CN100509943C - Method for preparing resin of polyvinyl chloride paste - Google Patents
Method for preparing resin of polyvinyl chloride paste Download PDFInfo
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- CN100509943C CN100509943C CNB2007100112524A CN200710011252A CN100509943C CN 100509943 C CN100509943 C CN 100509943C CN B2007100112524 A CNB2007100112524 A CN B2007100112524A CN 200710011252 A CN200710011252 A CN 200710011252A CN 100509943 C CN100509943 C CN 100509943C
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- vinyl chloride
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- pvc resin
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Abstract
This invention discloses a method for preparing poly (vinyl chloride) paste resin. The method comprises: (1) preparing poly(vinyl chloride) emulsion A with particle sizes of 0.15-0.20 mu.m and poly(vinyl chloride) emulsion B with particle sizes of 0.80-1.5 mu.m from chloroethylene monomer via emulsion polymerization and suspension polymerization in the presence of water, emulsifier, initiator and other additives; (2) mixing the two kinds of poly(vinyl chloride) latexes at a weight ratio of 1.0:(2.0-3.0), adding 0.6-0.9% of nonionic surfactant such as sodium dodecyl benzenesulfonate or sodium dodecyl sulfate, stirring at normal temperature for 30-50 min, and spray-drying to obtain poly(vinyl chloride) paste resin with double peak distribution of particle sizes. The method has such advantages as high paste-forming ability, low paste viscosity, high foamability, high stability, and adjustable product quality.
Description
Technical field
The present invention relates to chemical industry for making chlorine and alkali industry chloroethylene polymerization technical field, specifically a kind of preparation method of pvc resin paste grade.
Background technology
Pvc resin paste grade is the thermal plasticity high polymer that is formed by polymerization of vinyl choride monomer, and pvc resin paste grade generally adopts letex polymerization or microsuspension chloroethylene polymerization mode to produce.Emulsion polymerization of VC is to carry out in the presence of monomer, water soluble starter, emulsifying agent, water and other auxiliary agent, and microsuspension is similar to emulsion polymerization, just adopts oil-soluble initiator.Stick with paste when resin and softening agent stir together and form stable plastipaste, produce end article.The main application is that PVC wallpaper, leatheroid, foam floor etc. are processed in coating.One-tenth paste property and paste viscosity and thermostability are the main quality index of this series products, and the size of polyvinylchloride latex particle diameter and distribution directly influence the paste viscosity of pvc resin paste grade.The emulsion polymerization latex particle diameter is approximately (0.1-0.5) micron, and the microsuspension latex particle size is approximately (0.8-1.5) micron.Latex particle unimodal is meant that latex particle in the polymer is through the particle diameter instrument or be called the Pu Feng that the high speed sedimentation analysis gets and be unimodal distribution, this depends primarily on production technology and decides, the latex finished product of unimodal distribution, under a certain shearing rate, it is very high that its paste viscosity has rising, need consume big energy for overcoming this viscosity.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method that can control the polyvinylchloride latex grain freely through the pvc resin paste grade of size and distribution.
The object of the present invention is achieved like this, earlier with vinyl chloride monomer, at water, emulsifying agent, initiator and relevant auxiliary agent exist down, adopt emulsion polymerization technique and microsuspension technology respectively, prepare primary particle diameter and be respectively the polyvinylchloride latex A of 0.15-0.20 μ m and the polyvinylchloride latex B of 0.80-1.50 μ m, it is characterized in that: polyvinylchloride latex A is mixed by the 1.0:2.0-3.0 ratio of weight and number with polyvinylchloride latex B, the nonionogenic tenside that adds the 0.6-1.0% that accounts for otal investment again, after normal temperature down stirs even blending in 30-50 minute, go out the pvc resin paste grade finished product that particle diameter is bimodal distribution with this latex is spray-dried.
The above-mentioned ionic surfactant pack that adopts is drawn together: propylene oxide block polymer (PPP), epoxidized ethylene alkyl ester RCOO (CH
2CH
2O)
mH, epoxidized ethylene polyvalent alcohol alkyl ester RO (CH
2CH
2)
mH, alkylol amide RCON (CH
2CH
2OH)
2, epoxy soybean oil or dibutyl tin laurate.
1, chemical principle
This reaction belongs to radical polymerization
Chain initiation: I
2---→ 2I
I+M---→ IM M is a monomer
Chainpropagation: IM+nM---→ Imn+
1
Chain termination: disproportionation and coupling termination
2, working method
2.1 monomer and auxiliary agent are added polymeric kettle by prescription, through deoxygenation, inflated with nitrogen, under agitation condition, be warming up to polymerization temperature, maintain polymerization under this temperature, treat pressure decline (0.1～0.15) MP
aThe time, the cooling pressure release gets latex A, puts into the latex storage tank.
2.2 monomer and auxiliary agent are added polymeric kettle by prescription, open the homogenizing pump, homogenizing (10～20) min through deoxygenation, inflated with nitrogen, is warming up to polymerization temperature under agitation condition, maintain polymerization under this temperature, treats pressure decline (0.1～0.15) MP
aThe time, the cooling pressure release gets latex B, puts into the latex storage tank.
