CN105175603A - Method for preparing vinisol through mixing technology - Google Patents
Method for preparing vinisol through mixing technology Download PDFInfo
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- CN105175603A CN105175603A CN201410268480.XA CN201410268480A CN105175603A CN 105175603 A CN105175603 A CN 105175603A CN 201410268480 A CN201410268480 A CN 201410268480A CN 105175603 A CN105175603 A CN 105175603A
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- vinyl chloride
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- vinyl acetate
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Abstract
The invention discloses a method for preparing vinisol through a mixing technology. The method comprises the following steps: carrying out a polymerization reaction on a composite emulsifier, an initiator, desalinized water, a pH adjusting agent, seeds, vinyl acetate and a vinyl chloride monomer under anoxic closed conditions at 40-60DEG C for 3-10h to prepare a vinyl chloride-vinyl acetate copolymer water suspension, and collecting the vinyl chloride-vinyl acetate copolymerization paste resin from the above obtained reaction product. The reaction speed is fast due to liquid drop polymerization, so the production ability is improved, the process is simple, the controllable range of latex particle sizes is large, the paste resin has low paste viscosity at high and low shearing rates, the paste viscosity reduces with the increase of the shearing rate, and the paste becomes thin with shearing; and the flow curve is a curve going through the origin of coordinates and being convex to the shearing stress axis, so the plasticized paste has the characteristics of a pseudoplastic fluid, and has wide post-processing applicability range.
Description
Technical field
The present invention relates to the preparation method that resin stuck with paste by chlorine vinegar.
Background technology
Vinyl chloride-vinyl acetate copolymer resins and PVC paste resin-phase ratio, owing to embedded in vinyl acetate between to for plastic ester molecule in PVC molecule, the closelypacked vinylchlorid segment rigid structure be present in homopolymer has suffered destruction, reduce intermolecular polarity, reduce intermolecular gravitation, make its performance there occurs change.Be mainly reflected in: the vinyl chloride-vinyl acetate copolymer paste resin PVC paste resin more similar than molecular mass has lower gelling temp and melt temperature (low 30 ~ 40 DEG C); In addition, the introducing of ester group in molecule, can improve the dissolution rate of softening agent to resin, increases the bounding force of resin and various adhesive substrate.
Vinyl chloride-vinyl acetate copolymer resins, as the important means reducing processing temperature, improve plasticizing rate, improve product properties, is widely used in PVC automobile plastisol (comprising chassis stone-impact-resistapaint paint, vehicle body weld joint sealant spot welding glue, filter core glue etc.), PVC square carpet backing binding agent, printing inks, heat-sensitive fabric coating, slush moulding heel, tarpaulin and chemical foaming goods etc.Chlorine vinegar is stuck with paste resin and can be used alone, and also can use with PVC paste resin complex.
The performance of vinyl chloride-vinyl acetate copolymer resins depends primarily on the mean polymerisation degree of multipolymer and the composition of multipolymer.Mean polymerisation degree is mainly by the impact that polymerization temperature and multipolymer form.The composition of multipolymer then depends on the factor such as proportioning and transformation efficiency of the add-on of vinyl acetate, water and monomer.Preparation for the interpolymer paste resin of a certain composition the most important thing is the polymerization technology condition determining required mean polymerisation degree.
In addition, preparative chemistry forms homogeneous multipolymer is very important theoretical question.Vinylchlorid and vinyl acetate are the two kinds of monomers being easy to occur copolymerization, although reactivity ratio has different (but with vinylchlorid with compared with other monomer copolymerization, the reactivity ratio of these two kinds of monomers relatively) when these two kinds of monomers carry out copolymerization.Because the reactivity ratio (r1) of vinylchlorid is larger than the reactivity ratio (r2) of vinyl acetate, namely during copolymerization, vinylchlorid is slightly faster than vinyl acetate reaction.In order to preparative chemistry forms homogeneous multipolymer, polymerization technique can divide vinyl acetate and add several times.
But in order to simplify the operation, the gained copolymerized product performance that once feeds intake the while of usual two kinds of monomers also can meet service requirements.When feeding intake, the massfraction of vinyl acetate should be slightly larger than the massfraction of expection multipolymer.
