CN103788281A - Core-shell structure processing agent for rigid polyvinyl chloride and synthetic method thereof - Google Patents
Core-shell structure processing agent for rigid polyvinyl chloride and synthetic method thereof Download PDFInfo
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- CN103788281A CN103788281A CN201410079078.7A CN201410079078A CN103788281A CN 103788281 A CN103788281 A CN 103788281A CN 201410079078 A CN201410079078 A CN 201410079078A CN 103788281 A CN103788281 A CN 103788281A
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Abstract
The invention discloses a core-shell structure processing agent for rigid polyvinyl chloride and a synthetic method of the core-shell structure processing agent. The raw materials of the core-shell structure processing agent comprise, by weight, 100 parts of acetic acid vinyl ester monomers, 250-300 parts of water, 0.01-0.1 part of dispersing agents, 0.1-5.0 parts of emulsifying agents, 0.5-2.0 parts of alkaline media, 0.02-0.1 part of initiators and 20-50 parts of monomer methyl methacrylate. The core-shell structure processing agent is high in yield, the yield reaches above 97 percent, and emulsion stability is good. On the premise of guaranteeing the plasticification degree, melt strength and balance torque are greatly improved, the core-shell structure processing agent is suitable for different processing ranges, the water resistance, alkali resistance and heat resistant performance of a copolymer are improved, and cost is low.
Description
Technical field
The present invention relates to one and use novel modifier, relate in particular to a kind of rigid polyvinyl chloride nucleocapsid structure processing aid and synthetic method thereof.
Background technology
China is that rigid polyvinyl chloride PVC Production and consumption big country of the world, relevant PVC goods have wide market environment, and existing dynamics has again range.Based on the fast development of urban and rural buildings engineering, traffic engineering, environmental engineering, the energy and hydro project etc., the market requirement of PVC material of construction, engineering materials improves day by day, is one of plastics variety of China's output maximum at present.Hard PVC is containing softening agent, therefore, easy-formation, be difficult for crisp, nontoxic pollution-free, the shelf time is long, is widely used in section bar, profiled material, sheet material, tubing, foamed board, building template, wood and the industry such as moulds, and has very large development and application values.
PVC work in-process need to by heat and shearing be separated into uniform molten state could moulding, but polyvinyl chloride resin itself is not strong to the transmission of heat and shearing force, fusion time is longer, the melt forming is inhomogeneous, affect products appearance and mechanical property, when adding after modifier, can obviously improve the characteristics such as fluidity of molten, thermal distortion and the product surface gloss of polyvinyl chloride resin.The modifier making through polyreaction roughly can be subdivided into following five large classes: methyl methacrylate-butyl acrylate random copolymers, methyl methacrylate-ethyl propenoate random copolymers, styrene-acrylonitrile random copolymers, esters of acrylic acid-styrenic blending resin and be mixed with the mineral filler blending resin of nano modification.Its advantage of methyl methacrylate-butyl acrylate (or ethyl propenoate) multipolymer is to have excellent processing characteristics, resistance toheat, can give the wider processing temperature scope of goods, higher melt strength, good surface smoothness and dimensional stability; The styrene-propene nitrile modifier esters of acrylic acid modifier of comparing, there is obvious cost advantage, but because vinylbenzene contains unsaturated double-bond, uvioresistant and ageing resistance are general, vinylbenzene and PVC consistency are poor simultaneously, work range is narrower, and melt plasticizing is slow, and product surface smooth finish is bad; The mineral filler blending resin that is mixed with nano modification is to be basis by above-mentioned two large class modifiers, then is equipped with the weighting materials such as nano-calcium carbonate, silicon-dioxide, mica powder, thereby reduces product price.Addition is larger, and the mechanical properties decrease of hard PVC goods is more obvious, and as goods fragility strengthens, in the course of processing, slowly, surface smoothness declines, dimensional stability cannot reach expectation index etc. in melt plasticizing.
