CN100547027C - PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier - Google Patents
PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier Download PDFInfo
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Abstract
PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier, be the nucleocapsid structure multipolymer, stratum nucleare is to carry out emulsion polymerization by butyl acrylate and linking agent, slightly acidic hole enlargement agent to form, shell at first is to proceed the letex polymerization graft reaction by methyl methacrylate and vinylbenzene on stratum nucleare, methyl methacrylate coats separately and forms second shell then, add the acrylic ester impact-resisting modifier separant after polymerization is finished in the emulsion, adding parts by weight is 2～5% of properties-correcting agent total amount.The particle diameter of the multipolymer that grafting of the present invention forms is all greater than more than the 450nm, and solved the compatibility problem of the high glue content of super-size anti-impact ACR and PVC, anti-impact ACR is dispersed in the PVC particle fast, thereby effective toughening PVC goods are widely used in the nontransparent goods of PVC.
Description
Technical field
The invention belongs to polyvinyl chloride (PVC) and use impact modifier, particularly a kind of ultra-large particle diameter high-fluidity acrylic ester impact modifier.
Background technology
Along with China's industrial expansion, the PVC industry is flourish, but the shock resistance ability of PVC self is poor, need add impact modifier.Impact modifier mainly contains kinds such as ACR, CPE, the CPE impact modifier exists shock strength low, the defective that work range is narrow, the ACR impact modifier has good impact property, work range is wide, but because China produces the unit research and development ability deficiency of ACR impact modifier, the result is more or less the same its shock strength and CPE impact modifier, because its production cost is higher, applies thereby restricted it.
Summary of the invention
Technical problem to be solved by this invention provides a kind of PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier, so that the PVC goods have good weather resisteant, good shock strength, work range is wideer.
PVC of the present invention ultra-large particle diameter high-fluidity acrylic ester impact modifier, it is characterized in that being the nucleocapsid structure multipolymer, stratum nucleare is by butyl acrylate and linking agent, slightly acidic hole enlargement agent is carried out emulsion polymerization and is formed, linking agent is 1～2% of a butyl acrylate weight, slightly acidic hole enlargement agent is 1～2% of a butyl acrylate weight, shell at first is to proceed the letex polymerization graft reaction by methyl methacrylate and vinylbenzene on stratum nucleare, methyl methacrylate and cinnamic weight proportion are 80～90%: 10～20%, methyl methacrylate coats separately and forms second shell then, with stratum nucleare and shell polymerization single polymerization monomer gross weight is 100% calculating, the stratum nucleare polymerization single polymerization monomer accounts for 90～95% of total polymerization amount of monomer, the first shell polymerization single polymerization monomer accounts for 2～3% of total polymerization amount of monomer, second shell accounts for 2～8% of total polymerization amount of monomer, add alkene esters of gallic acid impact modifier separant after polymerization is finished in the emulsion, adding parts by weight is 2～5% of properties-correcting agent total amount.
With stratum nucleare and shell polymerization single polymerization monomer total amount is 100% to calculate, at 0.01～0.05% initiator of stratum nucleare emulsion polymerization stage disposable adding polymerization single polymerization monomer total amount, account for 1～2% emulsifying agent of polymerization single polymerization monomer total amount.Water is generally 1.5～1.8 times of polymerization single polymerization monomer total amount.
The preferred Ethylene glycol dimethacrylate of described linking agent, allyl methacrylate(AMA) or O-phthalic allyl propionate.
Preferred Potassium Persulphate of described initiator or ammonium persulphate.
Described emulsifying agent can be sodium lauryl sulphate, sodium laurylsulfonate, potassium oleate, potassium stearate etc., preferably sodium dodecyl sulfate.
Described slightly acidic hole enlargement agent employing mass concentration is 10% acetic acid.
Described emulsion polymerization temperature is 60～80 ℃, and the stratum nucleare polyreaction adopts multistage to carry out, and preferably adopts 3～5 sections to carry out.
Alkene esters of gallic acid impact modifier separant is commercially available prod separant MB-1, be to carry out letex polymerization by n-BMA and methyl methacrylate to form, wherein n-BMA accounts for 0～10% of reaction monomers total mass, and methyl methacrylate accounts for 90～100% of reaction monomers total mass.The preparation method of separant is common emulsion polymerization.Need equally in the emulsion polymerization to add emulsifying agent and initiator, emulsifying agent is generally 1～2% of reaction monomers total amount, and initiator is generally 0.01～0.1% of reaction monomers total amount.Emulsifying agent and initiator all adopt the component of the common usefulness of emulsion polymerization, are sodium lauryl sulphate as emulsifying agent, and initiator adopts Potassium Persulphate or ammonium persulphate.