With the chlorine vinegar interpolymer paste resin that microsuspension technique general is at present obtained, size distribution is wide, resin is applicable to the goods that in manufacture requirements, low paste viscosity is shaping, this method process characteristic is that vinyl chloride monomer and Vinyl Acetate Monomer are by means of emulsifying agent and high-shear mechanical force (high-speed pump, homogenizing pump) act in water and disperse into about about 1 μm drop, adopt oil-soluble initiator initiated polymerization, also need in polymerization process constantly to add monomer.Therefore technological process relative complex, process parameter control difficulty is large, and quality is wayward, and productivity is lower.
The object of this invention is to provide a kind of hybrid system and prepare the method that resin stuck with paste by chlorine vinegar, to overcome the defect that prior art exists.
Method of the present invention, comprises the steps:
By compound emulsifying agent, initiator, de-salted water, pH adjusting agent, seed, vinyl acetate and vinyl chloride monomer, under anaerobic air tight condition, polyreaction, polymerization temperature is 40 ~ 60 DEG C, time is 3 ~ 10 hours, obtained vinyl chloride-vinyl acetate copolymer water supernatant liquid, then collects vinyl chloride-vinyl acetate copolymer paste resin from reaction product.
The method of described collection is, by described vinyl chloride-vinyl acetate copolymer water supernatant liquid, spraying dry, can obtain vinyl chloride-vinyl acetate copolymer paste resin.
The parts by weight ratio of each component is:
Described compound emulsifying agent is the mixture of I and II, and emulsifying agent I and emulsifying agent II weight ratio are 0.8 ~ 1.8:1.
I: hexadecanol, 16 alcohol mixtures, stearyl alcohol, palmitic acid, TETRADECONIC ACID, laurostearic acid, n-Hexadecane or octadecane etc.;
II: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, nonyl aryl polyethers ethanol, ammonium laurate, polyoxyethylene nonylphenol ether or polyoxyethylene octylphenol ether etc.
The preparation method of described compound emulsifying agent, comprises the steps:
A certain amount of de-salted water is warming up to 60 ~ 70 DEG C in the Preparation tank of whipping appts, adds wherein by mentioned emulsifier I and II, open and stir, rotating speed is 120 ~ 150rpm, is incubated 30 ~ 50 minutes.The weight concentration of prepared compound emulsifying agent is 3 ~ 6%, and described emulsifying agent I and II weight ratio is between the two 0.8 ~ 1.8:1.Can obtain the compound emulsifying agent that particle diameter is 300 ~ 700nm, its feed way can be divided into and once add or add in batches.
Described initiator comprise in Potassium Persulphate, ammonium persulphate, sodium bisulfite, t-butyl hydrogen peroxide, copper sulfate, formaldehyde sodium sulfoxylate, peroxy dicarbonate ethylhexyl one or more; Its feed way can be divided into and disposablely add or add in batches.
It is one in the ammoniacal liquor of 10 ~ 20% that said pH adjusting agent comprises bicarbonate of ammonia, sodium hydroxide, SODIUM PHOSPHATE, MONOBASIC or weight concentration.
The preparation method of described seed, comprises the steps:
By emulsifying agent, pH adjusting agent, vinyl chloride monomer, de-salted water and initiator, under anaerobic air tight condition, polyreaction, polymerization temperature is 45 ~ 65 DEG C, and the time is 3 ~ 12 hours, obtained seed, for a kind of containing grain diameter be the emulsion of 110 ~ 130nm, weight solid content is 25 ~ 50%.
Described emulsifying agent is more than one in base sulfosuccinate sodium or ammonium laurate of Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, nonyl aryl polyethers ethanol, two; Its feed way can be divided into and once add or add in batches.
Described initiator is more than one in Potassium Persulphate, ammonium persulphate, sodium bisulfite, t-butyl hydrogen peroxide, copper sulfate, formaldehyde sodium sulfoxylate, Potassium Persulphate, peroxy dicarbonate ethylhexyl; Its feed way can be divided into and disposablely add or add in batches.
Said pH adjusting agent comprises the one in ammonium salt or ammoniacal liquor.
The parts by weight of each component are as follows:
Vinyl chloride monomer 100 parts, emulsifying agent 1.0 ~ 2.0 parts, pH adjusting agent 0.1 ~ 0.3 part, de-salted water 130 ~ 160 parts, initiator 0.220 ~ 0.260 part.