The inventor finds in research PVC modifier technological line and market application process, alkyl methacrylate, alkyl-acrylates resin and vinyl cyanide, styrene resin are having certain advantage aspect raising processing aid and PVC consistency and plasticizing, but along with the petrochemical complex prices of raw and semifnished materials go up and force the production of PVC modifier, application producer to have to by adding a large amount of mineral fillers, be lowered into and originally seek enterprise development with this.Final form vicious cycle, seriously hindered hard PVC goods industry integral level, depart from country's " moulding Dai Gang, to mould Dai Mu " overall plan.
Summary of the invention
The object of this invention is to provide a kind of rigid polyvinyl chloride nucleocapsid structure processing aid and synthetic method thereof, good emulsion stability; Greatly improve melt strength and balancing torque, improve water tolerance, alkali resistance and the resistance toheat of multipolymer, cost is low, and yield is high.
A kind of rigid polyvinyl chloride nucleocapsid structure processing aid of the present invention, in parts by weight, raw material composed as follows:
100 parts of vinyl acetate monomers, water 250-300 part, dispersion agent 0.01-0.1 part, emulsifying agent 0.1-5.0 part, alkaline medium 0.5-2.0 part, initiator 0.02-0.1 part, monomers methyl methacrylate 20-50 part.
Described dispersion agent is polyvinyl alcohol.
Dispersion agent is that one or both mixing in PVAC polyvinylalcohol-1788 or PVAC polyvinylalcohol-1799 are used.
Described emulsifying agent is that one or more mixing in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, OP-10 or tween-80 are used.
Emulsifying agent preferably sodium dodecyl sulfate mixes use with OP-10, the preferred 1:2 of both part by weight.
Described initiator is that one or more mixing in Potassium Persulphate, ammonium persulphate, sodium bisulfite or sodium bicarbonate are used.
Described alkaline medium is that one or both mixing in potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate or ammoniacal liquor are used.
The synthetic method of nucleocapsid structure processing aid for rigid polyvinyl chloride, first vinyl acetate monomer, water, dispersion agent, emulsifying agent, alkaline medium are added to reaction unit, logical nitrogen deoxygenation, under the stirring velocity of 50-300 rev/min, stir and within 2-5 hour, be warming up to 45 ℃-55 ℃, add initiator, control temperature of reaction below 60 ℃, reaction 2-5 hour, prepares stratum nucleare emulsion; Then monomers methyl methacrylate, emulsifying agent are added to stratum nucleare emulsion, logical nitrogen deoxygenation, under the stirring velocity of 50-300 rev/min, be warming up to 40 ℃-50 ℃, add initiator, control temperature of reaction below 55 ℃, reaction 2-3 hour, is then warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, the spray-dried rigid polyvinyl chloride nucleocapsid structure processing aid that obtains having nucleocapsid structure.
The polymer emulsion emulsion particle of synthesized is nucleocapsid structure, and wherein stratum nucleare is polyvinyl acetate, and shell is methyl methacrylate.
In nucleocapsid structure, nucleocapsid ratio is 10:2-10:5.
Raw material used in the present invention is commercially available.
Concrete preparation process of the present invention is:
First the water of 100 weight part vinyl acetate monomers, 250-300 weight part, 0.01-0.1 weight part dispersion agent, 0.05-2.0 weight part emulsifying agent, 0.5-2.0 weight part PH conditioning agent are added to reaction unit, logical nitrogen deoxygenation, under the stirring velocity of 50-300 rev/min, stir and within 2-5 hour, be warming up to 45 ℃-55 ℃, add 0.01-0.05 weight part initiator, control temperature of reaction below 60 ℃, reaction 2-5 hour, prepares the required emulsion of stratum nucleare structure; Then 20-50 weight parts monomers methyl methacrylate, 0.5-3.0 weight part emulsifying agent are added to above-mentioned emulsion, logical nitrogen deoxygenation, under the stirring velocity of 50-300 rev/min, be warming up to 40 ℃-50 ℃, add 0.01-0.05 weight part initiator, control temperature of reaction below 55 ℃, reaction 2-3 hour, is then warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, the spray-dried rigid polyvinyl chloride nucleocapsid structure processing aid that obtains having nucleocapsid structure.
