～32:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 4 among the embodiment 28～32, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 3.
The preparation embodiment of table 4 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | Stratum nucleare (g) | Changing factor |
| BA∶EHA∶DCPA | BA∶EHA∶DCPA | DCPA(％) | |
| 28 29 30 31 32 | 14∶3.5∶0.4 14∶3.5∶0.7 14∶3.5∶1.1 14∶3.5∶1.4 14∶3.5∶1.8 | 60∶15∶1.5 60∶15∶3.0 60∶15∶4.5 60∶15∶6.0 60∶15∶7.5 | 2 4 6 8 10 |
Embodiment 33～35:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 5 among the embodiment 33～35, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 4.
The preparation embodiment of table 5 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | 9/10 stratum nucleare (g) | 1/10 stratum nucleare (g) | Changing factor |
| BA∶EHA∶BDDA | BA∶EHA∶BDDA | BA∶EHA∶BDDA | BDDA(％) | |
| 33 34 35 | 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 | 54∶13.5∶0.7 54∶13.5∶0.7 54∶13.5∶0.7 | 6∶1.5∶2.8 6∶1.5∶4.7 6∶1.5∶6.5 | 4 6 8 |
Embodiment 36～38:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 6 among the embodiment 36～38, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 5.
The preparation embodiment of table 6 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | 9/10 stratum nucleare (g) | 1/10 stratum nucleare (g) | Changing factor |
| BA∶EHA∶ALMA | BA∶EHA∶ALMA | BA∶EHA∶ALMA | ALMA(％) | |
| 36 37 38 | 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 | 54∶13.5∶0.7 54∶13.5∶0.7 54∶13.5∶0.7 | 6∶1.5∶2.8 6∶1.5∶4.7 6∶1.5∶6.5 | 4 6 8 |
Embodiment 39～41:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 7 among the embodiment 39～41, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 6.
The preparation embodiment of table 7 polyacrylic ester compounded latex
| Embodiment number | Seed (g) | 9/10 stratum nucleare (g) | 1/10 stratum nucleare (g) | Changing factor |
| BA∶EHA∶DCPA | BA∶EHA∶DCPA | BA∶EHA∶DCPA | DCPA(％) | |
| 39 40 41 | 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 | 54∶13.5∶0.2 54∶13.5∶0.2 54∶13.5∶0.2 | 6∶1.5∶2.8 6∶1.5∶4.7 6∶1.5∶6.5 | 4 6 8 |
Embodiment 42～44:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 8 among the embodiment 42～44, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 7.
The preparation embodiment of table 8 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | 9/10 stratum nucleare (g) | 1/10 stratum nucleare (g) | Changing factor |
| BA∶EHA∶TMPTMA | BA∶EHA∶TMPTMA | BA∶EHA∶TMPTMA | TMPTMA(％) | |
| 42 | 14∶3.5∶0.2 | 54∶13.5∶0.7 | 6∶1.5∶2.8 | 4 |
| 43 44 | 14∶3.5∶0.2 14∶3.5∶0.2 | 54∶13.5∶0.7 54∶13.5∶0.7 | 6∶1.5∶4.7 6∶1.5∶6.5 | 6 8 |
Embodiment 45～50:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 9 among the embodiment 45～50, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 9.
The preparation embodiment of table 9 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | Stratum nucleare (g) | Changing factor |
| BA∶EHA∶ALMA | BA∶EHA∶ALMA∶ZT-203 | ZT-203(％) | |
| 45 46 47 48 49 50 | 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 | 60∶15∶0.8∶0 60∶15∶0.8∶1.8 60∶15∶0.8∶3.7 60∶15∶0.8∶5.5 60∶15∶0.8∶7.4 60∶15∶0.8∶9.2 | 0 2 4 6 8 10 |
Embodiment 51～55:
The preparation prescription of polyacrylic ester compounded latex (1) sees Table 10 among the embodiment 51～55, and synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 8.