Method of the present invention, by adding homemade compound emulsifying agent in polymerization system, has prepared the primary particle that emulsion particle diameter is 1.0 ~ 1.3um.Spray-dried, obtain BShi and stick with paste the lower vinyl chloride-vinyl acetate copolymer paste resin of viscosity.This preparation method has following features:
Owing to being polymerization of fluid drops, speed of response is fast, thus raising throughput, technique is simple, and latex particle size controlled range is large, stick with paste resin under high and low shearing rate, have lower paste viscosity, and paste viscosity increases with shearing rate and reduces, have the character of shear shinning, flow curve is by the convex curve to shear-stress axle of true origin, show that plastipaste is false plastotype fluid feature, post-treatment range of applicability is wide.
Embodiment
Embodiment 1
The preparation method of compound emulsifying agent:
The de-salted water of 30 kilograms is warming up to 65 DEG C in the Preparation tank of whipping appts, adds wherein by hexadecanol and sodium lauryl sulphate, open and stir, rotating speed is 120rpm, is incubated 30 minutes.Preparing weight concentration is 3.8%, and particle diameter is the compound emulsifying agent of 583nm.Described emulsifying agent hexadecanol and the weight ratio of sodium lauryl sulphate are 1.3:1.The preparation method of seed:
By emulsifying agent, pH adjusting agent, vinyl chloride monomer, de-salted water and initiator, under anaerobic air tight condition, polyreaction, polymerization temperature is 50 DEG C, and the time is 7 hours, obtained seed.
Seed contains the emulsion that grain diameter is 115nm, and weight solid content is 31%;
Emulsifying agent is Sodium dodecylbenzene sulfonate; Initiator is t-butyl hydrogen peroxide;
PH adjusting agent is the ammoniacal liquor of weight concentration 20%.
The parts by weight of each component are as follows:
Vinyl chloride monomer 100 parts, emulsifying agent 2.0 parts, pH adjusting agent 0.2 part, de-salted water 150 parts, initiator 0.250 part.
Vinyl chloride-vinyl acetate copolymer emulsion preparation method:
By compound emulsifying agent, initiator, de-salted water, pH adjusting agent, seed, vinyl acetate and vinyl chloride monomer, under anaerobic air tight condition, polyreaction, polymerization temperature is 50 DEG C, time is 6 hours, and obtained vinyl chloride-vinyl acetate copolymer water supernatant liquid, then reclaims reacted vinyl chloride monomer, collect emulsion, the micelle that mean diameter is greater than 1.0 microns can be obtained.Spray-dried, obtain vinyl chloride-vinyl acetate copolymer paste resin, the BShi at its 25 DEG C of temperature sticks with paste viscosity and is less than 6000mpa.s.
The parts by weight of each component are as follows:
Described initiator is t-butyl hydrogen peroxide;
Said pH adjusting agent is the ammoniacal liquor of weight concentration 15%.
Embodiment 2
The preparation method of compound emulsifying agent:
The de-salted water of 30 kilograms is warming up to 68 DEG C in the Preparation tank of whipping appts, adds wherein by 16 alcohol mixtures and sodium lauryl sulphate, open and stir, rotating speed is 140rpm, is incubated 35 minutes.Preparing weight concentration is 4.5%, and particle diameter is the compound emulsifying agent of 356nm.Described emulsifying agent 16 alcohol mixture and the weight ratio of sodium lauryl sulphate are 1.5:1.
The preparation method of seed is identical with embodiment 1.
Seed contains the emulsion that grain diameter is 115nm, and weight solid content is 31%.
Vinyl chloride-vinyl acetate copolymer emulsion preparation method:
By compound emulsifying agent, initiator, de-salted water, pH adjusting agent, seed, vinyl acetate and vinyl chloride monomer, under anaerobic air tight condition, polyreaction, polymerization temperature is 45 DEG C, time is 7 hours, and obtained vinyl chloride-vinyl acetate copolymer water supernatant liquid, then reclaims reacted vinyl chloride monomer, collect emulsion, the micelle that mean diameter is greater than 1.0 microns can be obtained.Spray-dried, obtain vinyl chloride-vinyl acetate copolymer paste resin, the BShi at its 25 DEG C of temperature sticks with paste viscosity and is less than 6000mpa.s.
