CN105273120A - Polymerization method used for reducing vinyl chloride/vinyl acetate copolymer blending resin glass transition temperature - Google Patents
Polymerization method used for reducing vinyl chloride/vinyl acetate copolymer blending resin glass transition temperature Download PDFInfo
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- CN105273120A CN105273120A CN201410276528.1A CN201410276528A CN105273120A CN 105273120 A CN105273120 A CN 105273120A CN 201410276528 A CN201410276528 A CN 201410276528A CN 105273120 A CN105273120 A CN 105273120A
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- vinyl chloride
- acetate copolymer
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Abstract
The invention discloses a polymerization method used for reducing vinyl chloride/vinyl acetate copolymer blending resin glass transition temperature. The polymerization method comprises following steps: vinyl chloride monomer, vinyl acetate monomer, a dispersing agent, a size stabilization agent, an initiating agent, and desalted water are delivered into a polymerization kettle for reaction; temperature is increased to 48 to 52, and is maintained for 1 to 2h, and then is increased naturally to 60 to 65 DEG C; when reaction pressure is reduced to 200 to 300KPa, a terminating agent and an antifoaming agent are added to end the reaction so as to obtain a vinyl chloride/vinyl acetate copolymer blending resin slurry emulsion; an alkaline liquor is added, and the vinyl chloride/vinyl acetate copolymer blending resin is collected from a reaction product. According to the polymerization method, the vinyl chloride/vinyl acetate copolymer blending resin is relatively low in glass transition temperature Tg, excellent in fluidity, flexibility, toughness, and thermoplasticity, is convenient to process, can be adhered with metal surfaces easily, and can be widely used for preparing plastic floor, transparent packaging sheets, artificial leather, protective paint, magnetic binders, and printing plates.
Description
Technical field
The invention provides a kind of polymerization process reducing chlorine mixing resin of chloroacetic copolymerization second-order transition temperature.
Background technology
In polyvinyl chloride polymerization process, add Vinyl Acetate Monomer and carry out copolyreaction, form vinyl chloride-vinyl acetate copolymer resin, thus the second-order transition temperature (T of polyvinyl chloride can be reduced
g); make forming process temperature low; good fluidity and be easy to processing; there is good flexibility, toughness, thermoplastically; easily be adhered to the features such as metallic surface, chemical stability is good at normal temperatures, acid-fast alkali-proof; low to the transmitance specific absorption of water vapour, can be widely used in manufacturing many aspects such as plastic floor, packaging slide, leatheroid, protective cover, tape tackiness agent, printing plate.
Chlorine mixing resin of chloroacetic copolymerization is compared with common polyvinyl chloride (PVC) RESINS, owing to embedded in vinyl acetate between to for plastic ester molecule in polyvinyl chloride molecule, the closelypacked vinylchlorid segment rigid structure be present in homopolymer has suffered destruction, reduce intermolecular polarity, reduce intermolecular gravitation, and make its performance there occurs change.Be mainly reflected in chlorine mixing resin of chloroacetic copolymerization, than the polyvinyl chloride (PVC) RESINS of similar mass, there is comparatively low gel temperature and melt temperature (reducing by 30 ~ 40 DEG C).On the other hand, the introducing of ester group in molecule, can improve the dissolution rate of softening agent to resin, increases the adhesive power of resin and various bonding base material.
Vinyl acetate plays self-plasticizing action in the copolymer, can reduce the second-order transition temperature (T of chlorine mixing resin of chloroacetic copolymerization
g) and glutinous stream temperature, reduce melt viscosity, improve rheological performance, improve the processing characteristics of chlorine mixing resin of chloroacetic copolymerization.
At present, existing working method, method disclosed in 02136103.7 patent, the chlorine mixing resin of chloroacetic copolymerization second-order transition temperature obtained is generally 78 ~ 85 DEG C, and rheological performance is poor, and plasticity-is low, is difficult to the requirement meeting branch of industry.
Summary of the invention
The object of this invention is to provide a kind of polymerization process reducing chlorine mixing resin of chloroacetic copolymerization second-order transition temperature, to solve the defect that prior art exists.
