CN1053202C - Method for prodn. of high transparent and high impact resilience PVC - Google Patents
Method for prodn. of high transparent and high impact resilience PVC Download PDFInfo
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- CN1053202C CN1053202C CN97100116A CN97100116A CN1053202C CN 1053202 C CN1053202 C CN 1053202C CN 97100116 A CN97100116 A CN 97100116A CN 97100116 A CN97100116 A CN 97100116A CN 1053202 C CN1053202 C CN 1053202C
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Abstract
The present invention relates to a process for preparing polyvinyl chloride with high transparency and shock resistance, which is characterized in that an amount of electrolyte solution is added when emulsion for stem grafting is manufactured to make emulsion particles aggregate, and thus, the light transmittance, the shock resistance and the weatherability of PVC graft polymers are improved.
Description
The present invention relates to a kind of manufacture method of polychloroethylene composition, this composition also has high transparency and low turbidity except the weathering resistance with high impact, excellence.
Polyvinyl chloride (PVC) is one of plastics variety that purposes is the widest in the world.Yet not shock-resistant because its processing difficulties, shortcoming such as not weather-proof has limited its application.So people attempt to improve its performance with the whole bag of tricks (blend, chemical modification etc.).But,, in its processing characteristics and mechanical property improvement, all lose polyvinyl chloride institute inherent light transmission inevitably because the refractive index of properties-correcting agent and polyvinyl chloride is different.
Qi Teng etc. have proposed the imagination that emulsion particle can be assembled (Cluster) at research MBS when (MBS), have prepared the MBS properties-correcting agent that has shock-resistant and two kinds of performances of printing opacity concurrently (polymer, 1973 22 phase 463 pages).Yet, because MBS is not weather-proof, so do not improve the weathering resistance of PVC.Thereby limited the open air application of transparent material.
Chinese patent CN1008099B discloses a kind of production method of making the used thermoplastic composition of molded parts that resistance to impact shock, the transparency, any surface finish and weathering resistance all be improved.At first, in emulsion, make nuclear/shell polymeric by water-soluble or oil-soluble initiator initiation, this nuclear/shell polymeric is that the crosslinked polystyrene with the optics better performances is that hard kernel, the crosslinked polypropylene that can improve impact property are the rubber-type elastic container, in aqueous suspension medium solution vinyl chloride monomer is coated on nuclear/shell polymeric surface by polyreaction then.Because in letex polymerization, the size of emulsion particle diameter is bigger to the performance impact of vinyl chloride graft copolymer, according to people's such as Qi Teng research theory, and the emulsion modified polyvinyl chloride resin of macroparticle, help improving impact property, and the emulsion modified polyvinyl chloride resin of small-particle is favourable to improving light transmission.Have only and control particle diameter and morphological structure effectively, just can make the performance of the mutual restriction such as shock-resistant, weather-proof, printing opacity of polyvinyl chloride resin reach best unification.Particle shape structure how to control emulsion effectively is to improve the performance of vinyl chloride graft copolymer, and is not open in the method.
The present invention is on the basis of above-mentioned prior art, a kind of manufacture method of high transparent and high impact resilience PVC has been proposed, be characterized in when making grafting, adding an amount of electrolyte solution, improve the printing opacity of PVC graftomer, shock-resistant and weather resistance so that emulsion particle is assembled with emulsion.
To describe manufacture method of the present invention in detail below.
A kind of manufacture method of high transparent and high impact resilience PVC, it is to be that raw material is made after the emulsion vinyl chloride monomer in the grafting by aromatic vinyl monomers and acrylate, it is characterized in that, comprises the steps:
(1) preparation of emulsion:
Under polymerizing condition, temperature of reaction is 70～90 ℃, carries out emulsion polymerization by following prescription:
The composition parts by weight
Deionized water 100
Acrylate/cross-linking agent solution 13.5～22.6
Aromatic vinyl monomers/cross-linking agent solution 18.5～9.7
Initiator 0.015～0.33
Emulsifying agent 0.12～5.06
Complexing agent 0.08～0.32
In the above-mentioned emulsion preparation process or in emulsion, make back adding ionogen, gross weight in acrylate and aromatic vinyl monomers, electrolytical add-on is 100～10000ppm, and emulsion particle diameter is 0.05～0.08 μ m, and the aggregate particles morphological structure is a thyrsiform;
(2) add alkaline matter in above-mentioned emulsion, regulating the pH value is 8～10;
(3) graft polymerization of vinyl chloride monomer:
With the emulsion of step (2) gained, adopt vinyl chloride monomer in the method grafting of suspension polymerization again, reaction solution composed as follows:
The composition parts by weight
Vinyl chloride monomer 100
Deionized water 200～283
Initiator 0.10～0.15
Complexing agent 0.07～0.36
The emulsion 45.1～49.5 of step (2) gained
Composite dispersing agent 10.5～20.5
Under oxygen free condition, temperature was reacted 5～8 hours down for 40～60 ℃, promptly obtained vinyl chloride graft copolymer after washing, drying with above-mentioned reaction solution.
