CN101775105B - Preparation method of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin - Google Patents
Preparation method of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin Download PDFInfo
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Abstract
The invention relates to the technical field of vinyl chloride resin, in particular to a preparation method of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin. A single emulsifier and a single initiator are adopted by the original synthesis process, and tests proof that the single emulsifier can enable polymer latex not to be stable, and therefore, a stable polymerization product can not be obtained; the single initiator enables a polymerization system not to be stable, and reaction is difficult to control; freezing demulsification, filtering, washing, drying and the like are adopted as treatment processes of a vinyl chloride grafting copolymer emulsion to form a thick and big aggregated particle structure, and the product performance is low; moreover, much wastewater and many waste residues are generated in the process. In the invention, the stability of the latex is ensured by adopting a compound emulsifier and a compound initiator, which ensures that the latex has better average particle diameter, the polymerization system is stable and the reaction is easy to control; centrifugal spray drying is adopted to treat emulsion resin, and thereby, a good resin product with even particle size distribution and good processing performance can be obtained; and the wastewater and the waste residues are not generated, the process flow is short and the energy can be saved and the consumption can be lowered.
Description
Technical field
The present invention relates to the vinyl chloride resin technical field, specifically a kind of production method of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin.
Background technology
China is PVC production and consumption big country, and along with improving constantly of living standards of the people, the demand growth of PVC goods is very fast, has driven PVC impact modifier ACR growth of requirement simultaneously.But China's rosin products mid and low-end products proportion is bigger, the main dependence on import of high-end product (as ACR, CPE, MBS, CPVC etc.), and the polrvinyl chloride product ageing resistance of interpolation ACR is good, applied widely, develops very fast.In the U.S., the consumption of ACR has surpassed MBS, becomes the polyvinyl chloride (PVC) RESINS impact modifier of consumption maximum.But the restriction of aspect such as the technology of being subjected to, raw material, the PVC auxiliary agent industry development of China still can not satisfy domestic growing needs.In recent years, along with the operation of PVC imported unit, domestic PVC increase of production was rapid, to the also increase day by day of demand of ACR.And the output of domestic ACR resin and quality do not satisfy this demand far away, and product still needs a large amount of imports.
" preparation method of high-impact polyacrylate composite particles grafting vinyl chloride emulsion resin " patent of Hebei University of Technology (patent No. is: ZL02148636.0), find to remain in following defective:
What 1, adopt in the synthesis technique of high-impact polyacrylate grafting vinyl chloride copolymer resins is single emulsifying agent, when experiment showed, that by production single emulsifier concentration is too low, can make polymerization latex instability, can not obtain stable polymerization product; When emulsifier concentration was too high, then the median size of latex primary particle was little, and viscosity is big, and processing and the foaming effect of sticking with paste resin are all bad.The anionic emulsifier Sodium palmityl sulfate is the most frequently used and effect emulsifying agent preferably.But use this emulsifying agent merely, the emulsifying agent total concn that polymerization system needs is very big, can not obtained performance well stick with paste resin.
What 2, adopt in the synthesis technique of high-impact polyacrylate grafting vinyl chloride copolymer resins is single initiator, experiment showed, that by production single initiator makes polymerization system instability, reaction be difficult to control, the finished product size distribution is than broad, poor processability.
3, vinyl chloride graft copolymer emulsion treatment process has been adopted freezing breakdown of emulsion, filtration, washing, oven dry etc., formed thick agglomerating particles structure, product performance are low.
4, in the seed emulsion building-up process, employing be three one step preparation methods, technical process is longer, complicated operation is not easy to carry out Industry Promotion and uses.
Summary of the invention:
The production method that the purpose of this invention is to provide a kind of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin adopts compound emulsifying agent and composite initiator, makes polymerization system stable, and reaction is easy to control, can obtain stable polymerization product; Adopt the centrifugal spray dryer drying process, it is even to access size distribution, the good rosin products of good processability.
