CN101190992A - Transparent acrylic ester impact-resisting modifier for PVC - Google Patents
Transparent acrylic ester impact-resisting modifier for PVC Download PDFInfo
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- CN101190992A CN101190992A CNA2006100703271A CN200610070327A CN101190992A CN 101190992 A CN101190992 A CN 101190992A CN A2006100703271 A CNA2006100703271 A CN A2006100703271A CN 200610070327 A CN200610070327 A CN 200610070327A CN 101190992 A CN101190992 A CN 101190992A
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Abstract
The inventions relates to transparent type acrylic impact modifier used in PVC, which is core-shell structural copolymer. Crosslinking agent is added into the polymeric monomer butyl acrylate and the styrene to carry out emulsion polymerization, thus obtaining the core layer; the shell layer is obtained through continuous emulsion polymerization grafting reaction of polymeric monomer styrene and methyl methacrylate on the core layer. The core layer polymeric monomer accounts for 80-90 percent of total polymeric monomer, the polymeric monomer of the shell layer accounts for 10-20 percent of the total polymeric monomer and pH of emulsion is controlled between 2 and 7. The emulsifier and the pH of the emulsion are used for adjusting granulation size of the copolymer between 80-150nm so as to guarantee the uniform with the refractive index of the PVC, thereby the product has stress whitening resistance and transparency when is used in PVC. Besides having the property of MBS resin, the product also solves the weather resistant problem of the MBS resin and can be used in polyvinyl chloride PVC transparent exterior products.
Description
Technical field
The invention belongs to polyvinyl chloride (PVC) and use impact modifier, particularly a kind of transparent acrylic ester impact-resisting modifier.
Background technology
Polyvinyl chloride (PVC) has CPE (chlorinatedpolyethylene), MBS (MBS), anti-impact ACR (acrylic acid esters co-polymer) etc. with the principal item of impact modifier.Its characteristics are respectively:
1, CPE (chlorinatedpolyethylene) is the product after the high density polyethylene(HDPE) chlorination, and this type of impact modifier is used for polyvinyl chloride (PVC) and has shock resistance, winter hardiness, chemical proofing etc. preferably: its shortcoming is poor for the transparency, tensile strength is low etc.Can not be used for polyvinyl chloride (PVC) transparent article.
2, MBS (MBS) is the graft copolymer of methyl methacrylate-grafted styrene-butadiene latex or isobutylene-isoprene latex, this type of impact modifier is used for polyvinyl chloride (PVC) and has shock resistance, the transparency, surface smoothness etc. preferably: its shortcoming is that weather resisteant is poor, its goods are widely used in polyvinyl chloride (PVC) transparent article, but owing in the product the easy photolysis of undersaturated divinyl component is arranged, it is outdoor that its goods can not be used for.
3, anti-impact ACR (acrylic acid esters co-polymer) is the graft copolymer of methyl methacrylate-grafted acrylic ester elastomer, this type of impact modifier is used for polyvinyl chloride (PVC) and has shock resistance, winter hardiness, weather resisteant, chemical proofing, surface smoothness etc. preferably: its shortcoming for since the distribution of the primitive particle of product and with the equal reason of the refractive index of polyvinyl chloride (PVC), can not be used for polyvinyl chloride (PVC) transparent article.
In sum, polyvinyl chloride needs a kind of more outstanding impact modifier that is used for outdoor transparent article.
Summary of the invention
Technical problem to be solved by this invention provides a kind of PVC transparent acrylic ester impact-resisting modifier, has the white and transparency of folding and solve the weather resisteant of PVC goods in PVC uses.