Product of the present invention is acrylate nucleoid----shell graft copolymer (an anti-impact ACR LS-61 resin), adopt emulsion polymerization technique, make copolymer particle have super-size through slightly acidic hole enlargement agent hole enlargement, increase grafting site simultaneously, the particle diameter of the multipolymer that grafting forms is all greater than more than the 450nm, and adopt the mode of multistage coating at shell, solved the compatibility problem of the high glue content of super-size anti-impact ACR and PVC, anti-impact ACR is dispersed in the PVC particle fast, thus effective toughening PVC goods.Be widely used in the nontransparent goods of PVC.Separant MB-1 used in the present invention, its emulsion is added on after the anti-impact ACR grafting in the emulsion, adopts mechanical stirring to mix.MB-1 forms sealing coat between anti-impact ACR particle, remedy because behind the raising anti-impact ACR nuclear portion content (surpassing 90%), the grafting of anti-impact ACR shell portion is incomplete, the bad defective that causes of coating.Improve the flowability of anti-impact ACR, prevent caking.Solution is easy plugging line in spraying drying, problems such as dry difficulty.Improve flowability, the dispersiveness of anti-impact ACR finished product, MB-1 uses the nuclear portion content that can improve anti-impact ACR, to improve its resistance to impact shock.
The physical and chemical indexes of impact modifier LS-61 resin of the present invention is:
| Index | The LS-61 resin |
| Outward appearance | The white flowing powder |
| Apparent density (g/cm 2) | 0.50-0.55 |
| Fugitive constituent (%) | ≤1.0 |
| Nuclear core glass temperature ℃ | -45 |
| Notched Izod impact strength (+23 ℃) (kJ/m 2) | ≥12.0 |
| Granularity (40 mesh standard sieve percent of pass) (%) | ≥98 |
In the PVC goods, use LS-61 resin 5-8 part can make that the PVC goods have good weather resisteant, good shock strength, work range is wideer, fillet weld strength is higher, surface smoothness is higher, percent thermal shrinkage reduces and be adapted to extrude at a high speed, be the PVC impact modifier of excellent property.
Embodiment
Preparation technology is: add deionized water in glass-lined kettle, emulsifier sodium lauryl sulfate, open stirring, add butyl acrylate and linking agent, slightly acidic hole enlargement agent (mass concentration is 10% acetic acid) (being divided into three to five sections finishes), logical steam is warming up to 60-80 ℃, add Potassium Persulphate or ammonium persulphate, the control exothermic heat of reaction.The use of emulsifying agent and slightly acidic hole enlargement agent had not only guaranteed the stability of emulsion but also can reach the purpose of hole enlargement.Shell partly is divided into two stages, and first stage makes it to form the mutual string structure of network with methyl methacrylate and vinylbenzene blend or copolymerization between nuclear-shell.Second stage is the shell that coats separately with methyl methacrylate.Add acrylic ester impact-resisting modifier separant MB-1 after polymerization is finished, after mixing,, get product through pressure spray dryer.
Embodiment 1:
According to above-mentioned preparation technology, linking agent adopts Ethylene glycol dimethacrylate, and consumption is 2% of a butyl acrylate weight.Slightly acidic hole enlargement agent employing mass concentration is 10% acetum, and consumption is 1% of a butyl acrylate amount.The emulsifying agent consumption is 1% of total polymerization monomer (polymerization single polymerization monomer that comprises a stratum nucleare and shell) amount, and Potassium Persulphate or ammonium persulphate consumption are 0.02% of total polymerization amount of monomer.First shell is 100% in polymerization single polymerization monomer methyl methacrylate and vinylbenzene weight, and methyl methacrylate is 90%, and vinylbenzene is 10%.With stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, the stratum nucleare polymerization single polymerization monomer accounts for 90% of total polymerization amount of monomer, the first shell polymerization single polymerization monomer accounts for 3% of total polymerization amount of monomer, second shell accounts for 7% of total polymerization amount of monomer, add acrylic ester impact-resisting modifier separant MB-1 after polymerization is finished in the emulsion, adding parts by weight is 2% of properties-correcting agent total amount.
