CN1259368C - Prepn. of vinyl chloride-vinyl acetate copolymer resin - Google Patents
Prepn. of vinyl chloride-vinyl acetate copolymer resin Download PDFInfo
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- CN1259368C CN1259368C CN 02136103 CN02136103A CN1259368C CN 1259368 C CN1259368 C CN 1259368C CN 02136103 CN02136103 CN 02136103 CN 02136103 A CN02136103 A CN 02136103A CN 1259368 C CN1259368 C CN 1259368C
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- vinyl acetate
- chloroethylene
- acetate copolymer
- vinyl chloride
- copolymer resin
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Abstract
The present invention relates to a preparation method for chloroethylene-vinyl acetate copolymer mixed resin. The the preparation method comprises the following steps: adding chloroethylene, vinyl acetate ester, evocating agents, particle adjustants, pH stabilizing agents, dispersants, dispersion aids and water in a polymerization kettle, carrying out reaction for 3 to 8 hours at 40 to 70 DEG C, and adding terminators so as to obtain water suspension of the chloroethylene-vinyl acetate copolymer mixed resin; carrying out purification by a conventional method, eliminating unreacted chloroethylene monomer and unreacted vinyl acetate ester monomer, and carrying out centrifugal drying so as to obtain finished products. The present invention has the advantages of easy operation, simple equipment, compact granular structure of prepared chloroethylene-vinyl acetate resin, even and fine granules, concentrative distribution and low oil absorbency; the present invention can reduce plasticization temperature in vast scale, improve the storage stability of plastisol and improve the flow thixotropy of the plastisol. The present invention can be extensively used as adhesive for artificial leather, floor leather, wallpaper, etc., marine paint, steel plate coating layers, sealing glue for automobiles, antirust paint and stone stroke resistant paint for automobile chassis.
Description
Technical field
The present invention relates to the method that a kind of suspension method prepares the vinyl chloride-vinyl acetate resin.
Background technology
In poly vinyl chloride plastisol, add vinyl chloride-vinyl acetate copolymer resin, can reduce the solidification value of polyvinyl chloride significantly, reduce and stick with paste viscosity and improve plastipaste stability, improve colloid toughness and plasticity, strengthen anti-impact force and anti-shearing force, can strengthen bonding force simultaneously various matrix (as metal, fiber).
The vinyl chloride-vinyl acetate copolymer resin that is used for blending should have better physical and chemical property, and its viscosity number should be 80～100, and apparent density should be more than 0.5mg/ml, and oil absorbency should be below 14%.Therefore, appropriate preparation method has become the focus that each production firm pays close attention to.Chinese patent 85108354 grades disclose the preparation method of ethene-vinyl acetate copolymer resins, but the method that this patent provided can't prepare vinyl chloride-vinyl acetate copolymer resin.The preparation method of the vinyl chloride-vinyl acetate copolymer resin that traditional and CN85108354, CN86103607 patent are provided, exist all that resin particle is thick partially, the defective of structure undertighten and viscosity reducing effect difference, therefore providing a kind of practicable method for preparing vinyl chloride-vinyl acetate copolymer resin, is that institute of relevant branch of industry is very expected.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of preparation method of vinyl chloride-vinyl acetate copolymer resin, thick partially to overcome the resin particle that prior art makes, afterwards viscosity reducing effect is poor with becoming paste for the structure undertighten, is easy to generate defectives such as precipitation, satisfies the demand of branch of industry.
The vinyl chloride-vinyl acetate resin of being addressed is the polymkeric substance with following structure fragment:
Polymerization degree n wherein, the numerical range of m exists respectively: 770～890, between 30～110.
Be the good paste vinyl chloride-vinyl acetate copolymer resin of obtained performance, the selection of dispersion agent that reaction system adopted and dispersion aids and add-on thereof, reaction process condition is very crucial, the contriver has proposed technical scheme as described below through a large amount of tests:
Method of the present invention comprises the steps:
Vinylchlorid, vinyl acetate, initiator, whole granula, pH stablizer, dispersion agent, dispersion aids and water are added in the polymeric kettle, under 40～70 ℃ temperature, reacted 3～8 hours, add terminator, can obtain the aqeous suspension of vinyl chloride-vinyl acetate copolymer resin, adopt conventional method purifying then, remove unreacted intact with vinyl chloride monomer and Vinyl Acetate Monomer, centrifugal drying promptly obtains finished product.Wherein:
The parts by weight of each component are that benchmark is with 100 parts of monomers:
Initiator 0.02～0.8
Whole granula 0.05～0.1
PH stablizer 0.02～0.1
Dispersion agent 0.05～1.0
Dispersing auxiliary 0.01～0.5
Terminator 0.01～0.05
Water 100～400.
