CN101550208A - Continuous extrusion method by bulk polymerization of acrylate rubber - Google Patents
Continuous extrusion method by bulk polymerization of acrylate rubber Download PDFInfo
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- CN101550208A CN101550208A CNA2008102075986A CN200810207598A CN101550208A CN 101550208 A CN101550208 A CN 101550208A CN A2008102075986 A CNA2008102075986 A CN A2008102075986A CN 200810207598 A CN200810207598 A CN 200810207598A CN 101550208 A CN101550208 A CN 101550208A
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Abstract
A continuous extrusion method by the bulk polymerization of acrylate rubber is characterized in that: a reaction component I, a reaction component II, an initiator and an addition agent are mixed according to a proportioning ratio to form a mixed solution according to a certain mixture ratio; then the mixed solution is injected into an extruder protected under N2 for reaction and extrusion; and finally solid materials of various shapes are obtained. According to parts by weight, the mixed solution comprises: 100 parts of the component I, 0-30 parts of the component II, 0.01-5 parts of the initiator and 0-5 parts of the addition agent. The method has the following advantages of: pure polymer in the bulk polymerization and lower ash content, simple synthesis formula and less intermittent equipment, and less working procedures due to reaction under the solvent-free condition, shortened process, reduced cost and improved production efficiency.
Description
Technical field
The present invention relates to the reaction continuous extrusion method of acrylic elastomer mass polymerization, relate in particular to the mass polymerization of acrylic elastomer synthetic and on forcing machine, react the realization of extruding continuously.
Background technology
Reaction is extruded principle and is applied to the synthetic of superpolymer, comes across the sixties in 20th century the earliest, and that has realized at present using has urethane, a poly(lactic acid) etc.
Synthetic suspension polymerization, solution polymerization process, the emulsion polymerization of mainly containing of present industrial acrylic elastomer, wherein letex polymerization is comparatively general, but emulsion, suspension, three kinds of methods of solution all are faced with a series of problems, need recycling as a large amount of solvents or water, the synthesis technique complexity, the auxiliary agent that remains in the polymkeric substance makes troubles also for the processing and utilization in later stage.The tradition bulk polymerization is difficult to control because of heat of polymerization, so acrylic elastomer mass polymerization industrialization can't realize.And present method makes it in time carry out heat exchange with barrel wall by screw rod rotation and shear material is disperseed, thins, and whole process of while is continuous, has reduced residence time of material, and then has reduced the possibility of heat built-up.So seek that a kind of technology is simple, the synthetic polymkeric substance is pure, change product flexibly, the material high-temperature residence time is short, process environments is friendly, cost of investment is low method becomes a kind of trend.
Summary of the invention
Purpose of the present invention gets the mass polymerization of Voncoat R 3310 and multipolymer thereof and well realizes and application, with the forcing machine is reactor, the building-up reactions that is controlled to be by screw speed and temperature condition provides the suitable reaction compartment and the residence time, and then solves the disengaging problem of reaction conversion ratio and reactive component.In addition, under strong stirring, shearing action, weakened the disadvantageous effect that gel effect (viscosity that is polymerization system increases, and active chain end is by the phenomenon of embedding) is brought.Thereby make molecular weight distribution reasonable, make the degree that mixes between material bed attenuation increase reactive component, make its in time and barrel wall carry out heat exchange, whole process is continuous simultaneously, reduce residence time of material, and then reduced the possibility of heat built-up, reduced the thermograde of storeroom, solved the reaction heat control problem of mass polymerization, finally realized reacting and extruded continuously.
The present invention is achieved in that
The reaction continuous extrusion method of this acrylic elastomer mass polymerization is characterized in that: reactive component one, component two, initiator, auxiliary agent are mixed the back mixing solutions by proportioning inject N
2React in the forcing machine of protection and extrude.
Mixing solutions comprises in the composition of parts by weight among the present invention:
Component 1
Component 2 0～30
Initiator 0.01～5
Auxiliary agent 0～5.
Component one is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, ethyl acrylate, methacrylic acid, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, the butyl methacrylate.