In above-mentioned preparation method, the described emulsifying agent of letex polymerization can adopt Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, nonionogenic tenside, be preferably sodium lauryl sulphate, its consumption is 0.37～1.57wt% (in a deionized water weight), is suitable for 0.75～1.1wt%.
In above-mentioned preparation method, the initiator of described letex polymerization can adopt thermolysis type and oxidation-reduction type two classes.The thermolysis type can be selected two kinds of peroxide and azo classes, superoxide can adopt ammonium persulphate, Potassium Persulphate, Sodium Persulfate, the azo class can adopt azo two isonitrile, azo two miaow base propane hydrochloride salt, is preferably ammonium persulphate, azo two miaow base propane hydrochloride salt; Oxidation-reduction type can be selected hydrogen phosphide cumene-formolation S-WAT (CHP-SFS), hydrogen peroxide-ferrous salt, be preferably hydrogen phosphide cumene-formolation S-WAT, consumption is 0.05～1wt% (in the gross weight of acrylate and aromatic vinyl monomers), is preferably 0.15～0.3wt%
In above-mentioned preparation method, described linking agent can adopt a kind of in Vinylstyrene, Phthalic acid, diallyl ester, diacrylate 1,4-butanediol ester, the diallyl maleate or their mixture.Its consumption is 0.5～2wt% (in the gross weight of acrylate and aromatic vinyl monomers), is preferably 1wt%.
In above-mentioned preparation method, adding electrolytical purpose in emulsion is to make not influence transparent small-particle emulsion aggregation together, form the thyrsiform structure, this accumulative emulsion particle has not only improved the shock strength of vinylchlorid grafts, do not influence simultaneously the transparency of vinylchlorid grafts yet, reached and improved the vinylchlorid grafts transparency and the two effect of taking into account of impact property.Described electrolytical choice criteria should be emulsion particle is assembled, and don't makes the material of emulsion breaking.Can adopt KCl, NaCl, CaCl
2, a kind of among the HCl or their mixture, be preferably KCl, because K
+Light transmission is had no adverse effects; Its add-on is 100～10000ppm (in the gross weight of acrylate and aromatic vinyl monomers), is preferably 500～1000ppm.
In above-mentioned preparation method, before the vinylchlorid graft polymerization, should add a certain amount of alkaline matter and regulate the emulsion meta-alkalescence, generally the pH value is controlled at 8～10, be preferably 8～9.The alkaline matter that adds is NaOH or Na
2CO
3, generally be made into the solution of concentration below 2wt% in use, the solution of concentration below 1wt% preferably, its consumption is as the criterion with the pH value of emulsion.Because the emulsion of making as stated above has certain subacidity, when it is used for the vinylchlorid graft polymerization,, after adding, dispersion agent can produce the phenomenon of breakdown of emulsion simultaneously because the existence of emulsifying agent can consume certain dispersion agent.Therefore need regulate the pH value of emulsion before the vinylchlorid graft polymerization, the vinyl chloride graft copolymer particle that uses the meta-alkalescence emulsion to obtain simultaneously is more even, and particle form is better.
In above-mentioned preparation method, described composite dispersing agent is for selecting water soluble cellulose and derivative thereof as the mixture of Walocel MT 20.000PV, hydroxypropylcellulose, Vltra tears at least a and polyvinyl alcohol wherein.When suspension polymerization, unsettled monomer oil droplet is smashed by churned mechanically shearing force in water, and is subjected to the effect of oil droplets tensile and is dispersed into little grain pearl, and dispersed grain pearl still has the trend that reassociates.In order to prevent reassociating of a pearl, just need add the dispersion agent protective colloid and make it stable.Single dispersion agent is for example: water soluble cellulose and derivative thereof etc., though dispersion effect is better, it is relatively poor to protect the glue ability, and just can play the effect that makes dispersive monomer grain pearl be difficult for reassociating after adding the stronger polyvinyl alcohol of protective capability.