Technical scheme of the present invention is: be main raw material with the acrylic ester monomer, deionized water, compound emulsifying agent, composite initiator, linking agent are auxiliary material, and forming esters of acrylic acid rubber polymer and " shell " that " nuclear " is low cross-linking by the monomeric mode of continuous dropwise addition of acrylic acid ester is the polyacrylic ester latex particle that has than the polymkeric substance of high glass transition temperature; After in polymeric kettle, adding deionized water, polyacrylic ester latex particle and various auxiliary agent then, drip vinyl chloride monomer and carry out letex polymerization, make the high-impact polyacrylate grafting vinyl chloride copolymer resins of nuclear-shell inierpeneirating network structure, concrete production stage is as follows:
(1) preparation of seed emulsion stratum nucleare
Deionized water is added in the enamel reaction still, add compound emulsifying agent again, the anchor formula that with the rotating speed is 90r/min stirred 20 minutes, feed the air in the nitrogen replacement still, add composite initiator, add the mixing solutions of acrylic ester monomer and linking agent then, begin after mixing to heat up, temperature is controlled at 70 ± 2 ℃, keeps reaction 1.5 hours, obtains the esters of acrylic acid rubber polymer of low cross-linking;
(2) preparation of polyacrylic ester latex particle
In aforesaid reaction vessel, continue to add compound emulsifying agent and composite initiator, with the rotating speed is the anchor formula stirring of 90r/min, after waiting to mix, the mixing solutions of beginning dropwise addition of acrylic acid ester class and linking agent in still, rate of addition is 0.48Kg/min, is warming up to 83-85 ℃ simultaneously, after waiting to be added dropwise to complete, continue insulation 2 hours, form the polyacrylic ester compounded latex particle of rock steady structure;
(3) the high-impact polyacrylate grafting vinyl chloride copolymer resins is synthetic
Earlier to 1.5m
3Polymeric kettle in add deionized water and compound emulsifying agent, for 40r/min speed stirs composite initiator after 20 minutes, polyacrylic ester latex particle, restir 10 minutes is after mix fully with the rotating speed, regulating the pH value is 8.5-9.5; Close kettle cover, charge into the nitrogen pressurize 15 minutes of 0.6MPa, be evacuated to then-0.080MPa, pressurize 10 minutes, the flow dropping vinyl chloride monomer with 1.2L/min is warming up to 55 ℃ to polymeric kettle simultaneously, polymerization is 5.5 hours under this temperature condition, reaction terminating when pressure is reduced to 0.5MPa; Utilize still pressure handle material to be pressed into blow tank, open vent valve, be warming up to 70 ℃, when the still internal pressure is reduced to 0.02MPa by the time, handle with nitrogen replacement to blow tank; With the dnockout pump material is squeezed into the centrifugal spray dryer drying system, carry out drying, control dehumidification system inlet temperature is between 160-163 ℃, and temperature out is at 60-63 ℃, and in addition, the air quantity of control gas blower is 45-47m
3/ min; The water content of the finished product is≤0.4%.
Described compound emulsifying agent is sodium lauryl sulphate and polyoxyethylene alkylphenol ether-10, and both ratios are 2: 1; Described composite initiator is Potassium Persulphate and sodium bisulfite, and both ratios are 3.5-3.7: 1; Described linking agent is a 1,4 butanediol diacrylate.
Advantage of the present invention is effectively to control the particle diameter and the quantity of seed emulsion latex particle, and nucleocapsid structure is more even, the percentage of grafting of vinylchlorid and polyacrylic ester latex particle has also reached tangible raising, has further improved shock resistance, ageing resistance and the wear resistance etc. of product.The product secondary particle is coalescent closely, smooth surface, and shape is regular, and the softening agent of absorption is few, and paste viscosity is low, and fusion time shortens, and melt temperature reduces, and the processing moment of torsion obviously reduces, and is easy to processing.And directly graft polymerization can increase the bonding force of resin particle and matrix PVC, and the existence of grafts has improved alternate consistency in the resin, has improved rubber phase dispersed uniform degree, has greatly improved elastic utilization ratio.Adopt compound emulsifying agent can not only guarantee that latex is very stable, and can reduce emulsifying agent total concn in the polymerization system, make latex that better average be arranged, reduce the viscosity of sticking with paste resin, improve processing characteristics; Adopt composite initiator to guarantee the stable of latex, make latex that better average be arranged, polymerization system is stable, and reaction is easy to control; Emulsion resin handle to adopt centrifugal spray drying, can obtain the 0.2-1.5um particle diameter that is evenly distributed, the good rosin products of good processability, no waste water, waste residue generation.
Embodiment:
(1) preparation of seed emulsion stratum nucleare
The prescription and the controlled temperature of the preparation of table 1. seed emulsion stratum nucleare
Wherein
The compound emulsifying agent ratio is sodium lauryl sulphate among each embodiment: the ratio of polyoxyethylene alkylphenol ether=2: 1 composite initiator is a Potassium Persulphate: sodium bisulfite=3.5: 1
The composite initiator ratio is a Potassium Persulphate among the embodiment 2: sodium bisulfite=3.7: 1
The composite initiator ratio is a Potassium Persulphate among the embodiment 3: sodium bisulfite=3.7: 1
The composite initiator ratio is a Potassium Persulphate among the embodiment 4: sodium bisulfite=3.6: 1
Deionized water is added in the enamel reaction still, add compound emulsifying agent again, the anchor formula that with the rotating speed is 90r/min stirred 20 minutes, feed the air in the nitrogen replacement still, add composite initiator, add the mixing solutions of acrylic ester monomer and linking agent then, begin after mixing to heat up, temperature is controlled at 70 ± 2 ℃, keeps reaction 1.5 hours, obtains the esters of acrylic acid rubber polymer of low cross-linking.