Wherein: monomeric component and the weight percent content addressed are:
Vinyl chloride monomer 82～95%
Vinyl acetate 5～18%
Said initiator comprises one or more in peroxy dicarbonate ethylhexyl, dilauroyl peroxide, benzoyl peroxide, peroxy dicarbonate glycol wax ester, peroxidation two myristins, the new decane acid esters of peroxidation, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or peroxy dicarbonate two (the benzene oxygen ethyl) ester;
Said whole granula comprises one or more in EDTA, EDTA disodium, Sodium Nitrite, trisodium citrate or the anhydrous sodium sulphate;
Said pH stablizer comprises one or more in sodium bicarbonate, sodium hydroxide, Sodium phosphate dibasic or the ammonia;
Said dispersion agent comprises one or more in ether of cellulose, polyvinyl alcohol, polypeptide polymer (as gelatin), sodium polyacrylate, vinylbenzene or the MALEIC ANHYDRIDE interpolymer;
Said auxiliary agent comprises one or more in lauryl alcohol, hexadecanol, stearyl alcohol, hard ester acid, clorafin, trichloroethane or the propyl group dioctyl phthalate.
Said terminator comprises contract in the amido thiocarbamide one or more of dihydroxyphenyl propane or acetone.Preferred dispersing agent is ether of cellulose, polyvinyl alcohol, polypeptide polymer, and adding parts by weight is that benchmark is 10～50 with 100 parts of monomers, and preferred temperature of reaction is 55～60 ℃.
Adopt the GB5761-93 standard, the vinyl chloride-vinyl acetate resin that method of the present invention is prepared is tested, and the result is as follows: viscosity number (VN ml/g) is 80～100, and the plasticizer absorption rate is 7～14%, median size is 20～50 μ m, and apparent density is 0.50～0.758/ml.
Method of the present invention, processing ease, equipment is simple, prepared vinyl chloride-vinyl acetate resin, grain pattern is tight, and particle is thin and even, distributes and concentrates oil absorbency low, can reduce plasticization temperature significantly, improve the package stability of plastipaste, improve the mobile thixotropy of sticking with paste.Can be widely used in caking agents such as leatheroid, flooring laminate, wallpaper, marine finish, steel plate coating, automobile sealed glue, rust proof paint, automobile chassis stone-impact-proof paint.
Embodiment
Embodiment 1
With 14.25 kilograms of vinylchlorid, 0.75 kilogram vinyl acetate, 0.014 kilogram peroxidation two myristins, 0.016 kilogram trisodium citrate, 0.012 kilogram sodium bicarbonate, 0.015 kilogram Vltra tears and polypeptide polymer, 0.026 kilogram clorafin and 27 kg of water place polymeric kettle, under 58 ℃ temperature, reacted 7～8 hours, add 0.003 kilogram of acetone amido thiocarbamide that contracts, promptly obtain the aqeous suspension of vinyl chloride-vinyl acetate copolymer resin, use the water vapour stripping, remove unreacted intact vinylchlorid and Vinyl Acetate Monomer, centrifugal drying promptly obtains finished product.Adopt the GB5761-93 standard that the finished product that is obtained is tested, the results are shown in Table 1.
Embodiment 2
With 13.8 kilograms of vinylchlorid, 1.2 kilogram vinyl acetate, 0.014 kilogram peroxidation two myristins, 0.018 kilogram trisodium citrate, 0.012 kilogram sodium bicarbonate, 0.015 kilogram Vltra tears and polypeptide polymer, 0.026 kilogram 16,18 mixing acid and 27 kg of water place polymeric kettle, under 58 ℃ temperature, reacted 7～8 hours, add 0.003 kilogram of acetone amido thiocarbamide that contracts, promptly obtain the aqeous suspension of vinyl chloride-vinyl acetate copolymer resin, use the water vapour stripping, remove unreacted intact vinylchlorid and Vinyl Acetate Monomer, centrifugal drying promptly obtains finished product.Adopt the GB5761-93 standard that the finished product that is obtained is tested, the results are shown in Table 1.