Embodiment
Example 1
(1) preparation of vinylbenzene and butyl acrylate emulsion:
In the there-necked flask that reflux exchanger and stirring are housed, add the 400ml deionized water, drum N
2The qualified back of deoxygenation adds the sodium dodecyl sulfate solution (sodium lauryl sulphate of 1.6g and 20ml deionized water) of preparation in advance, be warming up to 80 ℃, under this temperature, add butyl acrylate/Phthalic acid, diallyl ester (BA/DAP=99/1) solution 18.9g of preparation in advance, stir after 10 minutes, add ammonium persulfate solution (the 0.8g ammonium persulphate: 10ml water), reacted 30 minutes for preparing in advance.
In above-mentioned solution, under the uniform temp condition, 230g vinylbenzene/the Vinylstyrene (St/DVB=99/1) and 4.8g sodium ethylene diamine tetracetate (EDTA) solution (concentration is 0.22wt%) that drip preparation in advance synchronously add 2 hours altogether, added afterreaction 0.5 hour, drip KCl solution (gross weight with acrylate and aromatic vinyl monomers is counted 1000ppm) then, after 10 minutes, drip 151.1gBA/DAP (99/1) and 339.43g initiator solution (concentration is 0.16wt%) synchronously, added afterreaction 1 hour, cooling discharge, obtaining the single particle particle diameter is the aggregate particles emulsion of 0.06～0.08 μ m.
(2) polymerization of vinylbenzene and butyl acrylate emulsion graft polymerization vinylchlorid:
Stirring is being housed, charging opening, in 2 liters of stainless steel polymeric kettles of nitrogen inlet and pump drainage mouth, add the 680ml deionized water, 0.38g azo two isobutyls fine (ABIN), 1g b diammonium edta sodium (EDTA) and 58g Vltra tears (HPMC) and polyvinyl alcohol solution (GH23, KZ05, Japan synthetic chemistry Co., Ltd., be the 2wt% aqueous solution), with concentration is that to transfer to pH value be 8 for the NaOH aqueous solution of 1wt%, continuous pump drainage is also mended nitrogen back adding for several times 283.36g vinyl chloride monomer, normal temperature stirred 15 minutes down, it is modulated to 8 aggregate particles emulsion 128g to add above-mentioned pH value then, and be warming up to 40 ℃ and kept 1 hour, be warming up to afterwards 60 ℃ react be 0.2～0.3MPa to the still internal drop after, the pressure release discharging, obtaining apparent density is 0.35g/ml, particle diameter is 60～140 purpose vinylchlorid graft copolymerization resins.
Measure notched Izod impact strength, transparency and the turbidity of vinyl chloride graft copolymer, the results are shown in Table 1.
The mensuration of emulsion particle diameter: adopt transmission electron microscope (TEM) to measure the size of emulsion particle.
The mensuration of vinyl chloride copolymer shock strength: adopt Italian CEAST company Instrument measuring simply supported beam notched Izod impact strength by GB1034.
The mensuration of vinyl chloride copolymer transparency and turbidity: press GB2410 and adopt NDG-20D numeral mist degree instrument to measure transparency and turbidity.
Example 2
(1) preparation of vinylbenzene and butyl acrylate emulsion:
Method is with example 1, and just the add-on of ionogen KCl solution changes 10000ppm (in the gross weight of acrylate and aromatic vinyl monomers) in the emulsion preparation process.
(2) polymerization of vinylbenzene and butyl acrylate emulsion graft polymerization vinylchlorid:
Carry out the vinylchlorid graft polymerization reaction by example 1 method, obtain vinyl chloride graft copolymer, and measure its notched Izod impact strength, transparency and turbidity, the results are shown in Table 1.
Example 3
(1) preparation of vinylbenzene and butyl acrylate emulsion:
In the there-necked flask that reflux exchanger and stirring are housed, add the 400ml deionized water, drum N
2The qualified back of deoxygenation adds the sodium dodecyl sulfate solution (sodium lauryl sulphate of 1.6g and 20ml deionized water) of preparation in advance, be warming up to 80 ℃, under this temperature, add butyl acrylate/Phthalic acid, diallyl ester (BA/DAP=99/1) solution 18.9g of preparation in advance, stir after 10 minutes, add ammonium persulfate solution (the 0.8g ammonium persulphate: 10ml water), reacted 30 minutes for preparing in advance.