PVC transparent acrylic ester impact-resisting modifier of the present invention, it is characterized in that being the nucleocapsid structure multipolymer, wherein stratum nucleare adds linking agent by polymerization single polymerization monomer butyl acrylate and vinylbenzene and carries out emulsion polymerization and form, in stratum nucleare polymerization single polymerization monomer gross weight is 100%, butyl acrylate is 50～70%, vinylbenzene is 30～50%, linking agent is 0.5～2% of a stratum nucleare polymerization single polymerization monomer total amount, shell is to proceed the letex polymerization graft reaction by polymerization single polymerization monomer vinylbenzene and methyl methacrylate on stratum nucleare to form, in shell polymerization single polymerization monomer total amount is 100%, methyl methacrylate is 40～50%, vinylbenzene is 50～60%, with stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, at disposable 0.01～0.05% the initiator that is incorporated as the polymerization single polymerization monomer total amount of stratum nucleare emulsion polymerization stage, account for 1～3% emulsifying agent of polymerization single polymerization monomer total amount, the stratum nucleare polymerization single polymerization monomer accounts for 80～90% of total polymerization amount of monomer, the shell polymerization single polymerization monomer accounts for 10～20% of total polymerization amount of monomer, and the PH of control emulsion is 2～7.
Described linking agent preferably adopts Ethylene glycol dimethacrylate, allyl methacrylate(AMA) or Phthalic acid, diallyl ester.
Preferred Potassium Persulphate of described initiator or ammonium persulphate.
Described emulsifying agent can be sodium lauryl sulphate, sodium laurylsulfonate, potassium oleate, potassium stearate or potassium rosinate.
Described emulsion polymerization temperature is 70～80 ℃, and the stratum nucleare polyreaction can adopt multistage (as 4～7 sections) to carry out, and each section polymerization single polymerization monomer amount is divided equally, when record transformation efficiency greater than 95% after, add next section polymerization single polymerization monomer again.The needed water yield of polyreaction is generally 1.5～1.8 times of polymerization single polymerization monomer total amount.
PVC carries out with transparent acrylic ester impact-resisting modifier (being called for short the LS-12 resin) the partially polymerized 4-7 of the being divided into section of stratum nucleare, adjust the grain of multipolymer all directly between 80-150nm with the potential of hydrogen of emulsifying agent and emulsion, thereby guarantee consistently with the refractive index of PVC, it is white and transparent to make this product have a folding in PVC uses.Be used for the PVC transparent article, can substitute the MBS resin.Product has also solved the weather resisteant problem of MBS resin except that the performance that has the MBS resin, can be widely used in the outer goods of polyvinylchloride transparent chambers.
Technical indicator sees Table:
| Project | Index |
| Outward appearance | The white flowing powder |
| Granularity (aperture 0.45mm standard sieve percent of pass) % | ≥98 |
| Fugitive constituent % | ≤1.0 |
The performance table look-up:
Above five assembly sides are proportionally caused 125 ℃ of dischargings coolings moulding at a high speed respectively in the mixer, the back is drawn into sheet material under 180 ℃ of conditions of 3 minutes on the twin-roll plastic mixing mill.Carry out performance detection respectively.
Through performance detects data as can be seen, and the Performance Detection data that contain the prescription of properties-correcting agent LS-12 of the present invention are optimum.
Embodiment
Embodiment 1:
In the 3000L glass-lined kettle, add 50～70% soft water (the emulsion total amount is by 100%), the sodium lauryl sulphate of 1% (accounting for the total polymerization amount of monomer), open stirring, add butyl acrylate, vinylbenzene and linking agent Ethylene glycol dimethacrylate, in butyl acrylate and cinnamic amount is 100%, butyl acrylate is 50%, vinylbenzene is 50%, Ethylene glycol dimethacrylate is 1% of stratum nucleare two polymerization single polymerization monomer total amounts, be incorporated as 0.01% Potassium Persulphate of stratum nucleare and shell total polymerization amount of monomer, polymerization single polymerization monomer can be divided into 4 sections and carry out letex polymerization, control reaction temperature 70-80 ℃.After heat release is finished, 80-85 ℃ of constant temperature 1 hour.Continuation adding polymerization single polymerization monomer methyl methacrylate and vinylbenzene issue lactogenesis liquid graft polymerization at 70-80 ℃ and obtain shell, are 100% in shell polymerization single polymerization monomer total amount, and methyl methacrylate is 50%, and vinylbenzene is 50%.The stratum nucleare polymerization single polymerization monomer accounts for 80% of total polymerization amount of monomer, and the shell polymerization single polymerization monomer accounts for 20% of total polymerization amount of monomer.The PH that regulates emulsion by oleic acid is 3, after reaction is finished, and the product of making through the low-temperature pressure spraying drying.