Component two is a vinylformic acid methoxy ethyl ester, vinylformic acid ethoxy ethyl ester, 2-chloroethyl vinyl ether, vinyl chloroacetate, the ring chloracetate, glycidyl acrylate, glycidyl methacrylate, the ethylidene bornylene, vinylformic acid alcoxyl ether-ether, polyalkylene glycol acrylate methoxyl group ester, maleic acid dimethoxy ethyl ester, 3-methyl-2-butene ester, vinylbenzene, vinyl cyanide, ethene, the maleic acid monoesters, vinylformic acid, methylene-succinic acid, the methylene-succinic acid monoesters, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-three-(2-methoxy ethoxy) silane, in the vinyl methyl dimethoxysilane one or more.It act as the crosslinking functionality that polymkeric substance is provided, and improves the polymkeric substance oil resistance.
Initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), isopropyl benzene hydroperoxide, tertbutyl peroxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, peroxy dicarbonate, hydrogen peroxide, ferrous sulfate, the mercaptan.It act as to decompose and obtains free radical, causes each component polymerization.
Auxiliary agent is stearic acid, sodium stearate, potassium stearate, aluminum stearate, lithium stearate, barium stearate, Zinic stearas, water, N, one or more in dinethylformamide, dimethyl silicone oil, polymethylphenyl siloxane fluid, the chlorophenylmethyl silicone oil.It act as the friction that reduces between mixed solution and forcing machine.
The reaction continuous extrusion method of acrylic elastomer mass polymerization among the present invention; by above-mentioned each amounts of components proportioning; put into temperature control and can rise to thorough mixing in the mixing kettle that 60 ℃, alr mode are spraying type or stirring-type at temperature control below 40 ℃ or in the presence of aerobic and the stopper; mixing solutions is directed into temperature control by mixing kettle and stores in temperature control below 40 ℃ or in the presence of aerobic and the stopper can rise to 60 ℃ material storage kettle; again by metering outfit, with mixing solutions be injected into nitrogen protection the forcing machine spout after the forcing machine reaction extrude continuously.Screw speed is lower than 500 rev/mins in the whole extrusion, 40 ℃～100 ℃ of pre-thermal induction sections, and 70 ℃～200 ℃ of conversion zones, 40 ℃～200 ℃ of extruding zones, the material of extruding places packing bag to preserve after treatment.
Compared with prior art, the present invention has following advantage:
The polymkeric substance of a, mass polymerization is pure, ash content is lower;
B, synthesizing formula are simple, easy to operate;
C, reaction time are short, and intermittent equipment is few;
D, can the telomerized polymer residence time, avoid polymkeric substance to be exposed to for a long time under the high temperature and cause decomposing, little crosslinked, branching;
E, handiness with very big replacing extruding polymerization species;
The no three wastes are handled after f, the unreacted components extracting, environmental friendliness;
G, under solvent-free condition, react, reduced operation, shortened flow process, reduced cost, improved productivity;
Embodiment
In conjunction with the embodiments content of the present invention is described further, each component is in parts by weight.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Component one | 100 | 100 | 100 |
| Component two | 5 | 2.5 | 0 |
| Initiator | 0.08 | 0.08 | 0.04 |
| Auxiliary agent | 0 | 1 | 0 |
The component one of embodiment 1 is an ethyl propenoate; Component two is a vinylformic acid; Initiator is a Diisopropyl azodicarboxylate;
The component one of embodiment 2 is an ethyl propenoate; Component two is a vinyl chloroacetate; Initiator is Diisopropyl azodicarboxylate/hydrogen phosphide cumene (wherein Diisopropyl azodicarboxylate is 0.04, and hydrogen phosphide cumene is 0.04); Auxiliary agent is a stearic acid
The component one of embodiment 3 is ethyl propenoate/butyl acrylate (wherein ethyl propenoate is 85, and butyl acrylate is 15); Initiator is a benzoyl peroxide
Embodiment 1 is set to
| Pre-thermal induction section | Conversion zone | Extruding zone | |
| The position | Spout is to 1/3rd long places of machine barrel | / 3rd to 3/4ths places that machine barrel is long | 3/4ths places of machine barrel length are to head |
| Temperature (℃) | 50～80 | 90～120 | 120～150 |
Embodiment 2 is set to
| Pre-thermal induction section | Conversion zone | Extruding zone | |
| The position | Spout is to 1/3rd long places of machine barrel | / 3rd to 3/4ths places that machine barrel is long | 3/4ths places of machine barrel length are to head |
| Temperature (℃) | 65～95 | 80～150 | 100～120 |
Embodiment 3 is set to
| Pre-thermal induction section | Conversion zone | Extruding zone | |
| The position | Spout is to 2/5ths long places of machine barrel | 2/5ths to five/everywhere of machine barrel length | Machine barrel long five/everywhere to head |
| Temperature (℃) | 70～100 | 100～140 | 100～120 |
| Embodiment one | Embodiment two | Embodiment three | Homemade sample | The import sample | |
| Mooney viscosity | 39.6 | 30.7 | 27.5 | 25～45 | 25～45 |
| Fugitive constituent (%) | 0.50 | 0.49 | 0.47 | 0.8 | 0.5 |
| Ash content (%) | 0.31 | 0.33 | 0.30 | 0.8 | 0.5 |
Mooney viscosity: shear the rubber that the disc type viscometer records or the viscosity of glue stuff compounding with Mooney, can characterize molecular weight rubber.Be the viscosity of rubber herein.