The preparation embodiment of table 10 polyacrylic ester compounded latex (1)
| Embodiment number | Seed (g) | Stratum nucleare (g) | Shell (g) | Changing factor |
| BA∶EHA∶ALMA | BA∶EHA∶ALMA | DCPA | DCPA(％) | |
| 51 52 53 54 55 | 12.4∶3.1∶0.2 10.6∶2.7∶0.2 10.1∶2.5∶0.2 9.5∶2.4∶0.2 8.9∶2.2∶0.2 | 46.8∶11.7∶0.6 42.6∶10.7∶0.6 40.3∶10.1∶0.6 37.9∶9.5∶0.6 35.5∶8.9∶0.6 | 0 7.4 11.1 14.8 18.5 | 0 10 15 20 25 |
Annotate: on show among the embodiment, seed, stratum nucleare and shell emulsifying agent are respectively 0.2g, 0.4g, 0.4g; Seed, stratum nucleare and shell initiator are respectively 0.1g, 0.1g, 0.04g; The DCPA add-on is the percentage ratio that accounts for the monomer total amount.
Embodiment 56～60:
Embodiment 56～60th, adopt synthetic poly acrylate composite emulsion among the embodiment 1 (1), carry out copolyreaction by prescription adding methyl methacrylate monomer and vinyl chloride monomer in step (2), vinyl chloride monomer adopts disposable feed way adding at intermittence.Concrete prescription is as shown in table 11.All the other operation stepss such as embodiment 1.
Table 11 polyacrylate grafting vinyl chloride composite particles prepares embodiment
| Embodiment number | Seed (g) | Stratum nucleare (g) | Comonomer (g) | Changing factor |
| BA∶EHA∶BDDA | BA∶EHA∶BDDA | MMA | MMA(％) | |
| 56 57 58 59 60 | 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 14∶3.5∶0.2 | 60∶15∶0.8 60∶15∶0.8 60∶15∶0.8 60∶15∶0.8 60∶15∶0.8 | 36.5 48.3 60.0 72.0 84.0 | 30 40 50 60 70 |
Annotate: comonomer MMA add-on is the percentage ratio that accounts for the vinyl chloride monomer total amount in the foregoing description.
Embodiment 61～66:
The preparation prescription of polyacrylic ester compounded latex (1) and table 9 basically identical among the embodiment 61～66 just change nuclear layer monomer BA into EA.Synthetic (2) of operation steps and polyacrylate grafting vinyl chloride composite particles are with embodiment 10.
Embodiment 67:
Change the vinyl chloride monomer add-on among the embodiment 1 (2) into 90g among the embodiment 67, the nucleocapsid ratio of gained properties-correcting agent is 60: 40, and all the other prescriptions and operation are all with embodiment 1.
Embodiment 68:
Change the vinyl chloride monomer add-on among the embodiment 18 into 90g among the embodiment 68, the nucleocapsid ratio of gained properties-correcting agent is 60: 40, and all the other prescriptions and operation are all with embodiment 18.
Embodiment 69:
Change the vinyl chloride monomer add-on among the embodiment 1 (2) into 180g among the embodiment 69, the nucleocapsid ratio of gained properties-correcting agent is 40: 60, and all the other prescriptions and operation are all with embodiment 1.
Embodiment 70:
Change the vinyl chloride monomer add-on among the embodiment 14 into 180g among the embodiment 70, the nucleocapsid ratio of gained properties-correcting agent is 40: 60, and all the other prescriptions and operation are all with embodiment 14.
Embodiment 71:
Change the vinyl chloride monomer add-on among the embodiment 1 (2) into 280g among the embodiment 71, the nucleocapsid ratio of gained properties-correcting agent is 30: 70, and all the other prescriptions and operation are all with embodiment 1.