Method of the present invention comprises the steps:
Vinyl chloride monomer, Vinyl Acetate Monomer, dispersion agent, whole granula, initiator and de-salted water are added in polymeric kettle and reacts, be warming up to 48 ~ 52 DEG C and maintain 1 ~ 2 hour, then 60 ~ 65 DEG C are naturally warming up to, during question response pressure drop 200 ~ 300KPa, add terminator and defoamer and terminate reaction, obtain the slurry emulsion of vinyl chloride-vinyl acetate copolymer resin, then add alkali lye, then from reaction product, the chlorine mixing resin of chloroacetic copolymerization described in collection;
The parts by weight of each component with 100 parts of monomers for benchmark is:
Described monomer component and weight percent content are:
Vinyl chloride monomer 85 ~ 93%
Vinyl Acetate Monomer 7 ~ 15%
Described initiator is Diisopropyl azodicarboxylate, peroxy dicarbonate two (2-ethylhexyl) ester or peroxidation (two) 3,5,5-trimethyl acetyl;
Described dispersion agent is the one in polyvinyl alcohol, Vltra tears or gelatin;
Described whole granula is one in sodium carbonate, sodium bicarbonate, bicarbonate of ammonia or sodium hydroxide or two or more compound use;
Described terminator is acetone semicarbazone thiocarbamide or dihydroxyphenyl propane;
Described defoamer elects silicon ether copolymer, organo-siloxane or polyethers as;
The product that the present invention obtains, its second-order transition temperature (T
g) lower, rheological performance is good, and plasticity-is high, can meet the requirement of branch of industry.
The present invention adopts two kinds of monomers feeding method, avoids the complicated technology that gradation adds, and effectively controls the vinyl acetic monomer content of resin, and this method technique is simple, and less investment, cost is low.
Adopt GB5761-93 standard, chlorine mixing resin of chloroacetic copolymerization prepared by method of the present invention is tested, result is as follows: viscosity number (VNml/g) is 80 ~ 100, plasticizer absorption rate is 7 ~ 15%, median size 25 ~ 38 μm, apparent density is 0.50 ~ 0.80g/ml, and whiteness is 85 ~ 95, and second-order transition temperature (Tg) is 70 ~ 75 DEG C;
Method of the present invention, processing ease, equipment is simple, prepared chlorine mixing resin of chloroacetic copolymerization, second-order transition temperature (T
g) lower; make forming process temperature low; good fluidity and be easy to processing; there is good flexibility, toughness, thermoplastically; easily be adhered to the features such as metallic surface, chemical stability is good at normal temperatures, acid-fast alkali-proof; low to the transmitance specific absorption of water vapour, can be widely used in manufacturing many aspects such as plastic floor, packaging slide, leatheroid, protective cover, tape tackiness agent, printing plate.
Embodiment
Embodiment 1
By 10.2kg vinylchlorid, 1.08kg vinyl acetate between to for plastic, 0.008kg initiator Diisopropyl azodicarboxylate, 0.006kg sodium bicarbonate, 0.0005kg sodium carbonate, 0.03kg Vltra tears and 16kg water are placed in polymeric kettle, be warming up to 52 DEG C and maintain 1 hour, then 60 DEG C are naturally warming up to, during question response pressure drop 300KPa, add 0.04kg terminator acetone semicarbazone thiocarbamide and 0.001kg defoamer organo-siloxane and terminate reaction, obtain the slurry emulsion of vinyl chloride-vinyl acetate copolymer resin, discharging is in blow tank, add the base extraction of the weight concentration 32.5% of 0.15kg, then stripping is carried out, centrifuge dehydration, air stream drying, obtain finished product.Adopt GB5761-93 standard to test the finished product obtained, the results are shown in Table 1.
Second-order transition temperature (Tg) is 70 ~ 75 DEG C.
Embodiment 2
By 11.5kg vinylchlorid, 0.9kg vinyl acetate between to for plastic, 0.009kg Diisopropyl azodicarboxylate, 0.006kg bicarbonate of ammonia, 0.0005kg sodium carbonate, 0.03kg polyethylene of dispersing agent alcohol and 16kg water are placed in polymeric kettle, be warming up to 48 DEG C and maintain 1 hour, then 65 DEG C are naturally warming up to, during question response pressure drop 200KPa, add 0.04kg terminator acetone semicarbazone thiocarbamide and 0.001kg defoamer silicon ether copolymer and terminate reaction, obtain the slurry emulsion of vinyl chloride-vinyl acetate copolymer resin, discharging is in blow tank, add 32.5% base extraction of 0.15kg, then stripping is carried out, centrifuge dehydration, air stream drying, obtain finished product.Adopt GB5761-93 standard to test the finished product obtained, the results are shown in Table 1.Second-order transition temperature (Tg) is 70 ~ 75 DEG C;
Embodiment 3
By 9.1kg vinylchlorid, 2.2kg vinyl acetate between to for plastic, 0.008kg Diisopropyl azodicarboxylate, 0.006kg sodium bicarbonate, 0.0005kg sodium carbonate, 0.03kg dispersion agent gelatin and 16kg water are placed in polymeric kettle, be warming up to 51 DEG C and maintain 1.5 hours, then 64 DEG C are naturally warming up to, during question response pressure drop 250KPa, reaction terminates, add 0.04kg terminator acetone semicarbazone thiocarbamide and 0.001kg defoamer polyethers and terminate reaction, obtain the slurry emulsion of vinyl chloride-vinyl acetate copolymer resin, discharging is in blow tank, add 32.5% base extraction of 0.15kg, then stripping is carried out, centrifuge dehydration, air stream drying, obtain finished product.Second-order transition temperature (Tg) is 70 ~ 75 DEG C; Adopt GB5761-93 standard to test the finished product obtained, the results are shown in Table 1.