In above-mentioned solution, under the uniform temp condition, 230g vinylbenzene/the Vinylstyrene (St/DVB=99/1) and 4.8g sodium ethylene diamine tetracetate (EDTA) solution (concentration is 0.22wt%) that drip preparation in advance synchronously add 2 hours altogether, added afterreaction 0.5 hour, drip 151.1gBA/DAP (99/1) and 339.43g initiator solution (concentration is 0.16wt%) more synchronously, added afterreaction 1 hour, drip KCl solution (gross weight with acrylate and aromatic vinyl monomers is counted 1000ppm), cooling discharge, obtaining the single particle particle diameter is the aggregate particles emulsion of 0.05～0.08 μ m.
(2) polymerization of vinylbenzene and butyl acrylate emulsion graft polymerization vinylchlorid:
Carry out the vinylchlorid graft polymerization reaction by example 1 method, obtain vinyl chloride graft copolymer, and measure its notched Izod impact strength, transparency and turbidity, the results are shown in Table 1.
Example 4:
(1) preparation of vinylbenzene and butyl acrylate emulsion:
Method does not just add ionogen KCl solution with example 1 in the emulsion preparation process.
(2) polymerization of vinylbenzene and butyl acrylate emulsion graft polymerization vinylchlorid:
Stirring is being housed, charging opening, in 2 liters of stainless steel polymeric kettles of nitrogen inlet and pump drainage mouth, add the 680ml deionized water, 0.38g Diisopropyl azodicarboxylate (ABIN), 1g b diammonium edta sodium (EDTA) and 58g Vltra tears (HPMC) and polyvinyl alcohol solution (PVA, LL02, Japan synthetic chemistry Co., Ltd., be the 2wt% aqueous solution), add ionogen KCl solution (in the gross weight 1000ppm of acrylate and aromatic vinyl monomers), with concentration is that to transfer to pH value be 8 for the NaOH aqueous solution of 1wt%, continuous pump drainage is also mended nitrogen back adding for several times 283.36g vinyl chloride monomer, normal temperature stirred 15 minutes down, it is modulated to 8 aggregate particles emulsion 128g to add above-mentioned pH value then, and be warming up to 40 ℃ and kept 1 hour, be warming up to afterwards 60 ℃ react be 0.2～0.3MPa to the still internal drop after, the pressure release discharging, obtain vinyl chloride graft copolymer, and measure its notched Izod impact strength, transparency and turbidity the results are shown in Table 1.
Comparative Examples 1:
(1) preparation of vinylbenzene and butyl acrylate emulsion:
Method does not just add ionogen KCl solution with example 1 in the emulsion preparation process.
(2) polymerization of vinylbenzene and butyl acrylate emulsion graft polymerization vinylchlorid:
Carry out the vinylchlorid graft polymerization reaction by example 1 method, obtain vinyl chloride graft copolymer, and measure its notched Izod impact strength, transparency and turbidity, the results are shown in Table 1.
Table 1
| Embodiment | The letex polymerization result | The graft polymerization result | ||||
| Ionogen adds mode | The ionogen add-on | Electronic Speculum result (TEM) | Shock strength (KJm -2) | Transparency (%) | Turbidity (%) | |
| Example 1 | In the emulsion preparation process, add | 1000ppm | 0.05 μ m aggregate particles | 40.7 | 79.2 | 15.1 |
| Example 2 | In the emulsion preparation process, add | 10000ppm | 0.05 μ m aggregate particles | 40.2 | 79.2 | 28.3 |
| Example 3 | In letex polymerization at the end | 1000ppm | 0.05～0.08um aggregate particles | 36.6 | 85.6 | 5.4 |
| Example 4 | When graft polymerization, add | 1000ppm | 49.2 | 79.6 | 14.4 | |
| Comparative Examples 1 | Do not add | 0.07～0.08um | 16.5 | 75.2 | 28.3 |
Example 5
Stirring is being housed, charging opening, in 2 liters of stainless steel polymeric kettles of nitrogen inlet and pump drainage mouth, add the 680ml deionized water, 0.38g Diisopropyl azodicarboxylate (ABIN), 1g b diammonium edta sodium (EDTA) and 30g Vltra tears (HPMC) and polyvinyl alcohol (PVA+LL02) solution (being the 2wt% aqueous solution), with concentration is that to transfer to pH value be 8 for the NaOH aqueous solution of 1wt%, continuous pump drainage is also mended nitrogen back adding for several times 283.36g vinyl chloride monomer, normal temperature stirred 15 minutes down, the aggregate particles emulsion (pH value is modulated to 8) that adds above-mentioned example 3 preparations of 128g then, and be warming up to 40 ℃ and kept 1 hour, be warming up to afterwards 60 ℃ react be 0.2～0.3MPa to the still internal drop after, the pressure release discharging, obtaining apparent density is 0.35g/ml, particle diameter is 60～140 purpose vinylchlorid graft copolymerization resins.And measure its notched Izod impact strength, transparency and turbidity, the results are shown in Table 2.
