CN103467663B - Preparation method of acrylic ester type processing aid with multilayer gradient core-shell structure - Google Patents
Preparation method of acrylic ester type processing aid with multilayer gradient core-shell structure Download PDFInfo
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Abstract
The invention relates to a preparation method of an acrylic ester type processing aid with a multilayer gradient core-shell structure, belonging to the field of modification of functional macromolecular materials. The preparation method comprises the following process steps: (1) under the condition of stirring at 30 DEG C, adding deionized water, an initiator A, an emulsifier, a co-emulsifier, a dispersant, a soft monomer and a crosslinking agent into a reaction kettle, and performing pre-emulsification to obtain a pre-emulsion; (2) heating the pre-emulsion to a temperature less than or equal to 90 DEG C, and performing a thermal reaction to obtain a soft monomer core layer emulsion; and (3) adding an initiator B, alpha olefin and a monomer which has a solubility parameter similar to that of PVC (polyvinyl chloride) into the soft monomer core layer emulsion, and sequentially polymerizing 1-5 layers of rigid polymer shells with a solubility parameter similar to that of polyvinyl chloride to obtain the acrylic ester type processing aid. The obtained PVC processing aid has the advantages of low price, good effect of promoting plasticization, excellent weathering resistance, capability of improving impact properties of a product and the like, and can be widely applied to the fields of PVC building door and window profiles, pipes, wires, cables, small-scale household appliances and the like.
Description
Technical field
The present invention relates to a kind of preparation method of PVC processing aid, specifically, relate to a kind of preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin, belong to the preparation and modification field of functional high molecule material.
Background technology
Polyvinyl chloride (PVC) is one of four large commodity polymer materials, is also the macromolecular material of non-petroleum base route rare in numerous polymer.Because PVC produces primarily of calcium carbide route, depend on petroleum resources hardly.The price of the mechanical property of its excellence, self-extinguishing and relative moderate has made it have a wide range of applications in fields such as toy, footwear industry, building, decoration, agriculturals.At present, the global output of PVC has broken through 4,000 ten thousand tons/year.And wherein have the manufacture being used to PVC material of construction more than 50% respectively, also just mean that PVC is in the course of processing, plasticizing promotor and the annual usage quantity of toughner will more than 2,000,000 tons.
ACR is the english abbreviation of esters of acrylic acid rubber, is also the most widely used analog assistant in current PVC field.Chemically with on space structure see, ACR is a kind of esters of acrylic acid nano material with nucleocapsid structure.Its current average market valency Yue Wei $2 ten thousand/ton.According to the difference of nanoparticle core shell volume ratio, plasticizing promotor (or plasticizing conditioning agent) and toughner two kinds can be divided into.Wherein, when the content of polymethylmethacrylate (PMMA) shell is relatively less, and stratum nucleare is called toughner when being the rubber such as lightly crosslinked butyl polyacrylate or polyhutadiene, this type of ACR toughner can increase substantially the shock resistance of material under the condition reducing PVC material intensity and rigidity hardly; The plasticizing promotor that then can be used as PVC when PMMA shell content is higher uses.Because rigidity PMMA has the solubility parameter close with PVC, excellent compatibility between the two on the one hand; On the other hand, in nanoparticle, the existence of stratum nucleare soft rubber phase can make material by the deformation of rubber, impact energy be dissipated when being subject to foreign impacts, thus reaches the object of anti-impact.But regrettably the preparation method of ACR and technique comparatively complicated, and space structure design is still perfect not, has to improve space greatlyr.
Chinese patent CN200510044443.1 discloses the method for one-step synthesis polyvinyl-chloride use acrylic ester impact-resisting modifier, formed by methyl methacrylate and n-butyl acrylate letex polymerization, it is characterized in that under pH is the alkaline condition of 7 ~ 10, n-butyl acrylate reacts at 60 ~ 80 DEG C, when reaction conversion ratio reaches 10 ~ 15%, add agglomerant, when reaction conversion ratio reach >=97% time, add methyl methacrylate, react rear discharging spraying dry, wherein in the total mass of methyl methacrylate and n-butyl acrylate for 100%, methyl methacrylate accounts for 10 ~ 50%, n-butyl acrylate accounts for 50 ~ 90%, agglomerant is 0.1 ~ 1% of n-butyl acrylate amount.Agglomerant can be vinylformic acid, methacrylic acid, magnesium sulfate, sodium-chlor or calcium chloride.The method is simple esters of acrylic acid random copolymers, and space structure is single, complex process, cost intensive.