The preparation of acrylic ester impact-resisting modifier separant MB-1 is in the 3000L glassed steel reaction vessels, add the 1650kg softening water, the 20kg sodium lauryl sulphate, open stirring, add methyl methacrylate 500kg, vinylbenzene 500kg, logical steam is warmed up to 60-80 ℃, adds 1.2kg Potassium Persulphate or ammonium persulphate, control reaction temperature 70-90 ℃, 85 ℃ of constant temperature obtained in 1.5 hours after heat release was finished.
Embodiment 2:
According to above-mentioned preparation technology, linking agent adopts allyl methacrylate(AMA), and consumption is 1% of a butyl acrylate weight.Slightly acidic hole enlargement agent employing mass concentration is 10% acetum, and consumption is 2% of a butyl acrylate amount.The emulsifying agent consumption is 2% of total polymerization monomer (polymerization single polymerization monomer that comprises a stratum nucleare and shell) amount, and Potassium Persulphate or ammonium persulphate consumption are 0.05% of total polymerization amount of monomer.First shell is 100% in polymerization single polymerization monomer methyl methacrylate and vinylbenzene weight, and methyl methacrylate is 80%, and vinylbenzene is 20%.With stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, the stratum nucleare polymerization single polymerization monomer accounts for 95% of total polymerization amount of monomer, the first shell polymerization single polymerization monomer accounts for 2% of total polymerization amount of monomer, second shell accounts for 3% of total polymerization amount of monomer, add acrylic ester impact-resisting modifier separant MB-1 after polymerization is finished in the emulsion, adding parts by weight is 5% of properties-correcting agent total amount.
The preparation of acrylic ester impact-resisting modifier separant MB-1 is with embodiment 1, but methyl methacrylate is 300kg, vinylbenzene 700kg.
Embodiment 3:
According to above-mentioned preparation technology, linking agent adopts allyl methacrylate(AMA), and consumption is 1% of a butyl acrylate weight.Slightly acidic hole enlargement agent employing mass concentration is 10% acetum, and consumption is 2% of a butyl acrylate amount.The emulsifying agent consumption is 2% of total polymerization monomer (polymerization single polymerization monomer that comprises a stratum nucleare and shell) amount, and Potassium Persulphate or ammonium persulphate consumption are 0.03% of total polymerization amount of monomer.First shell is 100% in polymerization single polymerization monomer methyl methacrylate and vinylbenzene weight, and methyl methacrylate is 85%, and vinylbenzene is 15%.With stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, the stratum nucleare polymerization single polymerization monomer accounts for 93% of total polymerization amount of monomer, the first shell polymerization single polymerization monomer accounts for 2% of total polymerization amount of monomer, second shell accounts for 5% of total polymerization amount of monomer, add acrylic ester impact-resisting modifier separant MB-1 after polymerization is finished in the emulsion, adding parts by weight is 5% of properties-correcting agent total amount.
The preparation of acrylic ester impact-resisting modifier separant MB-1 is with embodiment 1.
The comparative example:
According to above-mentioned preparation technology, stratum nucleare does not add slightly acidic hole enlargement agent, and linking agent adopts Ethylene glycol dimethacrylate, and consumption is 2% of a butyl acrylate weight.The emulsifying agent consumption is 1% of total polymerization monomer (polymerization single polymerization monomer that comprises a stratum nucleare and shell) amount, and Potassium Persulphate or ammonium persulphate consumption are 0.02% of total polymerization amount of monomer.With stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, 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, and shell adopts one deck, and monomer is a methyl methacrylate.