Embodiment 72:
Change the vinyl chloride monomer add-on among the embodiment 1 (2) into 480g among the embodiment 72, the nucleocapsid ratio of gained properties-correcting agent is 20: 80, and all the other prescriptions and operation are all with embodiment 1.
Comparative example
Composite particles properties-correcting agent in embodiment 1 table 1 prescription is removed, promptly do not added any properties-correcting agent, after suspension PVC and various auxiliary agent are prepared, be placed on and mix 10min. in the high-speed mixer.Then mixed material is placed on the twin-roll machine mixing, 170～175 ℃ of control roller temperature, the thin-pass number of times is 12 times, the about 0.9mm of slice thickness.With going out sheet material on request thickness overlay in the mould, preheating 12min in 180 ℃ of following hydropress is forced into 15MPa pressurize 4min, then is chilled to the room temperature slice under 12MPa, impacts and tensile bars usefulness for tailoring.
Shock strength test: above-mentioned sheet coupon is cut into the notch shock batten by the GB/T1043-93 standard with omnipotent sampling machine, at least after placing 24h, newly think carefully on the ZBC-4 type charpy impact test machine that company limited produces in Shenzhen and to carry out shock test, probe temperature is 23 ℃.
The tensile property test: institute's panel is cut into the dumbbell shape tensile bars by the GB/T1040-92 standard, tests its tensile strength with RGT-10A type microcomputer control electronics universal testing machine down at 23 ℃, draw speed is 20mm/min.
According to the test method of GB-1633-79 softening temperature (dimension card), measure thermoplastics in liquid heat-transfer medium, under certain load and certain constant heatingrate's condition, the temperature when sample is pressed into 1 millimeter by 1 millimeter 2 indentor point.Determining instrument is the thermal distortion of XWB-300F type, vicat softening point temperature determinator.
The notched Izod impact strength of the pure polyvinyl chloride that is obtained by comparative example is 3.4KJ/m
2, tensile strength is 54.0MPa, Vicat softening point is about 78 ℃.
Made composite particles properties-correcting agent and PVC intermingling material performance are listed in the table 12 among the above-mentioned part embodiment.
Synthetic composite particles properties-correcting agent blending and modifying PVC material property table look-up among table 12 embodiment
| Embodiment number | Changing factor | Properties-correcting agent nucleocapsid ratio | Vicat softening point (℃) | Notched Izod impact strength (KJ/m 2) | Tensile strength (MPa) |
| 1 11 12 13 14 15 2 17 23 24 25 26 27 3 23 24 25 26 27 9 46 47 48 49 50 51 8 52 53 54 55 | BDDA＝1％ BDDA＝2％ BDDA＝4％ BDDA＝6％ BDDA＝8％ BDDA＝10％ ALMA＝1％ ALMA＝2％ ALMA＝4％ ALMA＝6％ ALMA＝8％ ALMA＝12％ ALMA＝16％ DCPA＝1％ DCPA＝2％ DCPA＝4％ DCPA＝6％ DCPA＝8％ DCPA＝10％ ZT-203＝1％ ZT-203＝2％ ZT-203＝4％ ZT-203＝6％ ZT-203＝8％ ZT-203＝10％ DCPA＝0％ DCPA＝5％ DCPA＝10％ DCPA＝15％ DCPA＝20％ DCPA＝25％ | 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 100∶0 100∶0 100∶0 100∶0 100∶0 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 50∶50 | 75.9 77.4 76.1 76.6 75.8 78.6 77.6 78.0 76.4 77.8 78.4 77.0 76.9 78.3 79.5 79.0 78.8 79.0 79.4 76.6 77.3 77.0 78.6 77.8 77.4 79.2 78.9 80.5 78.4 79.2 81.0 | 6.4 8.3 6.6 6.4 7.4 6.7 6.1 6.4 4.0 4.5 4.3 4.2 5.4 22.7 22.4 23.2 23.9 17.7 14.6 103.0 100.9 100.9 96.9 99.1 87.5 11.1 14.2 10.7 10.6 8.2 10.2 | 51.0 49.3 48.5 49.7 50.8 51.6 49.5 50.1 40.7 43.0 42.8 44.3 45.2 48.8 50.3 50.0 49.5 48.1 48.9 48.1 47.2 47.8 46.7 48.1 48.7 49.8 49.6 49.6 49.5 49.5 49.3 |