Embodiment 3
With 12.75 kilograms of vinylchlorid, 2.25 kilogram Vinyl Acetate Monomer, 0.015 kilogram peroxidation two myristins, 0.02 kilogram trisodium citrate, 0.012 kilogram sodium bicarbonate, 0.018 kilogram Vltra tears and polypeptide polymer, 0.026 kilogram stearyl alcohol and 27 kg of water place polymeric kettle, under 58 ℃ temperature, reacted 7～8 hours, add 0.003 kilogram of dihydroxyphenyl propane, promptly obtain the aqeous suspension of vinyl chloride-vinyl acetate copolymer resin, use the water vapour stripping, remove unreacted intact vinylchlorid and Vinyl Acetate Monomer, centrifugal drying promptly obtains finished product.Adopt the GB576l-93 standard that the finished product that is obtained is tested, the results are shown in Table 1.
Embodiment 4～6
Respectively 100 gram embodiment 1,2 or 3 finished products, 4 gram stablizers, 8831,0.5 gram stearic acid being mixed, is that 60 rev/mins, fusion time are that the test rheological property the results are shown in Table 2 under 10 minutes the condition at the main frame motor rotary speed.
By table 2 as seen along with interpolymer molecule form in vinyl acetate content must increase, melt temperature reduces, the fusion time shortens, and shows that interpolymer plastifies easily, thereby can reduce processing temperature.
Embodiment 7～8
The plastipaste viscosimetric analysis
Plastipaste is formed: 65 grams are stuck with paste resin P440, and 35 gram vinyl chloride-vinyl acetate resins, 50 gram plasticizer DOPs select for use the vinyl chloride-vinyl acetate resin that vinyl acetate is identical, oil absorbency is different to test, and vinyl acetate content is 6.98%, the results are shown in Table 3.
Is made of identically the visible interpolymer of table 3, but resin gets the grain pattern difference, and person's viscosity reducing effect is poor, and the ageing poor stability for short texture (being the oil absorbency height), otherwise the tight person's viscosity reduction of structure is remarkable, and paste viscosity stability in storage is good.
From table 2 and table 3 the result can clearly illustrate that and realized that chlorine mixing resin of chloroacetic copolymerization of the present invention can reduce the resin plasticization temperature and can reduce the purpose of sticking with paste viscosity again significantly.
Table 1
| Viscosity number VN (ml/g) | Oil absorbency CPA (%) | Apparent density BD (g/ml) | Vinyl acetate content %W | |
| Embodiment 1 | 98 | 8.3 | 0.66 | 3.7 |
| Embodiment 2 | 97 | 8.4 | 0.65 | 6.98 |
| Embodiment 3 | 90 | 8.2 | 0.65 | 12.75 |
Table 2
| Vinyl acetate content %W | Fusion moment of torsion (Md) | Melt temperature (℃) | Fusion time (second) | Balancing torque (Md) | Equilibrium temperature (℃) | Starting time (second) | |
| Embodiment 1 | 3.7 | 2447 | 173 | 213 | 1586 | 188 | 586 |
| Embodiment 3 | 12.75 | 3355 | 147 | 159 | 2007 | 165 | 431 |
Table 3
| Oil absorbency % | Viscosity (CPS) | ||||
| 2 hours | 1 day | 3 days | 21 days | ||
| Embodiment 7 | 7.7 | 4300 | 5225 | 5275 | 5420 |
| Embodiment 8 | 17.2 | 9210 | 11200 | 11300 | 12500 |
| Comparative Examples * | 9000 | 14900 | 20600 | 21600 | |
*Sticking with paste resin with 100%P440 is in the same old way.