The present invention utilizes under alkaline medium, by graft polymerization process, methyl methacrylate-grafted is arrived to polyvinyl acetate surface, forms copolymer emulsion, the final spray-dried polyvinyl acetate/methylmethacrylate copolymer of preparing.This multipolymer can be widely used in the processing of hard PVC product, and such as section bar, profiled material, sheet material, tubing, foamed board, building template, wood such as mould at the industry, successfully substitutes current tradition and the single modifier of performance.
Compared with prior art, the present invention has following beneficial effect:
(1) yield is high, reaches more than 97% good emulsion stability;
(2) guaranteeing, under the prerequisite of degree of plasticification, greatly to improve melt strength and balancing torque, be suitable for different work range;
(3) water tolerance, alkali resistance and the resistance toheat of raising multipolymer;
(4) cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
First by the water of 100 weight part vinyl acetate monomers, 250 weight parts, 0.01 weight account polyethylene alcohol (PVA-1788), 2.0 weight part sodium lauryl sulphate, 0.5 weight part sodium carbonate adds reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 50 ℃, add 0.01 weight part Potassium Persulphate, control temperature of reaction below 60 ℃, react 2 hours, prepare stratum nucleare emulsion; Then 20 weight parts monomers methyl methacrylates, 0.5 weight part sodium lauryl sulphate are added to reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 40 ℃, add 0.01 weight part Potassium Persulphate, control temperature of reaction below 55 ℃, react 2 hours, then be warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, finally, by the final rigid polyvinyl chloride of spray-dried emulsion preparation nucleocapsid structure processing aid, its nucleocapsid ratio is 10:2.
Embodiment 2
First by the water of 100 weight parts monomers vinyl-acetic esters, 250 weight parts, 0.1 weight account polyethylene alcohol (PVA-1788), 0.05 weight part sodium lauryl sulphate, 0.5 weight part sodium carbonate adds reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 50 ℃, add 0.05 weight part initiator potassium persulfate, control temperature of reaction below 60 ℃, react 5 hours, then 50 weight parts monomers methyl methacrylates, 3.0 weight part sodium lauryl sulphate are added to reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 50 ℃, add 0.01 weight part initiator potassium persulfate, control temperature of reaction below 55 ℃, react 2 hours, then be warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, finally, by the final rigid polyvinyl chloride of spray-dried emulsion preparation nucleocapsid structure processing aid, its nucleocapsid ratio is 10:5.
Embodiment 3
First by the water of 100 weight parts monomers vinyl-acetic esters, 300 weight parts, 0.05 weight account polyethylene alcohol PVA-1799,1.0 weight part Sodium dodecylbenzene sulfonatees, 1 weight part sodium bicarbonate adds reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 45 ℃, add 0.01 weight part initiator potassium persulfate, 0.01 weight part sodium bisulfite, control temperature of reaction below 60 ℃, react 2 hours, then 30 weight parts monomers methyl methacrylates, 0.5 weight part emulsifying agent Sodium dodecylbenzene sulfonate are added to reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 45 ℃, add 0.01 weight part initiator potassium persulfate, control temperature of reaction below 50 ℃, react 5 hours, then be warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, finally, by the final rigid polyvinyl chloride of spray-dried emulsion preparation nucleocapsid structure processing aid, its nucleocapsid ratio is 10:3.
Embodiment 4
First by the water of 100 weight parts monomers vinyl-acetic esters, 300 weight parts, 0.05 weight account polyethylene alcohol PVA-1799,0.5 parts by weight O P-10,0.5 weight part sodium lauryl sulphate, 1 weight part sodium bicarbonate adds reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 45 ℃, add 0.03 weight part initiator potassium persulfate, control temperature of reaction below 60 ℃, react 2 hours, then by 40 weight parts monomers methyl methacrylates, 0.5 parts by weight O P-10,0.5 weight part sodium lauryl sulphate adds reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 45 ℃, add 0.03 weight part initiator potassium persulfate, control temperature of reaction below 50 ℃, react 5 hours, then be warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, finally, by the final rigid polyvinyl chloride of spray-dried emulsion preparation nucleocapsid structure processing aid, its nucleocapsid ratio is 10:4.