Comparative Examples 2:
Carry out graft polymerization by example 5 methods, only composite dispersing agent is changed into single dispersion agent Vltra tears (HPMC).And notched Izod impact strength, transparency and the turbidity of mensuration graft copolymer, the results are shown in Table 2.
Table 2
| Dispersant system | Apparent density | Screening result (%) | Polymer performance | ||||||
| g/ml | 60 orders | 80 orders | 100 orders | 120 orders | Shock strength KJ/m 2 | Transparency % | Notes degree % | ||
| Example 3 | HPMC+GH23+KZ05 | 0.35 | 14 | 67 | 19 | 36.6 | 85.6 | 5.4 | |
| Example 5 | HPMC+PVA+LL02 | 0.38 | 11.7 | 45.3 | 11.1 | 31.9 | 36.5 | 80.1 | 9.0 |
| Comparative Examples 2 | HPMC | 0.18 | 16.5 | 69.2 | 28.3 | ||||
Comparative Examples 3:
Method by example 5 is carried out graft polymerization, only the reaction solution in the polymeric kettle is adjusted to 8 with 1wt%NaOH solution after, and the uncomfortable pH value of emulsion.After obtaining vinyl chloride graft copolymer, measure notched Izod impact strength, transparency and the turbidity of graft copolymer, the results are shown in Table 3.(tracking pH value)
| Regulate the pH value method | Apparent density | Screening result (%) | Polymer performance | |||||||
| g/ml | 40 orders | 60 orders | 80 orders | 100 orders | 120 orders | Shock strength KJ/m 2 | Transparency % | Turbidity % | ||
| Example 5 | Divide and transfer pH value | 0.38 | 11.7 | 45.3 | 11.1 | 31.9 | 36.5 | 80.1 | 9.0 | |
| Comparative Examples 3 | The tracking pH value | 0.29 | 2.4 | 60.0 | 31.5 | 2.7 | 3.4 | 4.4 | 75.0 | 16.1 |
Claims (7)
1, a kind of preparation method of high transparent and high impact resilience PVC, it is to be that raw material is made after the emulsion vinyl chloride monomer in the grafting by vinylbenzene and butyl acrylate, it is characterized in that, comprises the steps:
(1) preparation of emulsion:
Under polymerizing condition, temperature of reaction is 70～90 ℃, carries out emulsion polymerization by following prescription:
The composition parts by weight
Deionized water 100
Butyl acrylate/cross-linking agent solution 13.5～22.6
Vinylbenzene/cross-linking agent solution 18.5～9.7
Initiator 0.015～0.33
Emulsifying agent 0.12～5.06
Complexing agent 0.08～0.32
Make back adding ionogen in the above-mentioned emulsion preparation process or in emulsion, in butyl acrylate and cinnamic gross weight, electrolytical add-on is 100～10000ppm, and emulsion particle diameter is 0.05～0.08 μ m, and the aggregate particles morphological structure is a thyrsiform;
(2) add alkaline matter in above-mentioned emulsion, regulating the pH value is 8～10;
(3) graft polymerization of vinyl chloride monomer:
With the emulsion of step (2) gained, adopt vinyl chloride monomer in the method grafting of suspension polymerization again, reaction solution composed as follows:
The composition parts by weight
Vinyl chloride monomer 100
Deionized water 200～283
Initiator 0.10～0.15
Complexing agent 0.07～0.36
The emulsion 45.1～49.5 of step (2) gained
Composite dispersing agent 10.5～20.5
Under oxygen free condition, temperature was reacted 5～8 hours down for 40～60 ℃, promptly obtained vinyl chloride graft copolymer after washing, drying with above-mentioned reaction solution.
