CN102850481B - Preparation method for branched-structure (methyl) acrylate polymer - Google Patents
Preparation method for branched-structure (methyl) acrylate polymer Download PDFInfo
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- CN102850481B CN102850481B CN201110180516.5A CN201110180516A CN102850481B CN 102850481 B CN102850481 B CN 102850481B CN 201110180516 A CN201110180516 A CN 201110180516A CN 102850481 B CN102850481 B CN 102850481B
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Abstract
The invention relates to a preparation method for a branched-structure (methyl) acrylate polymer. The method includes providing a comonomer, an auxiliary agent mixture, an initiator, and a chain-transfer agent into a fully-mixing type reactor, for polymerization at 130-150 DEG C., with conversion rate of 45 -75%; transferring obtained reaction mixture into a straight tube type reactor for reaction at 140-160 DEG C., with conversion rate of 60-90%. The initiator can be 2,2-bis(4,4-ditert-pentyl peroxy cyclohexyl) propane, 2,2-bis(4,4-ditert octyl peroxy cyclohexyl)propane, 2,2-bis-(4,4-di- Alpha-cumenyl phenyl cyclohexyl) propane, 2,2-bis-(4,4-ditert-butyl peroxy cyclohexyl) butane, or 2,2-bis-(4,4-ditert-octyl peroxy cyclohexyl)butane. The initiator is 0.0005 to 0.01 weight parts. The method has the advantages of high polymerization rate, high polymer molecular weight, good light transmittance, and good melt flow performance.
Description
Technical field
The present invention relates to the method for standby (methyl) acrylic polymer of a kind of continuous bulk polymerization legal system, relate in particular to the preparation method of a kind of branched structure (methyl) acrylic polymer.
Background technology
(methyl) acrylic polymer has the performances such as excellent optical characteristics, weathering resistance, chemical stability and Physical Mechanical thereof, and the transparent material of this excellence is widely used in various illuminating equipments, optical element, various instrument dial plate, case, scale card, advertisement, aircraft, automobile and the field such as medical.Especially in the miniaturization and the lightweight in automobile industry in field of electronics, (methyl) acrylic polymer shows many superiority.
In the course of processing, when requiring resin to there is high workability, after moulding, to there is good physical strength.In order to meet these requirements, researchist has in the past proposed reduce the molecular weight of polymkeric substance or adopt the suitable schemes such as comonomer.But when molecular weight is reduced to a certain degree, there is the problem that physical strength or solvent resistance decline; In adopting the method for comonomer, when interpolymer component concentration acquires a certain degree, there is degradation problem under second-order transition temperature decline, thermal denaturation temperature in polymkeric substance.
Japanese patent application publication No. 1994-306109 proposes the acrylic resin preparation method of copolymerization polyfunctional monomer and chain-transfer agent.Japanese patent application publication No. 1996-208746 also proposes similar preparation method, is wherein only mentioned to polyfunctional monomer.But above-mentioned two kinds of methods all adopt suspension polymerization.Adopting suspension polymerization to prepare the method for acrylic resin, have in process of production lot of advantages, but be subject to the impact of the dispersion stabilizer that suspension polymerization used, there is fatal problem in the optical characteristics of product.And while using polyfunctional monomer, gel content rises, and causes product appearance undesirable.
In order to overcome above-mentioned shortcoming, Japanese patent application publication No. 1995-095873 proposes the method that solution method is prepared branched structure polymkeric substance.But need desolventizing while adopting the method, not only facility investment is high, and resistance toheat also declines thereupon.
Energy consumption from the purity of product, quality, production and the aspects such as impact of environment are considered, mass polymerization is the best approach of preparing acrylic resin.The monomer that it is principal constituent by methyl methacrylate that Japanese patent application publication No. 2003-96105 proposes is injected into the method that complete mixed type reactor carries out mass polymerization.Reactive polymeric rate is that 40-70%, polymerization temperature are that 120-180 ℃, mean residence time are that 15～40 minutes, transformation period are in 1 minute.Such rapid polymerization speed has advantage in productivity, but needs accurately to control initiator, reactor pressure condition etc.Meanwhile, because of the transformation period short, make reactant reach uniform state, must improve the revolution of agitator, this highly energy-consuming is uneconomic in industrial production.