Embodiment 2:
Technological process is with embodiment 1, the amount of sodium lauryl sulphate that different is is 2% of a total polymerization amount of monomer, and initiator adopts ammonium persulphate, and consumption is 0.05% of a total polymerization amount of monomer, linking agent adopts allyl methacrylate(AMA), and consumption is 2% of a stratum nucleare polymerization single polymerization monomer total amount.The stratum nucleare butyl acrylate is 60%, and vinylbenzene is 40%, and the shell methyl methacrylate is 40%, and vinylbenzene is 60%, and the stratum nucleare polymerization single polymerization monomer accounts for 90% of total polymerization amount of monomer, and the shell polymerization single polymerization monomer accounts for 10% of total polymerization amount of monomer.Regulate the PH of emulsion 5 by vinylformic acid.
Embodiment 3:
Technological process is with embodiment 1, the amount of sodium lauryl sulphate that different is is 3% of a total polymerization amount of monomer, and initiator adopts ammonium persulphate, and consumption is 0.02% of a total polymerization amount of monomer, linking agent adopts Phthalic acid, diallyl ester, and consumption is 0.5% of a stratum nucleare polymerization single polymerization monomer total amount.The stratum nucleare butyl acrylate is 70%, and vinylbenzene is 30%.The shell methyl methacrylate is 50%, and vinylbenzene is 50%, and the stratum nucleare polymerization single polymerization monomer accounts for 80% of total polymerization amount of monomer, and the shell polymerization single polymerization monomer accounts for 20% of total polymerization amount of monomer.Regulate emulsion PH 2.
Claims (4)
1. PVC transparent acrylic ester impact-resisting modifier, it is characterized in that being the nucleocapsid structure multipolymer, wherein stratum nucleare adds linking agent by polymerization single polymerization monomer butyl acrylate and vinylbenzene and carries out emulsion polymerization and form, in stratum nucleare polymerization single polymerization monomer gross weight is 100%, butyl acrylate is 50～70%, vinylbenzene is 30～50%, linking agent is 0.5～2% of a stratum nucleare polymerization single polymerization monomer total amount, shell is to proceed the letex polymerization graft reaction by polymerization single polymerization monomer vinylbenzene and methyl methacrylate on stratum nucleare to form, in shell polymerization single polymerization monomer total amount is 100%, methyl methacrylate is 40～50%, vinylbenzene is 50～60%, with stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, at disposable 0.01～0.05% the initiator that is incorporated as the polymerization single polymerization monomer total amount of stratum nucleare emulsion polymerization stage, account for 1～3% emulsifying agent of polymerization single polymerization monomer total amount, the stratum nucleare polymerization single polymerization monomer accounts for 80～90% of total polymerization amount of monomer, the shell polymerization single polymerization monomer accounts for 10～20% of total polymerization amount of monomer, and the PH of control emulsion is 2～7.
2. PVC transparent acrylic ester impact-resisting modifier according to claim 1 is characterized in that described linking agent is Ethylene glycol dimethacrylate, allyl methacrylate(AMA) or Phthalic acid, diallyl ester.
3. PVC transparent acrylic ester impact-resisting modifier according to claim 1 is characterized in that described initiator is Potassium Persulphate or ammonium persulphate.