2, preparation method according to claim 1 is characterized in that, described linking agent adopts a kind of in Vinylstyrene, Phthalic acid, diallyl ester, diacrylate 1,4-butanediol ester, the diallyl maleate or their mixture.
3, preparation method according to claim 1 is characterized in that, described ionogen is selected KCl, NaCl, CaCl
2, a kind of among the HCl or their mixture.
4, preparation method according to claim 1 is characterized in that, described emulsifying agent adopts a kind of of Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, nonionogenic tenside or their mixture.
5, preparation method according to claim 1 is characterized in that, described composite dispersing agent is the mixture of Walocel MT 20.000PV, hydroxypropylcellulose, Vltra tears at least a and polyvinyl alcohol wherein.
6, preparation method according to claim 1 is characterized in that, described ionogen is KCl.
7, preparation method according to claim 1 is characterized in that, described electrolytical add-on is 500～1000ppm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100116A CN1053202C (en) | 1997-01-06 | 1997-01-06 | Method for prodn. of high transparent and high impact resilience PVC |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100116A CN1053202C (en) | 1997-01-06 | 1997-01-06 | Method for prodn. of high transparent and high impact resilience PVC |
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| CN1161345A CN1161345A (en) | 1997-10-08 |
| CN1053202C true CN1053202C (en) | 2000-06-07 |
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| CN97100116A Expired - Fee Related CN1053202C (en) | 1997-01-06 | 1997-01-06 | Method for prodn. of high transparent and high impact resilience PVC |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100354328C (en) * | 2004-12-14 | 2007-12-12 | 上海氯碱化工股份有限公司 | Method for producing polyvinyl chloride special for high-impact-resisting building material product |
| CN100402568C (en) * | 2005-09-29 | 2008-07-16 | 河北工业大学 | Polyurethane and its complex substance in-situ modified polyvinyl chloride resin and preparing method |
| CN101328239B (en) * | 2007-06-18 | 2011-05-11 | 山东瑞丰高分子材料股份有限公司 | Super high molecular weight high plasticization high brightness processing modifying agent for hard polychloroethylene |
| CN102659140B (en) * | 2012-05-02 | 2013-11-06 | 古舜起 | Special PVC (Poly Vinyl Chloride) raw material prepared by utilizing residuals obtained in production process of potash fertilizer |
| CN103113530B (en) * | 2013-02-01 | 2014-12-10 | 河北工业大学 | Preparation method of PVC (Polyvinyl Chloride) covalent bonding nanoparticle alloy resin |
| MX2015010335A (en) * | 2013-02-11 | 2016-09-19 | Vestolit Gmbh | Transparent article made of pvc graft copolymers. |
| CN107226968B (en) * | 2016-03-24 | 2019-04-12 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of preparation method of transparent impact-resistant polyvinyl chloride granules composition |
| CN107503165B (en) * | 2017-09-11 | 2019-09-20 | 浙江工贸职业技术学院 | A kind of sharkskin leather shoes |
| CN109929076A (en) | 2019-02-14 | 2019-06-25 | 山东东临新材料股份有限公司 | A kind of opaque high-impact MBS of PVC impact modifier and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101762A (en) * | 1985-03-26 | 1986-12-17 | 希尔斯-股份公司 | Production method with watered polyvinyl chloride of high-content acrylate elastomer |
| US5254630A (en) * | 1989-10-28 | 1993-10-19 | Huels Aktiengesellschaft | Process for the production of a vinyl chloride-butyl acrylate graft copolymer for processing by injection molding |
| EP0713892A1 (en) * | 1994-11-25 | 1996-05-29 | Solvay | Graft copolymers from vinylchloride with high impact resistance, their production process and use for the extrusion of profiles |
-
1997
- 1997-01-06 CN CN97100116A patent/CN1053202C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86101762A (en) * | 1985-03-26 | 1986-12-17 | 希尔斯-股份公司 | Production method with watered polyvinyl chloride of high-content acrylate elastomer |
| US5254630A (en) * | 1989-10-28 | 1993-10-19 | Huels Aktiengesellschaft | Process for the production of a vinyl chloride-butyl acrylate graft copolymer for processing by injection molding |
| EP0713892A1 (en) * | 1994-11-25 | 1996-05-29 | Solvay | Graft copolymers from vinylchloride with high impact resistance, their production process and use for the extrusion of profiles |
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| CN1161345A (en) | 1997-10-08 |
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