Summary of the invention
The object of this invention is to provide a kind of method of preparing (methyl) acrylic polymer that there is branched structure by continuous bulk.By introducing the Multifunctional initiator initiated polymerization of suitable transformation period, can prepare stably, expeditiously (methyl) acrylic resin moulding compound with excellent properties.This class multifunctional initiator contains a plurality of active groups, have from the ability of multiterminal initiating polymerization of vinyl monomer, there is higher efficiency of initiation, when having improved polymerization rate, can also obtain the polymkeric substance with higher molecular weight, thereby obtain the moulding compound product of excellent performance.In other words, compare with initiator in the past, by adding the seldom this initiator of amount, can within the desirable residence time, complete polyreaction, reduce the residual impact on polymkeric substance color and luster of initiator.In addition, dendritic polymer has the simple linear polymer of same molecular amount relatively with it, and molecular coil size is little, little with the intersegmental winding degree of chain in segment, so the melt viscosity of dendritic polymer is lower, possesses better processing flowability.
Continuous bulk polymerization reaction preparation of the present invention has the method for branched structure (methyl) acrylic polymer, in all mixed-type reactor and straight tubular reactor, to carry out high temperature continuous bulk polymerization, by introduce polyfunctional group radical initiator in (methyl) acrylic ester monomer, preparation has (methyl) acrylic polymer of branched structure.The step that this method comprises is as follows: by nitrogen system, the oxygen level of dissolving in comonomer and agent mixture is down to below 2ppm; In all mixed-type reactor, supply with comonomer and agent mixture, polyfunctional group radical initiator and chain-transfer agent continuously, polymerization temperature is controlled in 130-150 ℃, and control polymerisation conversion is 45-75%; The reaction mixture obtaining in all mixed-type reactor is sent into further polymerization in straight tubular reactor continuously, and temperature of reaction is controlled within the scope of 140-160 ℃, and controlling the final transformation efficiency of polymerization is 60-90%; By the polymkeric substance finally obtaining, deliver in vented twin-screw extruder, volatile matter is removed in separation continuously, finally by tablets press, makes moulding compound particle.
Comonomer of the present invention and agent mixture are by alkyl methacrylate 90～98 parts of (weight) and 2～10 parts of (weight) formations of alkyl acrylate.In the present invention, as (methyl) acrylic ester monomer, have no particular limits, for example, can use (methyl) alkyl acrylate with the alkyl that carbonatoms is 1-8, as (methyl) methyl acrylate, (methyl) ethyl propenoate.(methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) 2-EHA etc.These (methyl) acrylic ester monomers may be used alone, can also be used in combination.This patent selects take methyl methacrylate to carry out polymerization as main monomer.Aforesaid propylene acid alkyl ester can be exemplified as methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid 2-ethyl pentyl ester etc., or their two or more mixture.Preferred methyl acrylate and ethyl propenoate.
The polyfunctional group radical initiator adding of the present invention is that the transformation period under polymerization temperature is about the radical initiator of 1～10 minute.Preferably the transformation period under polymerization temperature is about the multifunctional initiator of 70sec～5 minute.The structural formula of this polyfunctional group radical initiator is as follows:
Wherein: R is that carbonatoms is the alkyl or phenyl of 1-5, R
1and R
2that carbonatoms is the alkyl of 1-2.
The polyfunctional group radical initiator with said structure formula comprises: 2,2-two (4,4-bis-tert-pentyl peroxide cyclohexyl) propane, 2, two (the tertiary octyl group peroxide of 4, the 4-bis-cyclohexyl) propane, 2 of 2-, 2-two (4,4-bis-α-cumyl peroxide cyclohexyl) propane, 2, two (4, the 4-di-t-butyl peroxide cyclohexyl) butane, 2 of 2-, two (the tertiary octyl group peroxide of 4,4-bis-cyclohexyl) butane of 2-etc.Above initiator can be used separately, also can use together with other initiator.
In preparation method of the present invention, the monomer mixture of take is benchmark as 100 parts (weight), and the amount of above-mentioned polyfunctional group radical initiator is 0.0005～0.01 part (weight).
Described chain-transfer agent is tertiary lauryl mercaptan, and weight is 0.2 part.
The melt flow rate (MFR) of the polymkeric substance that preparation method of the present invention obtains is within the scope of 3-15g/10min.
Polymerization temperature is controlled in the high temperature range of 130-160 ℃.When polymerization temperature is during lower than 130 ℃, rate of polymerization is low, and the residence time is long.And along with the carrying out of reaction, system viscosity increases gradually, cannot carry out stable polyreaction, cause final transformation efficiency to reduce.When polymerization temperature is during higher than 160 ℃, system viscosity can significantly reduce, although this is conducive to stable operation, now in polymerization system, easily generates a large amount of oligopolymer, and the molecular weight distribution of polymkeric substance broadens, and causes mechanical property and optical property to decline.