2.3 in proportion latex A, latex B, auxiliary agent are added mixing kettle, under agitation condition, keep (30～50) min.
2.4 latex is spray-dried after the blending, is finished product.
3, raw material and reaction conditions are to the influence of the every index of product
3.1 initiator amount is to the influence of the every index of product
Initiator amount is to the data sheet that influences of the every index of product
From this group data analysis, initiator amount has considerable influence to polymerization rate (polymerization time), and all other indexs are not had influence substantially.As long as heat transfer condition allows, can add initiator in right amount, shorten the reaction times.
3.2 the emulsifying agent consumption is to the influence of the every index of latex
The emulsifying agent consumption is to the data sheet that influences of the every index of latex
From this group data analysis, the emulsifying agent consumption does not have influence substantially to latex solid content, pH value, and is only influential through size and polymerization reaction time to latex granule.When the emulsifying agent consumption was high, polymerization velocity was fast, and latex granule is through little, and consumption is low excessively, causes polymerization velocity slow, can generate macrobead latex.
3.3 assistant for emulsifying agent A, B consumption proportion are to the influence of the every index of latex
Assistant for emulsifying agent A, B consumption proportion are to the data sheet that influences of the every index of latex
From this group data analysis, latex granule was through obviously increasing when assistant for emulsifying agent B proportioning was big.Thereby assistant for emulsifying agent B is bigger through influence to latex granule, and assistant for emulsifying agent A is less relatively through influence to latex granule.
3.3 latex A, B proportioning are to the influence of finished product Type B viscosity
Latex A, B proportioning are to the data sheet that influences of finished product Type B viscosity
From this group data analysis, latex A, B proportioning are when 30:70, and finished product Type B viscosity is less, and along with the increase of latex A proportioning, finished product Type B viscosity increases gradually.
The present invention makes through blending because polyvinylchloride latex is to adopt two kinds of polymerization technique preparations.Thereby the size of product cut size and distribute control easily and adjustment, thereby realized bimodal distribution.Bimodal distribution of the present invention is meant the narrow diameter distribution of latex particle, concentrates on two ranks.The paste resin of this bimodal distribution, its viscosity its paste viscosity under single shearing rate changes not obvious.Particle diameter is extremely important to sticking with paste its influence of viscosity, and its surface-area that particle diameter is big is little, and the plasticising dosage of surface adhesion is also few, helps viscosity and reduces.But it is also big that big its of particle diameter piled up the space, wherein needs the softening agent of filling also just many, and the corresponding minimizing of free softening agent impels and sticks with paste viscosity and increase, and the situation that particle diameter is little is just in time opposite.Be unified above-mentioned contradiction, the present invention adopts the particle of the different sizes of two kinds of different process preparations just, the method of scope collocation by a certain percentage solves, therefore preparation method of the present invention has into the paste excellent property, the paste viscosity is low, foam performance good, production stability is high, and the product technology quality index is easy to adjust.
Embodiment
The present invention will be further described by example below in conjunction with accompanying drawing, but following example only is the present invention's example wherein, the interest field of not representing invention and being limited.This interest field is as the criterion with claims.
Example 1
1, emulsion polymerization technique: add pure water 4000ml in the polymeric kettle, be dissolved in the sodium lauryl sulphate of the 58g in the 800ml pure water and the hexadecanol of 12g in advance, Potassium Persulphate 3g, ph value of mixture is adjusted to 10.
Add vinyl chloride monomer 3kg after the polymeric kettle deoxygenation, pour nitrogen 0.1MPa;
Polymeric kettle is warming up to 50 ℃, keeps temperature of reaction, (6-7) hour after pressure decline 0.1MP
aPolymerization finishes, and getting a solid content is 37.8%, and average particle size is the latex A of 0.188 μ m;
2, microsuspension technology: add pure water 4000ml in the polymeric kettle, be dissolved in the sodium lauryl sulphate of the 35g in the 800ml pure water and the higher alcohols of 15g in advance, 30g Sodium dodecylbenzene sulfonate and 6.8kg with 15ml with the 2.2-azo of toluene dissolving sodium two-the 2.4-dimethyl-penten is fine
Add vinyl chloride monomer 4kg after the polymeric kettle deoxygenation, mixture pours nitrogen 0.1MPa with homogenizing pump homogenizing 15min in the polymeric kettle;
Polymeric kettle is warming up to 50 ℃, keeps temperature of reaction, pressure decline 0.1MP after 9-10 hour
aPolymerization finishes, and getting a solid content is 44.5%, and average particle size is the latex B of 1.1 μ m.
3, latex A and latex B are added the latex blending still in the ratio of 30:70, add the propylene oxide block polymer (PPP) of otal investment 0.8%, normal temperature stirs 30min down; Latex is spray-dried after the blending, is finished product of the present invention.