For the above-mentioned defect of traditional ACR, if can adopt and ACR molecular structure and the similar method of space structure design, and the shell of traditional ACR is carried out gradient design, then can at the cost ensureing effectively to promote PVC plasticization and reduce ACR while improving melt strength to greatest extent, the remarkable in economical benefits of product.
Summary of the invention
The present invention is intended to provide a kind of preparation method with the processing aids acrylic resin of multi-gradient nucleocapsid structure for the deficiencies in the prior art.The present invention by using through appropriately crosslinked soft monomer polymkeric substance as kernel, on the surface of softer core, on grafting free radical is polymerized successively, multilayer and PVC have the rigid polymer shell of close solubility parameter again, thus obtain the gradient core shell structure processing aid being applicable to PVC.Present invention process is simple, and production cost is relatively low, and obtained processing aid has cheap, toughness reinforcing and promotes the feature that plasticizing efficiency is high, weathering resistance is excellent.For achieving the above object, the technical solution used in the present invention is as follows:
There is a preparation method for multi-gradient nucleocapsid structure processing aids acrylic resin, it is characterized in that: comprise following processing step:
(1) under 30 DEG C and agitation condition, add successively in reactor the deionized water of 45 ~ 55%, 0 ~ 2.5% initiator A, 0.25 ~ 4% emulsifying agent, 0 ~ 2% assistant for emulsifying agent, the dispersion agent of 0.005 ~ 0.025%, the soft monomer of 40 ~ 48% and 0 ~ 2.5% linking agent, pre-emulsification process obtains the pre-emulsion of particle size range at 100 ~ 300 nm after 15 minutes;
(2) by pre-emulsion from 30 DEG C be warming up to≤90 DEG C, and insulation reaction 1 ~ 6 hour under agitation, namely obtains soft monomer stratum nucleare emulsion after being cooled to normal temperature;
(3) in soft monomer stratum nucleare emulsion, add the initiator B of 0.5 ~ 5%, and alhpa olefin, with PVC, there is at least one in the monomer of close solubility parameter, stir, at the temperature of 30 ~ 90 DEG C successively after polyreaction 1 ~ 5 time, system temperature is cooled to normal temperature, must have 2 ~ 5 layers of gradient core shell structure, and polymer shell and PVC has the processing aids acrylic resin of close solubility parameter; The described quality with the polymer shell of 2 ~ 5 layers of gradient core shell structure accounts for 30 ~ 80% of whole polymkeric substance.By internal layer to outer, the concentration with PVC with the hard monomer of close solubility parameter is increased to 100% by 0% successively, and namely outermost layer is all the hard monomer with PVC with close solubility parameter.
It should be noted that, per-cent involved in the present invention is mass ratio.
Described initiator A is at least one in peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate or ammonium persulphate.
Described emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene (OP, NP, CO), tween or class of department.
Described assistant for emulsifying agent is at least one in Virahol, propyl carbinol, the trimethyl carbinol, octanol, enanthol or lauryl alcohol.
Described dispersion agent is at least one in polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, HPMC, carboxy cellulose, carboxy cellulose sodium, sodium alginate, gelatin, calcium carbonate, magnesiumcarbonate or talcum powder.
Described soft monomer is at least one in butyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, N-Hexyl methacrylate, Isooctyl methacrylate, soybean oil, rapeseed oil, Semen Maydis oil, peanut oil, sesame oil, sunflower seed oil, Oleum Gossypii semen, sweet oil, plam oil, the young oil of rubber, Oleum Verniciae fordii or Viscotrol C.
Described linking agent is at least one in Vinylstyrene, diene acrylate or maleic anhydride.
Described initiator B is radical polymerization initiator, is selected from least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate.