Embodiment 5
First by the water of 100 weight parts monomers vinyl-acetic esters, 300 weight parts, 0.05 weight account polyethylene alcohol PVA-1788,1.0 parts by weight O P-10,1.0 weight part Sodium dodecylbenzene sulfonatees, 1 weight part sodium bicarbonate adds reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 45 ℃, add 0.03 weight part initiator potassium persulfate, 0.03 weight part sodium bisulfite, control temperature of reaction below 60 ℃, react 2 hours, then by 40 weight parts monomers methyl methacrylates, 1.0 parts by weight O P-10,1.0 weight part Sodium dodecylbenzene sulfonatees add reaction unit, logical nitrogen deoxygenation; Under the stirring velocity of 300 revs/min, be warming up to 50 ℃, add 0.03 weight part initiator potassium persulfate, control temperature of reaction below 50 ℃, react 5 hours, then be warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, finally, by the final rigid polyvinyl chloride of spray-dried emulsion preparation nucleocapsid structure processing aid, its nucleocapsid ratio is 10:4.
Each 1.5 parts of the processing aid of above embodiment 1～5 preparation and pure acrylate class modifier PA-20 and styrenic modifier YM-02 joined respectively in 100 parts of polyvinyl chloride resins.
Wherein, PA-20 and YM-02 manufacturer are Shandong Shi Tuo macromolecular material limited-liability company.
Table 1 is that the rheological property to resin of embodiment 1-5, PA-20 and YM-02 compares.
Polyvinyl chloride base material formulation is PVC(SG-6) 100 parts, 2.5 parts of dibasic lead phosphites, 2.5 parts of tribasic lead sulfates, 0.5 part of calcium stearate, 0.15 part of stearic acid, 0.35 part of oxidized polyethlene wax, 10 parts of titanium dioxides, 20 parts, calcium carbonate, 2.6 parts of lead stearates.
The rheological property of table 1 embodiment 1-5, PA-20 and YM-02
Table 2 embodiment 1-5, PA-20 and YM-02 compare metal-stripping performance.
Test condition is for driving the two roller plasticizing of refining formula machine, and temperature is (preliminary roller 185, rear roller 180) ℃, and base material formulation is the same.
Table 2 embodiment 1-5, PA-20 and YM-02 are to metal-stripping performance
Claims (10)
1. a rigid polyvinyl chloride nucleocapsid structure processing aid, is characterized in that, in parts by weight, and raw material composed as follows:
100 parts of vinyl acetate monomers, water 250-300 part, dispersion agent 0.01-0.1 part, emulsifying agent 0.05-2.0 part, alkaline medium 0.5-2.0 part, initiator 0.01-0.05 part, monomers methyl methacrylate 20-50 part, emulsifying agent 0.5-3.0 part, initiator 0.01-0.05 part.
2. rigid polyvinyl chloride according to claim 1 nucleocapsid structure processing aid, is characterized in that, described dispersion agent is polyvinyl alcohol.
3. rigid polyvinyl chloride according to claim 2 nucleocapsid structure processing aid, dispersion agent is that one or both mixing in polyvinyl alcohol 1788 or polyvinyl alcohol 1799 are used.
4. rigid polyvinyl chloride according to claim 1 nucleocapsid structure processing aid, is characterized in that, described emulsifying agent is that one or more mixing in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, OP-10 or tween-80 are used.
5. rigid polyvinyl chloride according to claim 4 nucleocapsid structure processing aid, is characterized in that, emulsifying agent is that sodium lauryl sulphate is mixed use with OP-10.
6. rigid polyvinyl chloride according to claim 1 nucleocapsid structure processing aid, is characterized in that, described initiator is that one or more mixing in Potassium Persulphate, ammonium persulphate, sodium bisulfite or sodium bicarbonate are used.
7. rigid polyvinyl chloride according to claim 1 nucleocapsid structure processing aid, is characterized in that, described alkaline medium is that one or both mixing in potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate or ammoniacal liquor are used.