The parts by weight of each component are as follows:
Initiator is the mixture of persulfuric acid copper and formaldehyde sodium sulfoxylate, and weight ratio is 1:100;
PH adjusting agent is SODIUM PHOSPHATE, MONOBASIC.
Embodiment 3
The preparation method of compound emulsifying agent:
The de-salted water of 30 kilograms is warming up to 70 DEG C in the Preparation tank of whipping appts, adds wherein by TETRADECONIC ACID and sodium laurylsulfonate, open and stir, rotating speed is 130rpm, is incubated 40 minutes.Preparing weight concentration is 5.7%, and particle diameter is the compound emulsifying agent of 396nm.Described emulsifying agent TETRADECONIC ACID and the weight ratio of sodium laurylsulfonate are 1.8:1.The preparation method of seed is basic identical with embodiment 1.
Seed is be the emulsion of 115nm containing grain diameter, and weight solid content is 31%.
Vinyl chloride-vinyl acetate copolymer emulsion preparation method:
By compound emulsifying agent, initiator, de-salted water, pH adjusting agent, seed, vinyl acetate and vinyl chloride monomer, under anaerobic air tight condition, polyreaction, polymerization temperature is 42 DEG C, time is 5 hours, and obtained vinyl chloride-vinyl acetate copolymer water supernatant liquid, then reclaims reacted vinyl chloride monomer, collect emulsion, the micelle that mean diameter is greater than 1.0 microns can be obtained.Spray-dried, obtain vinyl chloride-vinyl acetate copolymer paste resin, the BShi at its 25 DEG C of temperature sticks with paste viscosity and is less than 6000mpa.s.
The parts by weight of each component are as follows:
Described initiator is t-butyl hydrogen peroxide;
Said pH adjusting agent is bicarbonate of ammonia.
Claims (6)
1. hybrid system prepares the method that resin stuck with paste by chlorine vinegar, it is characterized in that, comprise the steps: compound emulsifying agent, initiator, de-salted water, pH adjusting agent, seed, vinyl acetate and vinyl chloride monomer, under anaerobic air tight condition, polyreaction, polymerization temperature is 40 ~ 60 DEG C, and the time is 3 ~ 10 hours, obtained vinyl chloride-vinyl acetate copolymer water supernatant liquid, then collects vinyl chloride-vinyl acetate copolymer paste resin from reaction product.
2. method according to claim 1, is characterized in that, the method for described collection is, by described vinyl chloride-vinyl acetate copolymer water supernatant liquid, spraying dry, can obtain vinyl chloride-vinyl acetate copolymer paste resin.
3. method according to claim 1, is characterized in that, the parts by weight ratio of each component is:
4. method according to claim 1, is characterized in that, described compound emulsifying agent is the mixture of I and II, and emulsifying agent I and emulsifying agent II weight ratio are 0.8 ~ 1.8:1;
I: hexadecanol, 16 alcohol mixtures, stearyl alcohol, palmitic acid, TETRADECONIC ACID, laurostearic acid, n-Hexadecane or octadecane etc.;
II: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, nonyl aryl polyethers ethanol, ammonium laurate, polyoxyethylene nonylphenol ether or polyoxyethylene octylphenol ether.
5. method according to claim 1, it is characterized in that, described initiator comprise in Potassium Persulphate, ammonium persulphate, sodium bisulfite, t-butyl hydrogen peroxide, copper sulfate, formaldehyde sodium sulfoxylate, peroxy dicarbonate ethylhexyl one or more; Its feed way can be divided into and disposablely add or add in batches.
It is one in the ammoniacal liquor of 10 ~ 20% that said pH adjusting agent comprises bicarbonate of ammonia, sodium hydroxide, SODIUM PHOSPHATE, MONOBASIC or weight concentration.