Described alhpa olefin is at least one in methyl acrylate, ethyl propenoate, alkyl vinyl ether, vinyl acetate between to for plastic, vinylbenzene or vinyl cyanide.
The described monomer with PVC with close solubility parameter is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride or vinylidene chloride.
The PVC material adopting processing aids acrylic resin of the present invention to process, can be used for processing building doors and windows section bar, tubing, pipe fitting, electric wire, penetration pipe and small household appliances.
Compared with prior art, the outstanding advantages that the present invention has is:
1, the present invention using through appropriately crosslinked soft monomer polymkeric substance as kernel, especially 45 ~ 55% deionized water, 0 ~ 2.5% initiator A, 0.25 ~ 4% emulsifying agent, 0 ~ 2% assistant for emulsifying agent, the dispersion agent of 0.005 ~ 0.025%, the soft monomer of 40 ~ 48% and 0 ~ 2.5% linking agent composition reaction system under, pre-emulsification process obtains particle size range for 15 minutes after the pre-emulsion of 100 ~ 300 nm, be warming up to again≤90 DEG C, and insulation reaction 1 ~ 6 hour, soft monomer stratum nucleare emulsion.This processing parameter is reasonable, and technological process is simply easy to realize.
2, the present invention by adding initiator B, the alhpa olefin of 0.5 ~ 5% and have the monomer of close solubility parameter with PVC in obtained soft monomer stratum nucleare emulsion, under the temperature condition of 30 ~ 90 DEG C, the rigid polymer shell that upper multilayer and PVC have close solubility parameter can be polymerized through grafting free radical successively in the surface of softer core, thus obtains the processing aids acrylic resin with 2 ~ 5 layers of gradient core shell structure.The method adopts gradient core shell copolymerization technique, by the concentration gradient process of the methyl methacrylate with PVC in shell with close solubility parameter is effectively reduced materials and process cost, space structure design is reasonable, improve the impact resistance of PVC product while can meeting the existing performance of traditional ACR, and obtained processing aid has and promotes the feature that plasticizing efficiency is high, weathering resistance is excellent cheap, toughness reinforcing.
3, the processing aids acrylic resin with multi-gradient nucleocapsid structure prepared by the present invention can replace conventional processing additives type ACR and anti-impact type ACR completely, remarkable in economical benefits.
Accompanying drawing explanation
Fig. 1 is the chemical structure schematic diagram of multi-gradient nucleocapsid structure processing aids acrylic resin of the present invention
Fig. 2 is the plasticizing capacity correlation curve figure that the present invention has 4 layers of gradient core shell structure ACR and commercially available ACR.
Embodiment
Below by specific embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment is only for the invention will be further described; can not be interpreted as limiting the scope of the invention, the those of skill in the art in this field can make improvement and the adjustment of some unsubstantialities to the present invention according to the content of foregoing invention.
Embodiment 1
100 g deionized waters, 1 g Potassium Persulphate, 6 g tweens, 1 g Sodium dodecylbenzene sulfonate emulsifying agent, 4 g propyl carbinols, 0.1 g polyvinyl alcohol, 100 g soybean oil and 5 g Vinylstyrenes are added successively in the four-hole boiling flask carrying heating and whipping appts.Stir 15 minutes at 30 DEG C, obtain soybean oil pre-emulsion; Then, the temperature of reaction system is risen to 75 DEG C, insulation reaction is cooled to normal temperature and namely obtains processing aid kernel (i.e. stratum nucleare) emulsion after 2 hours.
1.5 g Potassium Persulphates, 6 g vinylbenzene and 20 g methyl methacrylates are added successively in above-mentioned 100g processing aid kernel emulsion.After stirring, gradually system temperature is increased to 75 DEG C, insulation reaction continues after 30 minutes to add 1.5 g Potassium Persulphates, 4 g vinylbenzene and 30 g methyl methacrylates in system, insulation reaction adds 1.5 g Potassium Persulphates and 50 g methyl methacrylates after 30 minutes again in reactor, system temperature, after 2 hours, is increased to 82 DEG C by insulation reaction further.Continue insulation reaction after 1 hour, system to be cooled to normal temperature and namely to obtain tool and to have three layers the processing aids acrylic resin of gradient core shell structure.