8. the synthetic method of a rigid polyvinyl chloride use nucleocapsid structure processing aid claimed in claim 1, it is characterized in that, first vinyl acetate monomer, water, dispersion agent, emulsifying agent, alkaline medium are added to reaction unit, logical nitrogen deoxygenation, under the stirring velocity of 50-300 rev/min, stir and within 2-5 hour, be warming up to 45 ℃-55 ℃, add initiator, control temperature of reaction below 60 ℃, reaction 2-5 hour, prepares stratum nucleare emulsion; Then monomers methyl methacrylate, emulsifying agent are added to stratum nucleare emulsion, logical nitrogen deoxygenation, under the stirring velocity of 50-300 rev/min, be warming up to 40 ℃-50 ℃, add initiator, control temperature of reaction below 55 ℃, reaction 2-3 hour, is then warming up to 80 ℃ of slakings, finally be cooled to 40 ℃ of dischargings, the spray-dried rigid polyvinyl chloride processing aid that obtains having nucleocapsid structure.
9. the synthetic method of nucleocapsid structure processing aid for rigid polyvinyl chloride according to claim 8, is characterized in that, the polymer emulsion emulsion particle of synthesized is nucleocapsid structure, and wherein stratum nucleare is polyvinyl acetate, and shell is methyl methacrylate.
10. the synthetic method of nucleocapsid structure processing aid for rigid polyvinyl chloride according to claim 8, is characterized in that, in nucleocapsid structure, nucleocapsid ratio is 10:2-10:5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262876A (en) * | 2014-10-15 | 2015-01-07 | 山东世拓高分子材料股份有限公司 | Modified antioxidant for polyvinyl acetate resin and preparation method of modified antioxidant |
| 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 |
| JP6091689B1 (en) * | 2016-08-04 | 2017-03-08 | 河村 良成 | Method for producing copolymer of vinyl acetate (VAc) and methyl methacrylate (MMA) |
| CN108219620A (en) * | 2016-12-09 | 2018-06-29 | 罗门哈斯公司 | The aqueous liquid dispersion of polymer particle with acorn form |
| CN114507404A (en) * | 2022-03-22 | 2022-05-17 | 宜兴市光辉包装材料有限公司 | Low-shrinkage cold-resistant PVC heat-shrinkable label film and preparation method thereof |
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| CN103467663A (en) * | 2013-09-13 | 2013-12-25 | 四川凯本新材料科技有限公司 | Preparation method of acrylic ester type processing aid with multilayer gradient core-shell structure |
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Patent Citations (2)
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| CN103351562A (en) * | 2013-07-25 | 2013-10-16 | 山东世拓高分子材料股份有限公司 | Multicomponent polymer for rigid polyvinyl chloride and preparation method of multicomponent polymer |
| CN103467663A (en) * | 2013-09-13 | 2013-12-25 | 四川凯本新材料科技有限公司 | Preparation method of acrylic ester type processing aid with multilayer gradient core-shell structure |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262876A (en) * | 2014-10-15 | 2015-01-07 | 山东世拓高分子材料股份有限公司 | Modified antioxidant for polyvinyl acetate resin and preparation method of modified antioxidant |
| 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 |
| JP6091689B1 (en) * | 2016-08-04 | 2017-03-08 | 河村 良成 | Method for producing copolymer of vinyl acetate (VAc) and methyl methacrylate (MMA) |
| CN108219620A (en) * | 2016-12-09 | 2018-06-29 | 罗门哈斯公司 | The aqueous liquid dispersion of polymer particle with acorn form |
| CN114507404A (en) * | 2022-03-22 | 2022-05-17 | 宜兴市光辉包装材料有限公司 | Low-shrinkage cold-resistant PVC heat-shrinkable label film and preparation method thereof |
| CN114507404B (en) * | 2022-03-22 | 2023-09-26 | 宜兴市光辉包装材料有限公司 | Cold-resistant PVC (polyvinyl chloride) heat-shrinkable label film with low shrinkage force and preparation method thereof |
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