Claims (4)
1. the preparation method of vinyl chloride-vinyl acetate copolymer resin is characterized in that comprising the steps:
To react in vinylchlorid, vinyl acetate, initiator, whole granula, pH stablizer, dispersion agent, dispersion aids and the water adding polymeric kettle, reacted 3～8 hours, add terminator, promptly obtain the aqeous suspension of vinyl chloride-vinyl acetate copolymer resin, wherein:
The parts by weight of each component are that benchmark is with 100 parts of monomers:
Initiator 0.02～0.8
Whole granula 0.05～0.1
PH stablizer 0.02～0.1
Dispersion agent 0.05～1.0
Dispersing auxiliary 0.01～0.5
Terminator 0.01～0.05
Water 100～400;
Wherein: monomeric component and the weight percent content addressed are:
Vinyl chloride monomer 82～95%
Vinyl acetate 5～18%;
Said initiator comprises one or more in peroxy dicarbonate ethylhexyl, dilauroyl peroxide, benzoyl peroxide, peroxy dicarbonate glycol wax ester, peroxidation two myristins, the new decane acid esters of peroxidation, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or peroxy dicarbonate two (the benzene oxygen ethyl) ester;
Said whole granula comprises one or more in EDTA, EDTA disodium, Sodium Nitrite, trisodium citrate or the anhydrous sodium sulphate;
Said pH stablizer comprises one or more in sodium bicarbonate, sodium hydroxide, Sodium phosphate dibasic or the ammonia;
Said dispersion agent comprises one or more in ether of cellulose, polyvinyl alcohol, polypeptide polymer, sodium polyacrylate, vinylbenzene or the MALEIC ANHYDRIDE interpolymer;
Said auxiliary agent comprises one or more in lauryl alcohol, hexadecanol, stearyl alcohol, hard ester acid, clorafin, trichloroethane or the propyl group dioctyl phthalate;
Said terminator comprises contract in the amido thiocarbamide one or more of dihydroxyphenyl propane or acetone.
2. the method for claim 1 is characterized in that, temperature of reaction is 40～70 ℃.
3. method as claimed in claim 2 is characterized in that, temperature of reaction is 55～60 ℃.
4. the method for claim 1 is characterized in that, dispersion agent is ether of cellulose, polyvinyl alcohol or polypeptide polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136103 CN1259368C (en) | 2002-07-18 | 2002-07-18 | Prepn. of vinyl chloride-vinyl acetate copolymer resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136103 CN1259368C (en) | 2002-07-18 | 2002-07-18 | Prepn. of vinyl chloride-vinyl acetate copolymer resin |
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|---|---|
| CN1389506A CN1389506A (en) | 2003-01-08 |
| CN1259368C true CN1259368C (en) | 2006-06-14 |
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|---|---|---|---|
| CN 02136103 Expired - Lifetime CN1259368C (en) | 2002-07-18 | 2002-07-18 | Prepn. of vinyl chloride-vinyl acetate copolymer resin |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343348C (en) * | 2005-12-07 | 2007-10-17 | 江苏常铝铝业股份有限公司 | Hot sealing coating for calorifier aluminum foil, and its preparation method and coating method |
| DE102005058744A1 (en) * | 2005-12-08 | 2007-06-14 | Wacker Polymer Systems Gmbh & Co. Kg | Polyvinyl ester and poly (meth) acrylate solid resins with high polydispersity |
| CN101824193B (en) * | 2010-02-24 | 2013-01-30 | 杭州高新橡塑材料股份有限公司 | Cold-resistant PVC cable material and preparation method thereof |
| CN102344278B (en) * | 2011-07-03 | 2012-11-21 | 江苏德一新型建筑材料科技有限公司 | Permeable crystallization type cement-based waterproof mucilage |
| CN102775544A (en) * | 2012-08-08 | 2012-11-14 | 上海氯碱化工股份有限公司 | Closely spherical blending resin of vinyl chloride-vinyl acetate copolymer and preparation method thereof |
| CN105273120A (en) * | 2014-06-19 | 2016-01-27 | 上海氯碱化工股份有限公司 | Polymerization method used for reducing vinyl chloride/vinyl acetate copolymer blending resin glass transition temperature |
| CN107603305A (en) * | 2017-07-31 | 2018-01-19 | 无锡市永兴金属软管有限公司 | A kind of car repair paint special and preparation method thereof |
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- 2002-07-18 CN CN 02136103 patent/CN1259368C/en not_active Expired - Lifetime
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