(2) preparation of polyacrylic ester latex particle
The prescription and the controlled temperature of table 2. polyacrylic ester latex particle preparation
In aforesaid reaction vessel, continue to add compound emulsifying agent and composite initiator, with the rotating speed is the anchor formula stirring of 90r/min, after waiting to mix, the mixing solutions of beginning dropwise addition of acrylic acid ester class and linking agent in still, rate of addition is 0.48Kg/min, is warming up to 83-85 ℃ simultaneously, after waiting to be added dropwise to complete, continue insulation 2 hours, form the polyacrylic ester compounded latex particle of rock steady structure;
(3) the high-impact polyacrylate grafting vinyl chloride copolymer resins is synthetic
Table 3. high-impact polyacrylate grafting vinyl chloride copolymer resins synthesizing formula and control condition
Earlier to 1.5m
3Polymeric kettle in add deionized water and compound emulsifying agent, for 40r/min speed stirs composite initiator after 20 minutes, polyacrylic ester latex particle, restir 10 minutes is after mix fully with the rotating speed, regulating the pH value is 8.5-9.5; Close kettle cover, charge into the nitrogen pressurize 15 minutes of 0.6MPa, be evacuated to then-0.080MPa, pressurize 10 minutes, the flow dropping vinyl chloride monomer with 1.2l/min is warming up to 55 ℃ to polymeric kettle simultaneously, polymerization is 5.5 hours under this temperature condition, reaction terminating when pressure is reduced to 0.5MPa; Utilize still pressure handle material to be pressed into blow tank, open vent valve, be warming up to 70 ℃, when the still internal pressure is reduced to 0.02MPa by the time, handle with nitrogen replacement to blow tank; With the dnockout pump material is squeezed into the centrifugal spray dryer drying system, carry out drying, control dehumidification system inlet temperature is between 160-163 ℃, and temperature out is at 60-63 ℃, and in addition, the air quantity of control gas blower is 45-47m
3/ min; The water content of the finished product is≤0.4%.
(4) chloroethylene copolymer resin drying treatment
With the dnockout pump above-mentioned synthetic material is squeezed into the centrifugal spray dryer drying system, carry out drying, the air quantity of control gas blower is 45-47m
3/ min.
Table 4 chloroethylene copolymer resin drying treatment control condition
| Embodiment | Inlet temperature (℃) | Temperature out (℃) | Air quantity (m 3/min) |
| Embodiment 1 | 160 | 60 | 45 |
| Embodiment 2 | 162 | 61 | 47 |
| Embodiment 3 | 159 | 60 | 46 |
| Embodiment 4 | 161 | 61 | 47 |
Each embodiment graft copolymerization resin of table 5 and material property table look-up thereof
Claims (2)
1. the production method of a high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin, it is characterized in that with the acrylic ester monomer being main raw material, deionized water, compound emulsifying agent, composite initiator, linking agent are auxiliary material, and forming esters of acrylic acid rubber polymer and " shell " that " nuclear " is low cross-linking by the monomeric mode of continuous dropwise addition of acrylic acid ester is the polyacrylic ester latex particle that has than the polymkeric substance of high glass transition temperature; After in polymeric kettle, adding deionized water, polyacrylic ester latex particle and various auxiliary agent then, drip vinyl chloride monomer and carry out letex polymerization, make the high-impact polyacrylate grafting vinyl chloride copolymer resins of nuclear-shell inierpeneirating network structure, concrete production stage is as follows:
(1) preparation of seed emulsion stratum nucleare
Deionized water is added in the enamel reaction still, add compound emulsifying agent again, the anchor formula that with the rotating speed is 90r/min stirred 20 minutes, feed the air in the nitrogen replacement still, add composite initiator, add the mixing solutions of acrylic ester monomer and linking agent then, begin after mixing to heat up, temperature is controlled at 70 ± 2 ℃, keeps reaction 1.5 hours, obtains the esters of acrylic acid rubber polymer of low cross-linking;
(2) preparation of polyacrylic ester latex particle