Fugitive constituent: be used for the characterize polymers volatile content.
Ash content: be used for inorganic content after the characterize polymers calcination.
Claims (3)
1. the reaction continuous extrusion method of an acrylic elastomer mass polymerization is characterized in that: inject N after reactive component one, component two, initiator, auxiliary agent are mixed into mixing solutions by proportioning
2React in the forcing machine of protection and extrude the solid material of the different shape that finally obtains; Described mixing solutions comprises in the composition of parts by weight:
Component 1
Component 2 0～30
Initiator 0.01～5
Auxiliary agent 0～5.
2. method according to claim 1 is characterized in that: component one is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, ethyl acrylate, methacrylic acid, hydroxyethyl methylacrylate, Hydroxyethyl acrylate, the butyl methacrylate; Component two is a vinylformic acid methoxy ethyl ester, vinylformic acid ethoxy ethyl ester, 2-chloroethyl vinyl ether, vinyl chloroacetate, the ring chloracetate, glycidyl acrylate, glycidyl methacrylate, the ethylidene bornylene, vinylformic acid alcoxyl ether-ether, polyalkylene glycol acrylate methoxyl group ester, maleic acid dimethoxy ethyl ester, 3-methyl-2-butene ester, vinylbenzene, vinyl cyanide, ethene, the maleic acid monoesters, vinylformic acid, methylene-succinic acid, the methylene-succinic acid monoesters, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl-three-(2-methoxy ethoxy) silane, in the vinyl methyl dimethoxysilane one or more; Initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), isopropyl benzene hydroperoxide, tertbutyl peroxide, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, peroxy dicarbonate, hydrogen peroxide, ferrous sulfate, the mercaptan; Auxiliary agent is stearic acid, sodium stearate, potassium stearate, aluminum stearate, lithium stearate, barium stearate, Zinic stearas, water, N, one or more in dinethylformamide, dimethyl silicone oil, polymethylphenyl siloxane fluid, the chlorophenylmethyl silicone oil.
3. method according to claim 1; it is characterized in that: the reaction continuous extrusion method of acrylic elastomer mass polymerization; by described each the amounts of components proportioning of claim 1; put into temperature control and can rise to 60 ℃ at temperature control below 40 ℃ or in the presence of aerobic and the stopper; alr mode is a thorough mixing in the mixing kettle of spraying type or stirring-type; mixing solutions is directed into temperature control by mixing kettle and stores in temperature controllable below 40 ℃ or in the presence of aerobic and the stopper can rise to 60 ℃ material storage kettle; again by metering outfit, with mixing solutions be injected into nitrogen protection the forcing machine spout after the forcing machine reaction extrude continuously.Screw speed is lower than 500 rev/mins in the whole extrusion, 40 ℃～100 ℃ of pre-thermal induction sections, and 70 ℃～200 ℃ of conversion zones, 40 ℃～200 ℃ of extruding zones, the material of extruding places packing bag to preserve after treatment.