This patent has proposed a kind ofly to have compared with the method for (methyl) acrylic polymer of high productivity, relates in particular to the preparation method of a kind of branched structure (methyl) acrylic polymer.Under identical initiator concentration, the method rate of polymerization that this patent provides is fast, polymericular weight is high, light transmission good, and stably (methyl) acrylic resin moulding compound of processability excellence, and material melt flowability under processing shearing condition is good.
Embodiment
The polymkeric substance obtaining in following examples has carried out following properties evaluation:
Adopt the normal temperature gel permeation chromatograph of U.S. Waters company and weight average molecular mass and the absolute molecular mass that polymkeric substance is measured in the polygonal laser light scattering instrument coupling of U.S. Wyatt.
Adopt melt flow rate (MFR) determinator according to the melt flow rate (MFR) of ISO1133 (230 ℃, 3.8kg) test polymer.
Adopt the transmittance of transmittance/mist degree determinator WGT-S test polymer.
Adopt U.S. Labscan-XE color measurement instrument (wavelength region: the 400nm-700nm) yellowness index of test polymer.
Embodiment 1
In methyl methacrylate and methyl acrylate mixture, add two (4,4-di-t-butyl peroxide cyclohexyl) butane and the tertiary lauryl mercaptans of chain-transfer agent of 2,2-, above raw material is mixed in proportion.Mixture feed composition: the monomer mixture of take is benchmark as 100 parts (quality), 97 parts of methyl methacrylates, 3 parts of methyl acrylates, 0.003 part 2, two (4,4-di-t-butyl peroxide cyclohexyl) butane and the 0.2 part of tertiary lauryl mercaptan of 2-.
In material-compound tank and tundish, be filled with nitrogen, remove the oxygen of sneaking in monomer mixture solution, control oxygen level is wherein below 2ppm.With pump, in all mixed-type reactor through nitrogen replacement, add above raw material mixing solutions continuously.In all mixed-type reactor, temperature remains on 145 ℃.Remaining on mean residence time in this reactor is 1h, then polyblend is delivered in the straight tubular reactor of series connection with it by the toothed gear pump of all mixed-type reactor bottom, and the polymerization temperature in straight tubular reactor is 150 ℃.After mean residence time is 30 minutes, polymeric blends is sent into and in vented twin-screw extruder, carried out devolatilization separation, last extruding pelletization.In forcing machine, minute differing temps regional control temperature is within the scope of 200-230 ℃.The volatiles of collecting in a plurality of venting ports of forcing machine, carries out Separation and Recovery through recovery system, and the unreacted monomer obtaining is sent into recycle in material-compound tank.Polymkeric substance test result is listed in table 1.
Embodiment 2
Use the method identical with embodiment 1, in the composition of stock liquid, except two (4, the 4-di-t-butyl peroxide cyclohexyl) butane of 2,2-are increased to outside 0.006 part, other is identical with embodiment 1.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in table 1.
Embodiment 3
Use the method identical with embodiment 1, in the composition of stock liquid, comonomer is ethyl propenoate, and multifunctional initiator is that two (4,4-, bis-tert-pentyl peroxide cyclohexyl) the propane add-ons of 2,2-are 0.005 part, and other is identical with embodiment 1.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in table 1.
Embodiment 4
Use the method identical with embodiment 1, in the composition of stock liquid, except multifunctional initiator is that two (the tertiary octyl group peroxide of 4,4-bis-cyclohexyl) the propane add-ons of 2,2-are identical with embodiment 1 outside 0.005 part.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in table 1.
Embodiment 5
Use the method identical with embodiment 1, in the composition of stock liquid, the initiator adding is 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) mixture of two (4,4-, the bis-α-cumyl peroxide cyclohexyl) propane of butane and 2,2-, add-on is respectively 0.0025 part, and other component is identical with embodiment 1.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in table 1.
Comparative example 1
Use the method identical with embodiment 1, in the composition of stock liquid, except initiator is that two (t-butyl peroxy) hexanaphthene add-ons of 1,1-are identical with embodiment 1 outside 0.03 part.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in table 1.Result shows, although improved the add-on of this initiator, polymerisation conversion is lower, illustrates that the efficiency of initiation of this initiator is lower.