4. PVC transparent acrylic ester impact-resisting modifier according to claim 1 is characterized in that described emulsifying agent is sodium lauryl sulphate, sodium laurylsulfonate, potassium oleate, potassium stearate or potassium rosinate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100703271A CN100556951C (en) | 2006-11-18 | 2006-11-18 | The PVC transparent acrylic ester impact-resisting modifier |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100703271A CN100556951C (en) | 2006-11-18 | 2006-11-18 | The PVC transparent acrylic ester impact-resisting modifier |
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| CN101190992A true CN101190992A (en) | 2008-06-04 |
| CN100556951C CN100556951C (en) | 2009-11-04 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864121A (en) * | 2010-04-14 | 2010-10-20 | 西安中财型材有限责任公司 | Transparent section and preparation process thereof |
| CN101935372A (en) * | 2010-09-29 | 2011-01-05 | 山东瑞丰高分子材料股份有限公司 | Method for preparing styrene and acrylic ester monomer copolymer |
| CN102464786A (en) * | 2010-11-10 | 2012-05-23 | 上海华明高技术（集团）有限公司 | Polyacrylate elastomer emulsion and preparation method thereof |
| CN101875712B (en) * | 2009-04-30 | 2012-06-27 | 上海天坛助剂有限公司 | Production method of MBS (Methacrylate Butadiene Styrene) resin |
| CN103304727A (en) * | 2013-07-08 | 2013-09-18 | 济南源键新材料有限公司 | Core-shell structural elastic emulsion, coating containing emulsion and preparation method thereof |
| CN103613713A (en) * | 2013-11-26 | 2014-03-05 | 山东瑞丰高分子材料股份有限公司 | Preparation method for impact-resistant ACR (acrylate copolymer) assistant applied to transparent PVC (polyvinyl chloride) products |
| 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 |
| CN115232262A (en) * | 2022-03-09 | 2022-10-25 | 威海金合思化工有限公司 | Acrylate impact modifier for transparent PVC (polyvinyl chloride) products and preparation method thereof |
-
2006
- 2006-11-18 CN CNB2006100703271A patent/CN100556951C/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875712B (en) * | 2009-04-30 | 2012-06-27 | 上海天坛助剂有限公司 | Production method of MBS (Methacrylate Butadiene Styrene) resin |
| CN101864121A (en) * | 2010-04-14 | 2010-10-20 | 西安中财型材有限责任公司 | Transparent section and preparation process thereof |
| CN101864121B (en) * | 2010-04-14 | 2012-07-04 | 西安中财型材有限责任公司 | Transparent section and preparation process thereof |
| CN101935372A (en) * | 2010-09-29 | 2011-01-05 | 山东瑞丰高分子材料股份有限公司 | Method for preparing styrene and acrylic ester monomer copolymer |
| CN102464786A (en) * | 2010-11-10 | 2012-05-23 | 上海华明高技术（集团）有限公司 | Polyacrylate elastomer emulsion and preparation method thereof |
| CN102464786B (en) * | 2010-11-10 | 2013-09-18 | 上海华明高技术（集团）有限公司 | Polyacrylate elastomer emulsion and preparation method thereof |
| CN103304727A (en) * | 2013-07-08 | 2013-09-18 | 济南源键新材料有限公司 | Core-shell structural elastic emulsion, coating containing emulsion and preparation method thereof |
| CN103304727B (en) * | 2013-07-08 | 2016-04-06 | 济南源键新材料有限公司 | A kind of hud typed elastic emulsion, coating and preparation method thereof containing this kind of emulsion |
| CN103613713A (en) * | 2013-11-26 | 2014-03-05 | 山东瑞丰高分子材料股份有限公司 | Preparation method for impact-resistant ACR (acrylate copolymer) assistant applied to transparent PVC (polyvinyl chloride) products |
| CN103613713B (en) * | 2013-11-26 | 2016-03-30 | 山东瑞丰高分子材料股份有限公司 | Be applied to the preparation method of transparent PVC goods anti-impact ACR auxiliary agent |
| 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 |
| CN115232262A (en) * | 2022-03-09 | 2022-10-25 | 威海金合思化工有限公司 | Acrylate impact modifier for transparent PVC (polyvinyl chloride) products and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100556951C (en) | 2009-11-04 |
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Owner name: SANDONG RUIFENG POLYMER MATERIAL CO., LTD. Free format text: FORMER NAME: YIYUAN RUIFENG MACROMOLECULE MATERIALS CO., LTD. |
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Address after: Yiyuan County of Shandong Province, Zibo Bao Feng Lu 256100, No. 26 Patentee after: Shandong Ruifeng Polymer Material Co., Ltd. Address before: Yiyuan County of Shandong Province, Zibo Bao Feng Lu 256100, No. 26 Patentee before: Ruifeng Polymer Material Co., Ltd., Yiyuan County |
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Application publication date: 20080604 Assignee: Zibo Zhongnan Plastics Co., Ltd. Assignor: Ruifeng Polymer Material Co., Ltd., Yiyuan County Contract record no.: 2010370000108 Denomination of invention: Transparent acrylic ester impact-resisting modifier for PVC Granted publication date: 20091104 License type: Exclusive License Record date: 20100323 |