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| CN2008102075986A CN101550208B (en) | 2008-12-23 | 2008-12-23 | Continuous extrusion method by bulk polymerization of acrylate rubber |
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| CN2008102075986A CN101550208B (en) | 2008-12-23 | 2008-12-23 | Continuous extrusion method by bulk polymerization of acrylate rubber |
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| CN101550208B CN101550208B (en) | 2011-06-08 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942650A (en) * | 2012-11-09 | 2013-02-27 | 广州市高士实业有限公司 | Core-shell type double-active acrylate elastic body and preparation method thereof |
| CN102977536A (en) * | 2012-09-28 | 2013-03-20 | 天津金发新材料有限公司 | Acrylonitrile/acrylate/styrene copolymer resin and preparation method thereof |
| CN105949697A (en) * | 2016-07-22 | 2016-09-21 | 马晓均 | High-temperature-resisting acrylic rubber and preparation method thereof |
| CN110452442A (en) * | 2019-08-26 | 2019-11-15 | 西南交通大学 | A kind of percolate transports tubing and preparation method thereof |
| CN112011244A (en) * | 2020-09-02 | 2020-12-01 | 合肥工业大学 | Continuous production method of GMA acrylic resin powder coating |
| CN113174006A (en) * | 2021-03-11 | 2021-07-27 | 常州都铂高分子有限公司 | Method for preventing gelation and large particle generation of resin |
| CN114051506A (en) * | 2019-07-19 | 2022-02-15 | 日本瑞翁株式会社 | Acrylic rubber bag with excellent storage stability and water resistance |
| CN114163558A (en) * | 2020-09-10 | 2022-03-11 | 中国石油化工股份有限公司 | Acrylate rubber and preparation method and application thereof |
| CN114380940A (en) * | 2022-01-20 | 2022-04-22 | 上海高分子功能材料研究所 | Bulk polymerization method and crosslinking method of acrylate and silane binary copolymer |
-
2008
- 2008-12-23 CN CN2008102075986A patent/CN101550208B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977536A (en) * | 2012-09-28 | 2013-03-20 | 天津金发新材料有限公司 | Acrylonitrile/acrylate/styrene copolymer resin and preparation method thereof |
| CN102977536B (en) * | 2012-09-28 | 2014-10-15 | 天津金发新材料有限公司 | Acrylonitrile/acrylate/styrene copolymer resin and preparation method thereof |
| CN102942650A (en) * | 2012-11-09 | 2013-02-27 | 广州市高士实业有限公司 | Core-shell type double-active acrylate elastic body and preparation method thereof |
| CN102942650B (en) * | 2012-11-09 | 2015-09-09 | 广州市高士实业有限公司 | Core-shell type double-active acrylate elastic body and preparation method thereof |
| CN105949697A (en) * | 2016-07-22 | 2016-09-21 | 马晓均 | High-temperature-resisting acrylic rubber and preparation method thereof |
| CN114051506A (en) * | 2019-07-19 | 2022-02-15 | 日本瑞翁株式会社 | Acrylic rubber bag with excellent storage stability and water resistance |
| CN114051506B (en) * | 2019-07-19 | 2024-02-20 | 日本瑞翁株式会社 | Acrylic rubber bag excellent in storage stability and water resistance |
| CN110452442A (en) * | 2019-08-26 | 2019-11-15 | 西南交通大学 | A kind of percolate transports tubing and preparation method thereof |
| CN112011244A (en) * | 2020-09-02 | 2020-12-01 | 合肥工业大学 | Continuous production method of GMA acrylic resin powder coating |
| CN114163558A (en) * | 2020-09-10 | 2022-03-11 | 中国石油化工股份有限公司 | Acrylate rubber and preparation method and application thereof |
| CN113174006A (en) * | 2021-03-11 | 2021-07-27 | 常州都铂高分子有限公司 | Method for preventing gelation and large particle generation of resin |
| CN114380940A (en) * | 2022-01-20 | 2022-04-22 | 上海高分子功能材料研究所 | Bulk polymerization method and crosslinking method of acrylate and silane binary copolymer |
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| CN101550208B (en) | 2011-06-08 |
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