In aforesaid reaction vessel, continue to add compound emulsifying agent and composite initiator, with the rotating speed is the anchor formula stirring of 90r/min, after waiting to mix, the mixing solutions of beginning dropwise addition of acrylic acid ester class and linking agent in still, rate of addition is 0.48Kg/min, is warming up to 83-85 ℃ simultaneously, after waiting to be added dropwise to complete, continue insulation 2 hours, form the polyacrylic ester compounded latex particle of rock steady structure;
(3) the high-impact polyacrylate grafting vinyl chloride copolymer resins is synthetic
Earlier to 1.5m
3Polymeric kettle in add deionized water and compound emulsifying agent, for after 40r/min speed stirs 20 minutes, add composite initiator, polyacrylic ester latex particle with the rotating speed, restir 10 minutes is after mix fully, regulating the pH value is 8.5-9.5; Close kettle cover, charge into the nitrogen pressurize 15 minutes of 0.6MPa, be evacuated to then-0.080MPa, pressurize 10 minutes, the flow dropping vinyl chloride monomer with 1.2L/min is warming up to 55 ℃ to polymeric kettle simultaneously, polymerization is 5.5 hours under this temperature condition, reaction terminating when pressure is reduced to 0.5MPa; Utilize still pressure handle material to be pressed into blow tank, open vent valve, be warming up to 70 ℃, when the still internal pressure is reduced to 0.02MPa by the time, handle with nitrogen replacement to blow tank; With the dnockout pump material is squeezed into the centrifugal spray dryer drying system, carry out drying, control dehumidification system inlet temperature is between 160-163 ℃, and temperature out is at 60-63 ℃, and in addition, the air quantity of control gas blower is 45-47m
3/ min; The water content of the finished product is≤0.4%;
Described compound emulsifying agent is sodium lauryl sulphate and polyoxyethylene alkylphenol ether-10, and both ratios are 2: 1; Described composite initiator is Potassium Persulphate and sodium bisulfite, and both ratios are 3.5-3.7: 1; Described linking agent is a 1,4 butanediol diacrylate.
2. the production method of a kind of high-impact polyacrylate grafting vinyl chloride emulsion copolymer resin as claimed in claim 1, it is characterized in that described esters of acrylic acid is the mixture of n-butyl acrylate, 2-EHA, both blended ratios are 2-EHA: n-butyl acrylate=26-30: 100.
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| CN103570881B (en) * | 2012-07-20 | 2016-09-28 | 河北盛华化工有限公司 | A kind of polyacrylate grafting vinyl chloride composite resin and preparation method thereof |
| CN102807647B (en) * | 2012-09-03 | 2015-03-25 | 四川省金路树脂有限公司 | Polyacrylate latex subjected to suspension graft copolymerization with vinyl chloride |
| CN103724909A (en) * | 2013-12-19 | 2014-04-16 | 河北盛华化工有限公司 | High-impact-resistant PVC rigid tube and preparation method thereof |
| CN104776687B (en) * | 2014-09-05 | 2017-09-29 | 山东诚创医药技术开发有限公司 | The drying means of colesevelam hydrocholoride polymer |
| CN104804144A (en) * | 2015-04-15 | 2015-07-29 | 北京化工大学 | Preparation method of impact-resistant PVC (polyvinyl chloride) |
| CN108239239A (en) * | 2017-12-05 | 2018-07-03 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyvinyl chloride copolymer resins composite material |
| CN116731257A (en) * | 2023-06-29 | 2023-09-12 | 中盐安徽天辰化工有限公司 | Acrylic ester-chloroethylene copolymerization paste resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0700965A1 (en) * | 1994-09-08 | 1996-03-13 | Rohm And Haas Company | Impact-modified poly(vinylchloride) |
| CN1418898A (en) * | 2002-11-14 | 2003-05-21 | 河北工业大学 | Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin |
| CN1743371A (en) * | 2005-09-29 | 2006-03-08 | 河北工业大学 | Nucleocapsid structure polyvinyl chloride impact modifier, and its preparing method and use |
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| KR100484722B1 (en) * | 2002-01-25 | 2005-04-20 | 주식회사 엘지화학 | Acrylic impact modifier prepared by multi-stage polymerization and method for preparing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0700965A1 (en) * | 1994-09-08 | 1996-03-13 | Rohm And Haas Company | Impact-modified poly(vinylchloride) |
| CN1418898A (en) * | 2002-11-14 | 2003-05-21 | 河北工业大学 | Process for preparing high shock-resistance polyacrylic ester composite particle grafted vinyl chloride emulsion resin |
| CN1743371A (en) * | 2005-09-29 | 2006-03-08 | 河北工业大学 | Nucleocapsid structure polyvinyl chloride impact modifier, and its preparing method and use |
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