| Index | Embodiment 1 | Embodiment 2 | Embodiment 3 | The comparative example |
| Outward appearance | The white flowing powder | The white flowing powder | The white flowing powder | The white flowing powder |
| Apparent density (g/cm 2) | 0.55 | 0.5 | 0.53 | 0.45 |
| Mobile | Good | Good | Good | Difference |
| Notched Izod impact strength (+23 ℃) (kJ/m 2) | 17 | 18.2 | 18 | 15.0 |
| Granularity (40 mesh standard sieve percent of pass) (%) | 98 | 98 | 98 | 96 |
Claims (6)
1, a kind of PVC ultra-large particle diameter high-fluidity acrylic ester impact modifier, it is characterized in that being the nucleocapsid structure multipolymer, the particle diameter of multipolymer is all greater than more than the 450nm, stratum nucleare is by butyl acrylate and linking agent, slightly acidic hole enlargement agent is carried out emulsion polymerization and is formed, linking agent is 1～2% of a butyl acrylate weight, slightly acidic hole enlargement agent is 1～2% of a butyl acrylate weight, shell at first is to proceed the letex polymerization graft reaction by methyl methacrylate and vinylbenzene on stratum nucleare, methyl methacrylate and cinnamic weight proportion are 80～90%: 10～20%, methyl methacrylate coats separately and forms second shell then, with stratum nucleare and shell polymerization single polymerization monomer total amount is 100% calculating, the stratum nucleare polymerization single polymerization monomer accounts for 90～95% of total polymerization amount of monomer, the first shell polymerization single polymerization monomer accounts for 2～3% of total polymerization amount of monomer, second shell accounts for 2～8% of total polymerization amount of monomer, after finishing, polymerization adds alkene esters of gallic acid impact modifier separant in the emulsion, adding parts by weight is 2～5% of properties-correcting agent total amount, described alkene esters of gallic acid impact modifier separant, be to carry out letex polymerization by n-BMA and methyl methacrylate to form, wherein n-BMA accounts for 0～10% of reaction monomers total mass, and methyl methacrylate accounts for 90～100% of reaction monomers total mass.
2, impact modifier according to claim 1, it is characterized in that with stratum nucleare and shell polymerization single polymerization monomer gross weight being 100% to calculate, at 0.01～0.05% initiator of stratum nucleare emulsion polymerization stage disposable adding polymerization single polymerization monomer total amount, account for 1～2% emulsifying agent of polymerization single polymerization monomer total amount.
3, impact modifier according to claim 1 is characterized in that described linking agent is Ethylene glycol dimethacrylate, allyl methacrylate(AMA) or O-phthalic allyl propionate.
4, impact modifier according to claim 2 is characterized in that described initiator is Potassium Persulphate or ammonium persulphate.
5, impact modifier according to claim 2 is characterized in that described emulsifying agent is a sodium lauryl sulphate.
6, impact modifier according to claim 1 is characterized in that described slightly acidic hole enlargement agent employing mass concentration is 10% acetic acid.
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| CN101649020B (en) * | 2009-09-17 | 2011-04-20 | 河北工业大学 | Method for preparing polyacrylic ester foaming regulator with multi-layer nuclear shell structure |
| CN101649019B (en) * | 2009-09-17 | 2011-06-15 | 河北工业大学 | Method for preparing polyacrylic ester foaming regulation agent with double-layer nuclear shell structure |
| CN102417679B (en) * | 2011-11-23 | 2014-05-07 | 山东瑞丰高分子材料股份有限公司 | External lubricant for polyvinyl chloride (PVC) resin forming and processing and production method thereof |
| CN103627125A (en) * | 2013-11-26 | 2014-03-12 | 山东瑞丰高分子材料股份有限公司 | Method of improving dispersibility of impact-resistant ACR (Acrylics) assistant |
| CN103626925B (en) * | 2013-11-26 | 2015-12-30 | 山东瑞丰高分子材料股份有限公司 | Be applied to the preparation method of outdoor PVC product high impact resistant ACR auxiliary agent |
| CN103772593B (en) * | 2013-12-09 | 2016-02-10 | 何小刚 | A kind of acrylic acid or the like elastic emulsion and preparation method thereof |
| CN104231151B (en) * | 2014-08-29 | 2016-08-24 | 台州学院 | Polyvinyl-chloride use big particle diameter acrylic ester impact-resisting modifier and preparation method thereof |
| CN105085772B (en) * | 2015-07-17 | 2017-12-05 | 中国石油天然气股份有限公司 | A kind of polystyrene methylmethacrylate and its synthetic method and application |
| CN108276656A (en) * | 2018-02-11 | 2018-07-13 | 盐城科迈特新材料有限公司 | A kind of plastic film composite auxiliary for processing and preparation method thereof |
| CN112851886A (en) * | 2021-02-01 | 2021-05-28 | 济南金昌树新材料科技有限公司 | Preparation method of PVC (polyvinyl chloride) hardening modifier and obtained product |
| CN117586459A (en) * | 2024-01-19 | 2024-02-23 | 山东三润助剂科技股份有限公司 | PVC processing aid and preparation method thereof |
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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: Ultra-large particle diameter high-fluidity acrylic ester impact-resisting modifier for PVC Granted publication date: 20091007 License type: Exclusive License Record date: 20100323 |
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