| 56 57 58 59 60 67 68 69 70 71 72 comparative examples | MMA＝30％ MMA＝40％ MMA＝50％ MMA＝60％ MMA＝70％ BDDA＝1％ ALMA＝4％ BDDA＝1％ BDDA＝8％ BDDA＝1％ BDDA＝1％ -- | 50∶50 50∶50 50∶50 50∶50 50∶50 60∶40 60∶40 40∶60 40∶60 30∶70 20∶80 -- | 76.6 76.8 76.7 75.9 76.7 76.2 78.3 76.0 76.3 76.0 76.8 78 | 7.8 9.6 8.8 9.8 10.0 5.6 4.2 7.0 5.5 7.2 4.8 54.0 | 51.7 51.1 52.3 51.9 52.4 52.6 51.6 48.9 46.6 49.7 52.2 3.4 |
Annotate: the changing factor add-on is the percentage ratio that accounts for the monomer total amount in the table.
By the performance of the listed embodiment of above-mentioned table 12 we as can be seen, all can make the impelling strength of PVC that in various degree raising is arranged after institute's synthetic properties-correcting agent and the PVC blend, wherein embodiment 9 intermingling material notched Izod impact strength can reach 103KJ/m
2Purer polyvinyl chloride is the highest to improve 30 times.And when impact property improved, stretching descends to some extent but fall is little.The purer PVC of part embodiment Vicat softening point also slightly rises.Wherein the purer PVC of the Vicat softening point among the embodiment 55 improves 3 ℃.
Claims (5)
1. preparation method with nucleocapsid structure polyvinyl chloride impact modifier of transition layer structure, it is characterized by this properties-correcting agent composite particles is made of rubber elastomer kernel, transition layer and plastics shell, properties-correcting agent particle kernel is mainly cross-linking type polyacrylate(s) elastomerics, kernel and transition layer account for 20～80% of composite particles gross weight, outer shell plastics phase component be ryuron or with vinylchlorid be main component with other monomeric multipolymer, account for 20～80% of composite particles gross weight, concrete preparation process is as follows:
(1) preparation of polyacrylic ester seed emulsion
Get rid of oxygen to reaction system drum nitrogen, carry out emulsion polymerization by following composition and consumption:
The composition parts by weight
Deionized water 200
The mixed solution 17.7～20.3 of seed comonomer and linking agent
Emulsifying agent 0.1～1.2
Initiator 0.2～0.4
Described emulsifying agent is a sodium lauryl sulphate, and initiator is a Potassium Persulphate, and the seed comonomer is an acrylate co-monomers in the mixed solution of seed comonomer and linking agent, and acrylate co-monomers is 17.5: 0.2～2.8 with the ratio of cross-linked dosage;
Heated up in the above-mentioned reaction mixture back that stirs, in 60～90 ℃ of reactions 1～4 hour down;
(2) polyacrylic ester with transition layer is examined emulsion preparation
The composition parts by weight
Comonomer and linking agent mixed solution 75.8～87.0
Emulsifying agent 0.1～1.2
Initiator 0.2～0.4
Described emulsifying agent is a sodium lauryl sulphate, and initiator is a Potassium Persulphate, and comonomer is an acrylate co-monomers, and acrylate co-monomers is 75: 0.8～12 with the dosage of crosslinking agent ratio;
The emulsifier solution of formula ratio above the disposable adding in the seed emulsion that obtains by step (1), after 15～20 minutes in this system the disposable initiator solution of adding or drip formula ratio; Then continuously drip 90% acrylate co-monomers with account for the mixed solution of the amount of comonomers that drips 1% linking agent;
Drip remaining 10% acrylate co-monomers and residue linking agent mixed solution then, perhaps drip remaining 10% acrylate co-monomers and be equivalent to remain the monomer that has functional groups of cross-linked dosage or the mixed solution of stablizer, the dropping time is 0.5～3 hour; After dropwising, continuing polyreaction 1～4 hour under the temperature equally with step (1), finish reaction, cooling discharge obtains the composite particles emulsion;