Claims (2)
1, a kind of preparation method of pvc resin paste grade, earlier with vinyl chloride monomer, at water, emulsifying agent, initiator and relevant auxiliary agent exist down, adopt emulsion polymerization technique and microsuspension technology respectively, prepare primary particle diameter and be respectively the polyvinylchloride latex A of 0.15-0.20 μ m and the polyvinylchloride latex B of 0.80-1.50 μ m, it is characterized in that: polyvinylchloride latex A is mixed by the 1.0:2.0-3.0 ratio of weight and number with polyvinylchloride latex B, the nonionogenic tenside that adds the 0.6-1.0% that accounts for otal investment again, after normal temperature down stirs even blending in 30-50 minute, go out the pvc resin paste grade finished product that particle diameter is bimodal distribution with this latex is spray-dried.
2, according to the production method of the described pvc resin paste grade of claim 1, it is characterized in that: nonionogenic tenside is selected from: epoxidized ethylene alkyl ester, epoxidized ethylene polyvalent alcohol alkyl ester, alkylol amide, epoxy soybean oil or dibutyl tin laurate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100112524A CN100509943C (en) | 2007-05-11 | 2007-05-11 | Method for preparing resin of polyvinyl chloride paste |
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|---|---|---|---|
| CNB2007100112524A CN100509943C (en) | 2007-05-11 | 2007-05-11 | Method for preparing resin of polyvinyl chloride paste |
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| CN101050293A CN101050293A (en) | 2007-10-10 |
| CN100509943C true CN100509943C (en) | 2009-07-08 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851309B (en) * | 2010-05-18 | 2011-09-07 | 武汉祥龙电业股份有限公司 | Production method for polyvinyl chloride powder for preparing baffle plate of lead acid storage battery |
| CN101955559B (en) * | 2010-09-21 | 2012-04-25 | 沈阳化工股份有限公司 | Paste resin with high thermostability and preparation method thereof |
| CN102952228A (en) * | 2011-08-26 | 2013-03-06 | 沈阳化工股份有限公司 | Production method for improving productivity of paste resin |
| TWI483952B (en) * | 2012-08-31 | 2015-05-11 | Formosa Plastics Corp | Production method of high concentration polyvinyl chloride latex |
| WO2015005476A1 (en) | 2013-07-12 | 2015-01-15 | ロンシール工業株式会社 | Antiviral vinyl chloride resin composition, antiviral vinyl chloride resin sheet, and method for manufacturing same, interior sheet, method for manufacturing interior sheet, polyvinyl chloride resin interior sheet, antiviral wallpaper, and method for manufacturing antiviral wallpaper |
| CN103351445B (en) * | 2013-07-17 | 2015-08-26 | 安徽天辰化工股份有限公司 | A kind of high viscosity alveolitoid polyvinyl chloride (PVC) paste resin PB110-4 occurred frequently and production method thereof |
| CN104211841B (en) * | 2014-08-14 | 2016-07-13 | 广西众昌树脂有限公司 | The preparation method of PVC paste resin |
| CN104530275A (en) * | 2014-12-31 | 2015-04-22 | 安徽天辰化工股份有限公司 | Low-viscosity high-foaming type polyvinyl chloride paste resin PB110-3 and production method thereof |
| CN112409712A (en) * | 2019-08-20 | 2021-02-26 | 贝内克-长顺汽车内饰材料（张家港）有限公司 | Composition comprising polyvinyl chloride, use thereof and artificial leather obtained therefrom |
| CN111267262A (en) * | 2020-01-20 | 2020-06-12 | 粟鹏程 | Paste resin modification method |
| CN111363275A (en) * | 2020-04-26 | 2020-07-03 | 安徽金喜龙新型建材有限公司 | Anti-aging PVC decorative molding |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292000A (en) * | 1998-01-27 | 2001-04-18 | 新第一氯乙烯株式会社 | Granular vinyl chloride resin for paste processing and process for producing same |
| CN1331258A (en) * | 2000-07-05 | 2002-01-16 | 钟渊化学工业株式会社 | Method for preparing vinyl chloride pasty resin |
| JP2005290022A (en) * | 2004-03-31 | 2005-10-20 | Kanto Leather Co Ltd | Vinyl chloride-based resin paste for decorative sheet |
| EP1702936A1 (en) * | 2005-03-18 | 2006-09-20 | VESTOLIT GmbH & Co. KG | Process for manufacturing polymers that can be made pasty |
-
2007
- 2007-05-11 CN CNB2007100112524A patent/CN100509943C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1292000A (en) * | 1998-01-27 | 2001-04-18 | 新第一氯乙烯株式会社 | Granular vinyl chloride resin for paste processing and process for producing same |
| CN1331258A (en) * | 2000-07-05 | 2002-01-16 | 钟渊化学工业株式会社 | Method for preparing vinyl chloride pasty resin |
| JP2005290022A (en) * | 2004-03-31 | 2005-10-20 | Kanto Leather Co Ltd | Vinyl chloride-based resin paste for decorative sheet |
| EP1702936A1 (en) * | 2005-03-18 | 2006-09-20 | VESTOLIT GmbH & Co. KG | Process for manufacturing polymers that can be made pasty |
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| CN101050293A (en) | 2007-10-10 |
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