6. method according to claim 1, is characterized in that, the preparation method of described seed, comprises the steps:
By emulsifying agent, pH adjusting agent, vinyl chloride monomer, de-salted water and initiator, under anaerobic air tight condition, polyreaction, polymerization temperature is 45 ~ 65 DEG C, and the time is 3 ~ 12 hours, obtained seed, for a kind of containing grain diameter be the emulsion of 110 ~ 130nm, weight solid content is 25 ~ 50%;
Described emulsifying agent is more than one in base sulfosuccinate sodium or ammonium laurate of Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate, nonyl aryl polyethers ethanol, two; Its feed way can be divided into and once add or add in batches;
Described initiator is more than one in Potassium Persulphate, ammonium persulphate, sodium bisulfite, t-butyl hydrogen peroxide, copper sulfate, formaldehyde sodium sulfoxylate, Potassium Persulphate, peroxy dicarbonate ethylhexyl; Its feed way can be divided into and disposablely add or add in batches;
Said pH adjusting agent comprises the one in ammonium salt or ammoniacal liquor;
The parts by weight of each component are as follows:
Vinyl chloride monomer 100 parts, emulsifying agent 1.0 ~ 2.0 parts, pH adjusting agent 0.1 ~ 0.3 part, de-salted water 130 ~ 160 parts, initiator 0.220 ~ 0.260 part.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410268480.XA CN105175603A (en) | 2014-06-16 | 2014-06-16 | Method for preparing vinisol through mixing technology |
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| CN201410268480.XA CN105175603A (en) | 2014-06-16 | 2014-06-16 | Method for preparing vinisol through mixing technology |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112252045A (en) * | 2020-09-11 | 2021-01-22 | 山东优尼科斯科技股份有限公司 | PVC bottom and back sizing agent for modular carpet and production process thereof |
| CN112812798A (en) * | 2021-01-26 | 2021-05-18 | 唐山钢铁集团有限责任公司 | Coking emulsion preparation device and process |
| CN113698517A (en) * | 2021-06-17 | 2021-11-26 | 济宁中银电化有限公司 | Polyvinyl chloride paste resin and preparation method thereof |
| CN115678300A (en) * | 2021-07-22 | 2023-02-03 | 东莞美哲塑胶制品有限公司 | Shell-plastic composite material, processing method and application thereof |
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| JP2000204122A (en) * | 1999-01-12 | 2000-07-25 | Denki Kagaku Kogyo Kk | Vinyl chloride-vinyl acetate-based copolymer and composition |
| CN102417556A (en) * | 2011-11-22 | 2012-04-18 | 上海氯碱化工股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer paste resin |
| CN102936308A (en) * | 2011-08-15 | 2013-02-20 | 沈阳欧陆科技发展有限公司 | Method for synthesizing vinyl chloride-vinyl acetate copolymer via solution method |
| CN103254343A (en) * | 2013-04-26 | 2013-08-21 | 上海氯碱化工股份有限公司 | Preparation method of chloroethylene-vinyl acetate copolymer paste resins with uniform chemical compositions |
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2014
- 2014-06-16 CN CN201410268480.XA patent/CN105175603A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000204122A (en) * | 1999-01-12 | 2000-07-25 | Denki Kagaku Kogyo Kk | Vinyl chloride-vinyl acetate-based copolymer and composition |
| CN102936308A (en) * | 2011-08-15 | 2013-02-20 | 沈阳欧陆科技发展有限公司 | Method for synthesizing vinyl chloride-vinyl acetate copolymer via solution method |
| CN102417556A (en) * | 2011-11-22 | 2012-04-18 | 上海氯碱化工股份有限公司 | Method for preparing vinyl chloride-vinyl acetate copolymer paste resin |
| CN103254343A (en) * | 2013-04-26 | 2013-08-21 | 上海氯碱化工股份有限公司 | Preparation method of chloroethylene-vinyl acetate copolymer paste resins with uniform chemical compositions |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112252045A (en) * | 2020-09-11 | 2021-01-22 | 山东优尼科斯科技股份有限公司 | PVC bottom and back sizing agent for modular carpet and production process thereof |
| CN112812798A (en) * | 2021-01-26 | 2021-05-18 | 唐山钢铁集团有限责任公司 | Coking emulsion preparation device and process |
| CN113698517A (en) * | 2021-06-17 | 2021-11-26 | 济宁中银电化有限公司 | Polyvinyl chloride paste resin and preparation method thereof |
| CN115678300A (en) * | 2021-07-22 | 2023-02-03 | 东莞美哲塑胶制品有限公司 | Shell-plastic composite material, processing method and application thereof |
| CN115678300B (en) * | 2021-07-22 | 2023-11-28 | 东莞美哲塑胶制品有限公司 | Shell-plastic composite material, processing method and application thereof |
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