Table 1
Table 1 continues
Claims (3)
1. reduce the polymerization process of chlorine mixing resin of chloroacetic copolymerization second-order transition temperature, it is characterized in that, comprise the steps: vinyl chloride monomer, Vinyl Acetate Monomer, dispersion agent, whole granula, initiator and de-salted water add in polymeric kettle and react, be warming up to 48 ~ 52 DEG C and maintain 1 ~ 2 hour, then 60 ~ 65 DEG C are naturally warming up to, during question response pressure drop 200 ~ 300KPa, add terminator and terminate reaction, obtain the slurry emulsion of vinyl chloride-vinyl acetate copolymer resin, add alkali lye again, then from reaction product, chlorine mixing resin of chloroacetic copolymerization described in collection.
2. method according to claim 1, is characterized in that, the parts by weight of each component with 100 parts of monomers for benchmark is:
Described monomer component and weight percent content are:
Vinyl chloride monomer 85 ~ 93%
Vinyl Acetate Monomer 7 ~ 15%.
3. method according to claim 1 and 2, is characterized in that, described initiator is Diisopropyl azodicarboxylate, peroxy dicarbonate two (2-ethylhexyl) ester or peroxidation (two) 3,5,5-trimethyl acetyl;
Described dispersion agent is the one in polyvinyl alcohol, Vltra tears or gelatin;
Described whole granula is one in sodium carbonate, sodium bicarbonate, bicarbonate of ammonia or sodium hydroxide or two or more;
Described terminator is acetone semicarbazone thiocarbamide or dihydroxyphenyl propane, and described defoamer elects silicon ether copolymer, organo-siloxane or polyethers as.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410276528.1A CN105273120A (en) | 2014-06-19 | 2014-06-19 | Polymerization method used for reducing vinyl chloride/vinyl acetate copolymer blending resin glass transition temperature |
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| CN201410276528.1A CN105273120A (en) | 2014-06-19 | 2014-06-19 | Polymerization method used for reducing vinyl chloride/vinyl acetate copolymer blending resin glass transition temperature |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189936A (en) * | 2016-07-21 | 2016-12-07 | 和县薛氏木制品制造有限公司 | A kind of high-temperature plastic plywood adhesive and preparation method thereof |
| CN111393548A (en) * | 2020-04-13 | 2020-07-10 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of polyvinyl chloride resin with high thermal stability |
| CN112062890A (en) * | 2020-09-19 | 2020-12-11 | 河北河汇新材料科技有限公司 | Preparation method of chloro-vinegar copolymer resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389506A (en) * | 2002-07-18 | 2003-01-08 | 上海天原集团天原化工有限公司 | Prepn. of vinyl chloride-vinyl acetate copolymer resin |
| CN1796424A (en) * | 2004-12-21 | 2006-07-05 | 天津渤天化工有限责任公司 | Method for fabricating mixing resin of chloroacetic copolymerization in use for polyvinyl chloride paste |
-
2014
- 2014-06-19 CN CN201410276528.1A patent/CN105273120A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1389506A (en) * | 2002-07-18 | 2003-01-08 | 上海天原集团天原化工有限公司 | Prepn. of vinyl chloride-vinyl acetate copolymer resin |
| CN1796424A (en) * | 2004-12-21 | 2006-07-05 | 天津渤天化工有限责任公司 | Method for fabricating mixing resin of chloroacetic copolymerization in use for polyvinyl chloride paste |
Non-Patent Citations (2)
| Title |
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| 张月芳等: "氯醋糊树脂的合成试验", 《聚氯乙烯》 * |
| 马学莲等: "悬浮法氯乙烯-醋酸乙烯酯共聚树脂生产技术及进展", 《聚氯乙烯》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106189936A (en) * | 2016-07-21 | 2016-12-07 | 和县薛氏木制品制造有限公司 | A kind of high-temperature plastic plywood adhesive and preparation method thereof |
| CN111393548A (en) * | 2020-04-13 | 2020-07-10 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of polyvinyl chloride resin with high thermal stability |
| CN112062890A (en) * | 2020-09-19 | 2020-12-11 | 河北河汇新材料科技有限公司 | Preparation method of chloro-vinegar copolymer resin |
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