Embodiment 2
120 g deionized waters, 1 g ammonium persulphate, 1.5 g alkylphenol polyoxyethylene polyoxyethylene nonylphenol ethers, 1 g sodium lauryl sulphate, 0.1 g carboxy cellulose, 100 g butyl acrylates and 8 g diene acrylate are added successively in the four-hole boiling flask carrying heating and whipping appts.Stir 15 minutes at 30 DEG C, obtain butyl acrylate pre-emulsion.Then, raise temperature of reaction system to 70 DEG C, insulation reaction is cooled to normal temperature and namely obtains processing aid kernel (i.e. stratum nucleare) emulsion after 2 hours.
In above-mentioned 20g processing aid kernel emulsion, order adds 1 g ammonium persulphate, 4 g vinylbenzene and 10 g methyl methacrylates.After stirring, gradually system temperature is increased to 70 DEG C, insulation reaction adds 1 g ammonium persulphate, 3 g vinylbenzene and 20 g methyl methacrylates in system after 30 minutes, insulation reaction adds 1 g ammonium persulphate, 2 g vinylbenzene and 30 g methyl methacrylates after 30 minutes again in reactor, insulation reaction adds 1 g ammonium persulphate, 1 g vinylbenzene and 40 g methyl methacrylates again after 30 minutes, continue insulation reaction 30 minutes.And then in reactor, adding 1g ammonium persulphate and 50 g methyl methacrylates, system temperature, after 2 hours, is increased to 82 DEG C by insulation reaction further.Continue insulation reaction 1 hour, obtain tool and to be of five storeys the processing aids acrylic resin of gradient core shell structure.
Embodiment 3
Pungent and the 50 g Vinylstyrenes of 1000 g deionized waters, 10 g ammonium persulphates, 25 g alkylphenol polyoxyethylene emulsifying agent NP, 10 g sodium lauryl sulphate, 5 g hydroxypropylcelluloses, 5 g polyvinyl alcohol, the different ester of 1000 g vinylformic acid are added successively in the stainless steel pressure reactor of jacketed and whipping appts.Stir 15 minutes at 30 DEG C, obtain Isooctyl acrylate monomer pre-emulsion.Then, raise temperature of reaction system to 50 DEG C, insulation reaction is cooled to normal temperature and namely obtains processing aid kernel emulsion after 2 hours.
In above-mentioned 20000g processing aid kernel emulsion, add 100 g peroxy dicarbonates, 2000 g vinyl cyanide, 3000 g vinylchlorid successively, after stirring, gradually system temperature is increased to 50 DEG C, heat-insulation pressure keeping reacts 30 minutes.With peristaltic meatering pump, the mixed solution of 200 g peroxy dicarbonates, 1000 g vinyl cyanide and 6000 g vinylchlorid is squeezed into reactor fast, be controlled in 15 minutes and mixed solution is all pumped into reactor; After heat-insulation pressure keeping reaction obviously occurs Pressure Drop to system, continue reaction 30 minutes.System temperature is cooled to normal temperature, obtains tool and to have three layers the processing aid of gradient core shell structure.
Embodiment 4
500 g deionized waters, 5 g ammonium persulphates, 10 g alkylphenol polyoxyethylene emulsifying agent CO, 5 g sodium lauryl sulphate, 3 g hydroxypropylcelluloses, 3 g polyvinyl alcohol, 500 g Oleum Verniciae fordiis and 50 g diene acrylate are added successively in the stainless steel pressure reactor of jacketed and whipping appts.Stir 15 minutes at 30 DEG C, obtain Oleum Verniciae fordii pre-emulsion.Then, raise temperature of reaction system to 90 DEG C, insulation reaction is cooled to normal temperature and namely obtains processing aid kernel emulsion after 2 hours.
