CN1312298A - Shock resisting polyvinyl chloride modifier - Google Patents
Shock resisting polyvinyl chloride modifier Download PDFInfo
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- CN1312298A CN1312298A CN 01107857 CN01107857A CN1312298A CN 1312298 A CN1312298 A CN 1312298A CN 01107857 CN01107857 CN 01107857 CN 01107857 A CN01107857 A CN 01107857A CN 1312298 A CN1312298 A CN 1312298A
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Abstract
The impact-resisting modifier for PVC is technically characterized by that its raw material emulsion composition contains (wt%) at least one kind of rubber phase 2-8c alkyl acrylate 50%-95%, at least two kinds of thermoplastic phase 1-4C alkyl methyl acrylates 4.5%-45% and methyl acrylic 2-4C ester 0.5%-5%. Said invention can raise resistance to impact of hard PVC, and can improve its working property and thermal sensitivity, and UV stability so as to ensure that said product possesses excellent weatherability.
Description
The present invention relates to a kind of organic chemistry class, specifically a kind of shock resisting polyvinyl chloride modifier.
We know, as the anti-impact modifier of polyvinylhalide (as PVC) _ _ the ACR resin, has good impact-resistance, weathering resistance, features such as good luster, but processing characteristics can not reach the requirement of goods preparation, as USP 3969431, patents such as E P700965, use the vinylformic acid 2_ ethyl of butyl acrylate 50_70 part and 30_50 part own for examining, account for 80%, ACR resin with 20% methyl methacrylate being the constituent preparation of shell has higher low-temperature impact resistance to PVC, extrudes or be injected into product requirements but needs interpolation processing aid etc. just can reach PVC.J P06_192535 is by the impact modifier of BA_MMA/EA_MAA constituent as PVC, and JP52_33991 is as properties-correcting agent by the BA_MMA constituent.
Purpose of the present invention is exactly in order to overcome above-mentioned the deficiencies in the prior art, provide a kind of properties-correcting agent can improve the shock resistance of rigid polyvinyl chloride, and improve its processing characteristics and, and then guarantee the excellent weathering resistance of goods to the susceptibility of heat and the stability of UV-light.
For achieving the above object, the present invention can realize by following measure: its technical characterictic is, feed composition (weight) is, the alkyl of at least a rubber phase (C atomicity 2_8) esters of acrylic acid 50%-95%, the alkyl of at least two kinds of thermoplastic phases (C atomicity 1_4) methyl acrylic ester 4.5%-45%, higher alkyl methacrylate (the C atomicity is 2-4) 0.5%-5%.
Shock resisting polyvinyl chloride modifier of the present invention can improve the shock resistance of rigid polyvinyl chloride, and improves its processing characteristics and to the susceptibility of heat and the stability of UV-light, and then guarantees the excellent weathering resistance of goods.
The invention will be further described below in conjunction with embodiment:
The present invention is in the shell of core/shell structure, add the higher alkyl methacrylate class, so both kept the impact-resistance of ACR resin, weathering resistance, introduce the higher alkyl methacrylate class of improving processibility again, make PVC in extrusion moulding, have fusion plastification and dispersing uniformity faster.The present invention is the polymkeric substance based on the multilayered structure of acrylate, internal layer has a kind of elastomeric elastomerics at least, skin has two kinds of thermoplastics constituents with methyl acrylic ester composition good with the PVC consistency at least, and promptly nuclear is the elastomerics that alkyl acrylate and insignificant monomer composition by the 2_8 carbon atom alkyl are polymerized.Shell is that the monomer mixture with alkylmethacrylate class of 1_4 carbon atom alkyl is polymerized.
Synthetic method of the present invention is with common used polymerization process, as modes such as letex polymerization, suspension polymerization, solvent polymerics, wherein be preferably emulsion polymerization, finally forming with the elastomerics is the core/shell structure of nuclear, this elastomer core, be alkyl acrylate and 0.05%_5.0% by at least 50% weight part, the cross-linkable monomer polymerization of mixtures of 0.1%_3.5% preferably, after the elastic kernel polymerization is finished, promptly after the polymerization of nuclear section monomer mixture exhausted, the inflexible shell was polymerized in the presence of the elasticity phase.Be preferably a spot of rigidity be penetrated into mutually elasticity mutually in, preferably all rigidity form on the surface of elasticity on mutually, and nuclear is wrapped, making does not have new particle to form in the latex.