(3) vinyl chloride monomer on polyacrylic ester composite particles surface and with the graft copolymerization graft polymerization reaction of other grams of monomer blend add form and consumption as follows:
The composition parts by weight
Deionized water 300～800
Emulsifying agent 0～1.2
Initiator 0.5～1.2
Composite particles emulsion 350～500
PH regulator agent 9～25
Acrylic ester copolymerization monomer 0～84
Vinyl chloride monomer 90～300
Emulsifying agent described in the above-mentioned preparation process is a sodium lauryl sulphate, and initiator is a Potassium Persulphate, and the pH regulator agent is ten water Sodium Tetraboratees, sodium bicarbonate, sodium hydroxide or yellow soda ash, and the pH scope is 6～12; Seed a and the described acrylate monomer of stratum nucleare b refer to other acrylate of butyl acrylate, 2-EHA or second-order transition temperature Tg＜-10 ℃ and their blend;
The composite emulsion of step (2) gained is joined in the autoclave, add other component except that vinyl chloride monomer simultaneously, reaction system is airtight, vacuumize, fill nitrogen, exhaust, after the repetitive operation three times, add vinyl chloride monomer, in 40～70 ℃ of following polymerizations 4～30 hours, polymerization pressure is between 0.4～1.2MPa, after question response pressure reduced by 0.2～0.6MPa, the fast cooling termination reaction was removed unreacted vinyl chloride monomer, the discharging sampling is with the freezing breakdown of emulsion of prepared graft copolymer emulsion, filter, washing, drying is just had the nucleocapsid structure polyvinyl chloride impact modifier of transition layer structure.
2. according to the described preparation method of claim 1 with nucleocapsid structure polyvinyl chloride impact modifier of transition layer structure, it is characterized in that selected linking agent is the acrylic ester cross-linking agent that has two or more active identical or inequality pair keys in step in the preparation process (1) and (2), be 1,4 butanediol diacrylate, allyl methacrylate(AMA), Viscoat 295, Phthalic acid, diallyl ester, trimethylolpropane trimethacrylate or (methyl) vinylformic acid double cyclopentenyl ester.
3. the preparation method with hud typed impact modifier of polyvinyl chloride of transition layer structure according to claim 1 is characterized in that the used monomer that has functional groups of transition layer is in the step (2): (methyl) vinylformic acid double cyclopentenyl ester, allyl methacrylate(AMA), have terminal hydroxy group organic block acrylated organo-siloxane, the acrylate with compliant section side group, methacrylic acid (3-trimethoxy silicon) propyl ester, vinyltriethoxysilane, have the N-substituted maleimide amine or the Phthalic acid, diallyl ester of heat-resisting group; The stablizer that has functional groups is the organic tin stablizer: the maleic acid ester butyl tin.
4. the preparation method with nucleocapsid structure polyvinyl chloride impact modifier of transition layer structure according to claim 1, it is characterized in that in the step (3) that other monomer except that vinylchlorid related in the shell refers to: other (methyl) acrylate of methyl methacrylate, ethyl propenoate, (methyl) vinylformic acid double cyclopentenyl ester or second-order transition temperature Tg＞-10 ℃.
5. according to the described preparation method of claim 1, it is characterized in that the vinyl chloride monomer feed way is that continuous charging or gap are reinforced in the preparation process with nucleocapsid structure polyvinyl chloride impact modifier of transition layer structure.
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