In above-mentioned 2000g processing aid kernel emulsion, add 50 g peroxy dicarbonates, 1000 g vinyl cyanide, 200 g vinylchlorid successively, after stirring, gradually system temperature is increased to 50 DEG C, heat-insulation pressure keeping reacts 30 points.With peristaltic meatering pump, the mixed solution of 50 g peroxy dicarbonates, 800 g vinyl cyanide and 300 g vinylchlorid is squeezed into reactor fast, be controlled in 15 minutes and mixed solution is all pumped into reactor; The mixed solution of 50 g peroxy dicarbonates, 400 g vinyl cyanide and 700 g vinylchlorid is squeezed into reactor with peristaltic pump after reacting 30 minutes by heat-insulation pressure keeping again fast; The mixed solution of 50 g peroxy dicarbonates and 1000 g vinylchlorid is squeezed into reactor with peristaltic pump after reacting 30 minutes by heat-insulation pressure keeping again fast, after heat-insulation pressure keeping reaction obviously occurs Pressure Drop to system, continues reaction 30 minutes.System temperature is cooled to normal temperature, the processing aid of 4 layers of gradient core shell structure must be had.
Experimental example 1 plasticizing capacity contrast experiment
For embodiment 4,4 layers of gradient core shell structure ACR and commercially available ACR will be had and contrast on plasticizing capacity, the results are shown in accompanying drawing 2.
Conclusion: can find out from accompanying drawing 2: same amount condition, 4 layers of gradient core shell structure ACR have the processing plasticizing performance similar with commercially available ACR; But from the plasticizing moment of torsion flow curve, the commercially available ACR's of plasticizing torque ratio of 4 layers of gradient core shell structure ACR is lower slightly.Show that 4 layers of gradient core shell structure ACR suitably can reduce the energy consumption in the course of processing while ensureing effectively to promote PVC plastic.
Claims (9)
1. there is a preparation method for multi-gradient nucleocapsid structure processing aids acrylic resin, it is characterized in that: comprise following processing step:
(1) under 30 DEG C and agitation condition, add successively in reactor the deionized water of 45 ~ 55%, 0 ~ 2.5% initiator A, 0.25 ~ 4% emulsifying agent, 0 ~ 2% assistant for emulsifying agent, the dispersion agent of 0.005 ~ 0.025%, the soft monomer of 40 ~ 48% and 0 ~ 2.5% linking agent, pre-emulsification process obtains the pre-emulsion of particle size range at 100 ~ 300 nm after 15 minutes;
(2) by pre-emulsion from 30 DEG C be warming up to≤90 DEG C, and insulation reaction 1 ~ 6 hour under agitation, namely obtains soft monomer stratum nucleare emulsion after being cooled to normal temperature;
(3) in soft monomer stratum nucleare emulsion, add the initiator B of 0.5 ~ 5%, and alhpa olefin, with PVC, there is at least one in the monomer of close solubility parameter, stir, at the temperature of 30 ~ 90 DEG C successively after polyreaction 1 ~ 5 time, system temperature is cooled to normal temperature, must have 2 ~ 5 layers of gradient core shell structure, and polymer shell and PVC has the processing aids acrylic resin of close solubility parameter; The described quality with the polymer shell of 2 ~ 5 layers of gradient core shell structure accounts for 30 ~ 80% of whole polymkeric substance;
Wherein, the alhpa olefin described in step (3) is at least one in methyl acrylate, ethyl propenoate, alkyl vinyl ether, vinyl acetate between to for plastic, vinylbenzene or vinyl cyanide.
2. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described initiator A is grafting polymerisation initiator, be selected from least one in peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate or ammonium persulphate.
3. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, is characterized in that: described emulsifying agent is at least one in sodium lauryl sulphate, sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, alkylphenol polyoxyethylene OP, alkylphenol polyoxyethylene NP, alkylphenol polyoxyethylene CO, tween or class of department.
4. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, is characterized in that: described assistant for emulsifying agent is at least one in Virahol, propyl carbinol, the trimethyl carbinol, octanol, enanthol or lauryl alcohol.
5. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, is characterized in that: described dispersion agent is at least one in polyvinyl alcohol, methylcellulose gum, hydroxypropylcellulose, HPMC, carboxy cellulose, carboxy cellulose sodium, sodium alginate, gelatin, calcium carbonate, magnesiumcarbonate or talcum powder.
6. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, is characterized in that: described soft monomer is at least one in butyl acrylate, Ethyl acrylate, Isooctyl acrylate monomer, butyl methacrylate, N-Hexyl methacrylate, Isooctyl methacrylate, soybean oil, rapeseed oil, Semen Maydis oil, peanut oil, sesame oil, sunflower seed oil, Oleum Gossypii semen, sweet oil, plam oil, rubber seed oil, Oleum Verniciae fordii or Viscotrol C.
7. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, is characterized in that: described linking agent is at least one in Vinylstyrene, diene acrylate or maleic anhydride.
8. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, it is characterized in that: described initiator B is radical polymerization initiator, be selected from least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dicumyl peroxide, peroxy dicarbonate, hydrogen peroxide, Potassium Persulphate, ammonium persulphate.
9. the preparation method with multi-gradient nucleocapsid structure processing aids acrylic resin according to claim 1, is characterized in that: the described monomer with PVC with close solubility parameter is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, vinylchlorid, Ethylene Dichloride or vinylidene chloride.
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| CN103788281A (en) * | 2014-03-05 | 2014-05-14 | 山东世拓化学科技有限公司 | Core-shell structure processing agent for rigid polyvinyl chloride and synthetic method thereof |
| CN103936932B (en) * | 2014-05-15 | 2016-09-14 | 齐齐哈尔大学 | A kind of top layer sub-synthetic method of hydroxyl core-shell latex particles |
| CN104327216B (en) * | 2014-10-15 | 2017-02-08 | 山东世拓高分子材料股份有限公司 | Terpolymer used for hard polyvinyl chloride and preparation method thereof |
| CN106366234B (en) * | 2016-08-30 | 2019-12-20 | 山东东临新材料股份有限公司 | Acrylate copolymer, preparation method and application thereof |
| CN108517138A (en) * | 2018-03-30 | 2018-09-11 | 天长市巨龙车船涂料有限公司 | A kind of fire resistant water-based coating |
| CN108498842B (en) * | 2018-05-15 | 2021-01-05 | 唐山市博世德医疗器械有限公司 | Medical dressing for in vitro wound care and preparation method thereof |
| CN110105489A (en) * | 2019-05-31 | 2019-08-09 | 高密浩翰木塑材料科技有限公司 | A kind of high solids content super high molecular weight Acrylate copolymerical emulsion production method |
| CN110396838B (en) * | 2019-07-19 | 2022-04-01 | 浙江海印数码科技有限公司 | Multi-stage structure based composite particle modified coating type ink for inkjet printing, and preparation method and application thereof |
| CN112812222B (en) * | 2021-03-05 | 2022-08-12 | 济南金昌树新材料科技有限公司 | Preparation method of AS resin modifier and obtained product |
| CN114149549A (en) * | 2021-12-31 | 2022-03-08 | 湖南高瑞电源材料有限公司 | Core-shell emulsion and preparation method and application thereof |
| CN118459674B (en) * | 2024-07-10 | 2024-09-06 | 山东广源化工材料有限公司 | Acrylic ester processing aid and preparation method and application thereof |
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| CN101967251A (en) * | 2010-09-21 | 2011-02-09 | 山东日科新材料有限公司 | Polyvinyl chloride mixture with excellent transparency, impact resistance and weatherability |
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Effective date of registration: 20210420 Address after: 525000 No.15, xiajie village, Dalu street, Magang Town, Dianbai County, Maoming City, Guangdong Province Patentee after: Huang Yanhong Address before: 225400 four access to Hongqiao Industrial Park, Taixing, Jiangsu Patentee before: JIAXU (JIANGSU) PLASTIC Co.,Ltd. |
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Effective date of registration: 20210709 Address after: 830000 chemical industry park, Midong District, Urumqi, Xinjiang Uygur Autonomous Region (No. 165, Hengzhi second lane, middle Petrochemical Road) Patentee after: URUMQI CITY HUATAILONG CHEMICAL AUXILIARIES Co.,Ltd. Address before: 525000 No.15, xiajie village, Dalu street, Magang Town, Dianbai County, Maoming City, Guangdong Province Patentee before: Huang Yanhong |
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