The mutually employed monomer of elasticity of the present invention has alkyl-acrylates, this alkyl is that carbonatoms is that the straight or branched of 2_8 can, as ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid 2_ ethylhexyl, Octyl acrylate etc., also these monomers can be mixed and use, the Tg of elasticity phase≤-10 ℃, preferably Tg≤-30 ℃.
The mutually employed monomer of rigidity of the present invention is an alkyl methacrylate, this alkyl is that carbonatoms is that the straight or branched of 1_4 all can, as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate etc., also these monomers can be mixed and use.The molecular weight of rigidity phase (all sticking) scope is 50000_600000, preferably at 50000_300000, and the Tg of rigidity phase 〉=20 ℃, preferably Tg 〉=50 ℃.
Ethene that can copolymerization with above-mentioned monomer is that unsaturated monomer also can use, as: aromatic vinyl derivatives such as vinylbenzene, alpha-methyl styrene.Ethylene halides such as vinylchlorid, bromine ethene, nitrilation ethene such as vinyl cyanide, methacrylonitrile.Vinyl ester such as vinyl acetate, vinyl propionate.
Cross-linkable monomer used in the present invention is general commonly used, as Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), trimethylammonium vinylformic acid trishydroxymethyl propyl ester, tetramethyl-vinylformic acid tetra methylol propyl ester, dimethacrylate dipropyl glycol ester and their pairing esters of acrylic acids.Vinyl-type cross-linking monomers such as Vinylstyrene, divinyl adipic acid ester, allyl type cross-linking monomers such as adjacent this dioctyl phthalate diallyl, diallyl maleate, allyl acrylate, isocyanuric acid triallyl also can also be used by two kinds of monomers.
For above-mentioned polyfunctional group cross-linkable monomer, its addition is not done special restriction, but certain scope is arranged.Addition very little, when doing the moulding of PVC properties-correcting agent, nuclear, shell is destroyed, and loses its shock-resistance; Addition is too much, makes degree of crosslinking excessive, and rubbery kernel Tg raises, and loses its rubber property, does not also reach toughness reinforcing requirement, and resin combination is mobile poor.Therefore, cross-linked dosage is advisable for the 0.05%_5% weight part with respect to amount of monomer, is more preferably 0.1%_3.5%.
The present invention's employed emulsifying agent in letex polymerization be anionic or non-ionic type or both and usefulness, as nonionic emulsifier such as the emulsifying agent of anionics such as sodium oleate, potassium oleate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, alkyl diphenyl base ether sodium disulfonate, polyoxyethylene lauroyl ether, polyoxyethylene nonylplenyl ether, polyoxyethylene propylene-based block copolymers.
Initiator used in the present invention has, and is water miscible and oil-soluble.Water miscible initiator has the persulfuric acid salt, as Potassium Persulphate, Sodium Persulfate, ammonium persulphate and hydrogen peroxide etc.Oil-soluble initiator has, benzoyl peroxide, lauroyl peroxide, hydrogen phosphide cumene, di-isopropylbenzene hydroperoxide also can be the thermal initiation systems, or oxidation-reduction system etc., can also add oxidation inhibitor as required in addition, auxiliary agents such as pH value conditioning agent.
In letex polymerization, particularly the shock resistance influence is very big to the polymkeric substance mechanical property for nuclear section particle diameter.The median size of latex is emulsification dosage and the kind of using along with polymerization in letex polymerization, the kind of initiator and consumption, the variation of monomeric adding mode changes, routinely emulsion polymerization, median size generally about 350 , differs greatly from desired 1000 -1500 .It increases the effective means of particle diameter for reducing the consumption of emulsifying agent and initiator, but consumption is low excessively, and stability of emulsion is poor, and polymerization rate is slow, can't implement industrial.
The present invention adopts and changes monomer and auxiliary agent addition manner, can reach the requirement that increases particle diameter, and promptly emulsion polymerization technique can adopt pre-emulsification technology, and monomer and auxiliary agent be adding technology and seeding polymerization method respectively.
The so-called technology that drips is to add deionized water and an amount of seed emulsion in polymeric kettle, after filling the nitrogen deoxidation, being warmed up to certain temperature, monomer and auxiliary agent is added dropwise to the polymerization of still respectively.
So-called seeding polymerization method promptly in monomer dropping method or pre-emulsification technology, generates seed latex with monomer or the first polymerization of pre-emulsification earlier, after this drips residual monomer or pre-emulsion again and carries out the polymeric method.