Comparative example 2
Use the method identical with embodiment 1, in the composition of stock liquid, comonomer is ethyl propenoate, and initiator is that peroxidized t-butyl perbenzoate add-on is 0.05 part, and other is identical with embodiment 1.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in table 1.Result shows, although improved the add-on of this initiator, polymerisation conversion is lower, illustrates that the efficiency of initiation of this initiator is lower.
As shown in Table 1, use the seldom multifunctional initiator of amount within the desirable time, to complete polyreaction, obtain the polymkeric substance with better performance, product transmittance is high, and glossiness is good, and has good processing fluidity.The value that the relative average molecular mass recording by GPC due to dendritic polymer records than the linear pattern polymkeric substance with molecular mass is little, and multiple angle laser light scattering instrument is measured, be absolute molecular mass, so Mw*/Mw has generated dendritic polymer much larger than 1 explanation.
Table 1
Wherein, I reactor is all mixed-type reactor
II reactor is straight tubular reactor
absolute molecular mass for polygonal determination of laser light scattering
A:2, two (4, the 4-di-t-butyl peroxide cyclohexyl) butane of 2-
B:2, two (4,4-, the bis-tert-pentyl peroxide cyclohexyl) propane of 2-
C:2, two (the tertiary octyl group peroxide of 4,4-bis-cyclohexyl) the propane D:2 of 2-, two (4,4-, the bis-α-cumyl peroxide cyclohexyl) propane of 2-
E:1, two (t-butyl peroxy) hexanaphthenes of 1-
F: peroxidized t-butyl perbenzoate
Claims (1)
1. a preparation method for branched structure (methyl) acrylic polymer moulding compound particle, is characterized in that: by nitrogen system, the oxygen level of dissolving in comonomer and agent mixture is down to below 2ppm; In all mixed-type reactor, supply with comonomer and agent mixture, initiator and chain-transfer agent continuously, polymerization temperature is controlled within the scope of 130-150 ℃, and control polymerisation conversion is 45-75%; The reaction mixture obtaining in all mixed-type reactor is sent into further polymerization in straight tubular reactor continuously, and temperature of reaction is controlled within the scope of 140-160 ℃, and controlling the final transformation efficiency of polymerization is 60-90%; By the polymkeric substance finally obtaining, deliver in vented twin-screw extruder, volatile matter is removed in separation continuously, finally by tablets press, makes moulding compound particle;
Described comonomer and agent mixture consist of alkyl methacrylate 90～98 weight parts and alkyl acrylate 2～10 weight parts;
Described initiator is 2,2-two (4,4-bis-tert-pentyl peroxide cyclohexyl) propane, 2, two (the tertiary octyl group peroxide of 4, the 4-bis-cyclohexyl) propane, 2 of 2-, 2-two (4,4-bis-α-cumyl peroxide cyclohexyl) propane, 2, two (4, the 4-di-t-butyl peroxide cyclohexyl) butane or 2 of 2-, two (the tertiary octyl group peroxide of 4, the 4-bis-cyclohexyl) butane of 2-; Take monomer mixture as 100 weight parts, and the weight of initiator is 0.0005～0.01 part;
Described chain-transfer agent is tertiary lauryl mercaptan, and weight is 0.2 part.
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| CN113461854A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | PMMA continuous bulk polymerization process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254650A (en) * | 1988-07-22 | 1993-10-19 | Kayaku Akzo Corporation | Process for the preparation of styrene or styrene derivative-containing copolymers |
| CN1576285A (en) * | 2003-07-08 | 2005-02-09 | 三菱丽阳株式会社 | Process for producing methacrylate polymer |
| CN101724120A (en) * | 2008-10-22 | 2010-06-09 | 中国石油天然气股份有限公司 | Preparation method of (methyl) acrylic polymer |
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| JP2923822B2 (en) * | 1992-08-26 | 1999-07-26 | キヤノン株式会社 | Electrophotographic carrier |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254650A (en) * | 1988-07-22 | 1993-10-19 | Kayaku Akzo Corporation | Process for the preparation of styrene or styrene derivative-containing copolymers |
| CN1576285A (en) * | 2003-07-08 | 2005-02-09 | 三菱丽阳株式会社 | Process for producing methacrylate polymer |
| CN101724120A (en) * | 2008-10-22 | 2010-06-09 | 中国石油天然气股份有限公司 | Preparation method of (methyl) acrylic polymer |
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| Title |
|---|
| JP特开平6-75435A 1994.03.18 |
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