Above-mentioned various polymerization technique can increase the particle diameter of latex effectively, reduces condensation product.
Constituent of the present invention also should add common stablizer with the polyvinylhalide blend time, lubricant and other additive.The proportioning of its blend is composed as follows:
100 parts of PVC
7 parts of ACR
4 parts of one package stabilizers
4 parts of titanium dioxides
8 parts in lime carbonate
0.1 part of polyethylene wax
Embodiment 1: have stirring, thermometer, reflux exchanger, monomer, auxiliary agent, in the 3M3 polymerization reaction kettle of inlet such as nitrogen, drop into the 800L deionized water earlier, 1.45Kg sodium lauryl sulphate, after 25_30 ℃ stirring makes the sodium lauryl sulphate dissolving down, charge into nitrogen, after removing the interior oxygen of still, drop into butyl acrylate 58Kg, Potassium Persulphate 0.17Kg, 1,4_ butylene glycol diacrylate 0.58Kg, temperature is raised to 70 ± 2 ℃, after about 30 minutes, exothermic peak can appear, treat temperature-stable after 70 ℃, begin dropwise addition of acrylic acid butyl ester 522Kg respectively, 1,4_ butylene glycol diacrylate 5.22Kg and sodium lauryl sulphate 4.35Kg, Potassium Persulphate 1.57Kg is dissolved in the 360L deionized water, and rate of addition stabilizes to suitable with the control temperature in the kettle, generally dripped off at 3_4 hour, after monomer and auxiliary agent are added dropwise to complete, be incubated 1 hour, be raised to 90 ℃ again, kept 1 hour, so far nuclear section polymerization is finished, and is cooled to about 75 ℃, begins to drip respectively methyl methacrylate 180Kg, butyl methacrylate 40Kg and Potassium Persulphate 0.66Kg, be dissolved in the 330L deionized water about 1.5_2.0 hour and drip off, be raised to 90 ℃ again, be incubated 1 hour, so far polyreaction finishes, monomer conversion 〉=99.5% cools to≤50 ℃, puts into storage tank.
Latex after the polymerization is pumped into the spraying drying column overhead with metering and carries out drying with being not less than 150 ℃ warm air and flowing to into drying tower, gets particle diameter≤30 orders, the powder-like product of water content≤1%.Or with latex with 0.5% the aluminum chloride aqueous solution, in the time of 〉=40 ℃, carry out the breakdown of emulsion flocculation, filter, washing, 60_70 ℃ dry down, pulverize≤30 order granulated products.
Embodiment 2: except that substituting the butyl methacrylate with the 40Kg Jia Jibingxisuanyizhi, other together
Embodiment 1.
Embodiment 3: shell section monomer consumption is methyl methacrylate 180Kg, and butyl methacrylate is that 20Kg and Jia Jibingxisuanyizhi are outside the 20Kg, and other are with embodiment 1.
Embodiment 4: shell section monomer consumption is methyl methacrylate 160Kg, butyl methacrylate 40Kg and Jia Jibingxisuanyizhi 20Kg, and other are with embodiment 1.
Embodiment 5: nuclear section monomer consumption is butyl acrylate 420Kg, and vinylformic acid 2_ ethylhexyl is 180Kg, and shell section monomer consumption is methyl methacrylate 180Kg, and the butyl methacrylate consumption is 20Kg, and other are with embodiment 1.
Claims (1)
1, a kind of shock resisting polyvinyl chloride modifier, it is characterized in that feed composition (weight) is, the alkyl of at least a rubber phase (C atomicity 2_8) esters of acrylic acid 50%-95%, the alkyl of at least two kinds of thermoplastic phases (C atomicity 1_4) methyl acrylic ester 4.5%-45%, higher alkyl methacrylate (the C atomicity is 2-4) is 0.5%-5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01107857 CN1125828C (en) | 2001-03-07 | 2001-03-07 | Shock resisting polyvinyl chloride modifier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01107857 CN1125828C (en) | 2001-03-07 | 2001-03-07 | Shock resisting polyvinyl chloride modifier |
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| Publication Number | Publication Date |
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| CN1312298A true CN1312298A (en) | 2001-09-12 |
| CN1125828C CN1125828C (en) | 2003-10-29 |
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| CN 01107857 Expired - Fee Related CN1125828C (en) | 2001-03-07 | 2001-03-07 | Shock resisting polyvinyl chloride modifier |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344660C (en) * | 2002-01-25 | 2007-10-24 | Lg化学株式会社 | Acrylic impact modifier prepared by multi-stage polymerization and method for preparing the same |
| CN101544719B (en) * | 2009-05-11 | 2011-05-04 | 芜湖融汇化工有限公司 | Method for producing chlorinated polyvinyl chloride processing modified adjuvant |
| CN101328241B (en) * | 2007-06-18 | 2011-07-20 | 山东瑞丰高分子材料股份有限公司 | Processing modifying agent for polychloroethylene foaming moulding products |
| CN102464839A (en) * | 2010-11-10 | 2012-05-23 | 上海华明高技术（集团）有限公司 | Composite toughening modifier for plastics and preparation method thereof |
| CN105754041A (en) * | 2016-05-18 | 2016-07-13 | 江西岳峰高分子材料有限公司 | Weather-proof resin for plastic-steel doors and windows and preparation method of weather-proof resin |
| CN104327216B (en) * | 2014-10-15 | 2017-02-08 | 山东世拓高分子材料股份有限公司 | Terpolymer used for hard polyvinyl chloride and preparation method thereof |
| CN109616882A (en) * | 2018-11-15 | 2019-04-12 | 广东求精电气有限公司 | A kind of power distribution cabinet |
| CN109651728A (en) * | 2018-11-15 | 2019-04-19 | 广东求精电气有限公司 | One kind having high-intensitive, antistatic power distribution cabinet shell and preparation method thereof |
| CN109851936A (en) * | 2018-11-15 | 2019-06-07 | 广东求精电气有限公司 | A kind of antistatic, anticorrosion power distribution cabinet shell and preparation method thereof |
| CN114736468A (en) * | 2022-03-30 | 2022-07-12 | 兰州金睿合新材料科技有限责任公司 | High-toughness PVC (polyvinyl chloride) blending material and preparation method thereof |
-
2001
- 2001-03-07 CN CN 01107857 patent/CN1125828C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344660C (en) * | 2002-01-25 | 2007-10-24 | Lg化学株式会社 | Acrylic impact modifier prepared by multi-stage polymerization and method for preparing the same |
| CN101328241B (en) * | 2007-06-18 | 2011-07-20 | 山东瑞丰高分子材料股份有限公司 | Processing modifying agent for polychloroethylene foaming moulding products |
| CN101544719B (en) * | 2009-05-11 | 2011-05-04 | 芜湖融汇化工有限公司 | Method for producing chlorinated polyvinyl chloride processing modified adjuvant |
| CN102464839A (en) * | 2010-11-10 | 2012-05-23 | 上海华明高技术（集团）有限公司 | Composite toughening modifier for plastics and preparation method thereof |
| CN102464839B (en) * | 2010-11-10 | 2014-04-16 | 上海华明高技术（集团）有限公司 | Composite toughening modifier for plastics and preparation method thereof |
| CN104327216B (en) * | 2014-10-15 | 2017-02-08 | 山东世拓高分子材料股份有限公司 | Terpolymer used for hard polyvinyl chloride and preparation method thereof |
| CN105754041A (en) * | 2016-05-18 | 2016-07-13 | 江西岳峰高分子材料有限公司 | Weather-proof resin for plastic-steel doors and windows and preparation method of weather-proof resin |
| CN109616882A (en) * | 2018-11-15 | 2019-04-12 | 广东求精电气有限公司 | A kind of power distribution cabinet |
| CN109651728A (en) * | 2018-11-15 | 2019-04-19 | 广东求精电气有限公司 | One kind having high-intensitive, antistatic power distribution cabinet shell and preparation method thereof |
| CN109851936A (en) * | 2018-11-15 | 2019-06-07 | 广东求精电气有限公司 | A kind of antistatic, anticorrosion power distribution cabinet shell and preparation method thereof |
| CN114736468A (en) * | 2022-03-30 | 2022-07-12 | 兰州金睿合新材料科技有限责任公司 | High-toughness PVC (polyvinyl chloride) blending material and preparation method thereof |
| CN114736468B (en) * | 2022-03-30 | 2023-10-20 | 兰州金睿合新材料科技有限责任公司 | High-toughness PVC (polyvinyl chloride) blending material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1125828C (en) | 2003-10-29 |
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