CN102850481A - Preparation method for branched-structure (methyl) acrylate polymer - Google Patents
Preparation method for branched-structure (methyl) acrylate polymer Download PDFInfo
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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 excellent performances such as 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 the automobile industry in field of electronics, (methyl) acrylic polymer shows many superiority.
In the course of processing, to have preferably physical strength after the moulding when requiring resin to have high workability.In order to satisfy these requirements, researchist has in the past proposed to reduce the molecular weight of polymkeric substance or has adopted the suitable schemes such as comonomer.But when molecular weight is reduced to a certain degree, the problem that physical strength or solvent resistance descend appears; In the method that adopts comonomer, when the interpolymer component concentration acquired a certain degree, degradation problem under second-order transition temperature decline, the thermal denaturation temperature appearred 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, wherein only is mentioned to polyfunctional monomer.But above-mentioned two kinds of methods all adopt suspension polymerization.Adopt suspension polymerization to prepare the method for acrylic resin, have in process of production lot of advantages, but be subjected to the impact of the employed dispersion stabilizer of suspension polymerization, there is fatal problem in the optical characteristics of product.And when 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 prepares the branched structure polymkeric substance.But need desolventizing when adopting the method, not only facility investment is high, and resistance toheat also descends 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 preparation acrylic resin.It is that the monomer of principal constituent is injected into the method that complete mixed type reactor carries out mass polymerization that Japanese patent application publication No. 2003-96105 proposes methyl methacrylate.The 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 control initiator, reactor pressure condition etc.Simultaneously, 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 purpose of this invention is to provide and have the method for branched structure (methyl) acrylic polymer a kind of the preparation 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, have higher efficiency of initiation, when having improved polymerization rate, can also obtain to have the polymkeric substance of 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, finish polyreaction, reduce the residual impact on the polymkeric substance color and luster of initiator.In addition, dendritic polymer has the simple linear polymer of same molecular amount relatively with it, and the molecular coil size is little, and is little with the intersegmental winding degree of chain in the 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 the high temperature continuous bulk polymerization, by introduce the 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 the agent mixture is down to below the 2ppm; Supply with comonomer and agent mixture, polyfunctional group radical initiator and chain-transfer agent continuously in all mixed-type reactor, polymerization temperature is controlled in 130-150 ℃, and the control polymerisation conversion is 45-75%; The reaction mixture that obtains in all mixed-type reactor is sent into further polymerization in the straight tubular reactor continuously, and temperature of reaction is controlled in the 140-160 ℃ of scope, and the final transformation efficiency of control polymerization is 60-90%; With the polymkeric substance that finally obtains, deliver in the vented twin-screw extruder, separate continuously and remove volatile matter, make the moulding compound particle by tablets press at last.
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 to have carbonatoms and be (methyl) alkyl acrylate of the alkyl of 1-8, such 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.Polymerization is carried out in this patent selection take methyl methacrylate as main monomer.The aforesaid propylene acid alkyl ester can be exemplified as methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid 2-ethyl pentyl ester etc., or their mixture more than 2 kinds.Preferred methyl acrylate and ethyl propenoate.
The polyfunctional group radical initiator of adding of the present invention is that the transformation period under polymerization temperature is about 1～10 minute radical initiator.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.
Polyfunctional group radical initiator with said structure formula comprises: 2,2-two (4,4-two tert-pentyl peroxide cyclohexyl) propane, 2, two (4,4-, the two uncle's octyl group peroxide cyclohexyl) propane, 2 of 2-, 2-two (4,4-two α-cumyl peroxide cyclohexyl) propane, 2, two (4, the 4-di-t-butyl peroxide cyclohexyl) butane, 2 of 2-, two (4,4-, two uncle's octyl group peroxide cyclohexyl) butane of 2-etc.Above initiator can use separately, also can use with other initiator.
Among the preparation method of the present invention, take monomer mixture as 100 parts (weight) as benchmark, the amount of above-mentioned polyfunctional group radical initiator is 0.0005～0.01 part (weight).
Described chain-transfer agent is uncle's 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 in the 3-15g/10min scope.
Polymerization temperature is controlled in 130-160 ℃ the high temperature range.When polymerization temperature was lower than 130 ℃, rate of polymerization was low, and the residence time is long.And along with the carrying out of reaction, system viscosity increases gradually, can't carry out stable polyreaction, causes final transformation efficiency to reduce.When polymerization temperature was higher than 160 ℃, system viscosity can significantly reduce, although this is conducive to stable operation, easily generate a large amount of oligopolymer in the polymerization system this moment, and the molecular weight distribution of polymkeric substance broadens, and causes mechanical property and optical property to descend.
This patent has proposed a kind of method that has than (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 the processing shearing condition is good.
Embodiment
The polymkeric substance that obtains 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 the 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
Add two (4,4-di-t-butyl peroxide cyclohexyl) butane and the chain-transfer agent uncle lauryl mercaptans of 2,2-in methyl methacrylate and methyl acrylate mixture, above raw material is mixed in proportion.The mixture feed composition: take monomer mixture as 100 parts (quality) as benchmark, 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 uncle's lauryl mercaptan of 2-.
Be filled with nitrogen in material-compound tank and tundish, remove the oxygen of sneaking in the monomer mixture solution, control oxygen level wherein is below 2ppm.With pump continuously in all mixed-type reactor of nitrogen replacement, adding above raw material mixing solutions.Temperature remains on 145 ℃ in all mixed-type reactor.Remaining on the interior mean residence time of this reactor is 1h, and the toothed gear pump by all mixed-type reactor bottom is delivered to polyblend in the straight tubular reactor of series connection with it again, and the polymerization temperature in the straight tubular reactor is 150 ℃.After mean residence time is 30 minutes, polymeric blends is sent into carry out devolatilization in the vented twin-screw extruder and separate last extruding pelletization.Minute differing temps regional control temperature is in 200-230 ℃ of scope in the forcing machine.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 that obtains is sent into recycle in the material-compound tank.The polymkeric substance test result is listed in the table 1.
Embodiment 2
Use the method identical with embodiment 1, in the composition of stock liquid, except 2,2-pair of (4,4-di-t-butyl peroxide cyclohexyl) butane 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 the table 1.
Embodiment 3
Use the method identical with embodiment 1, comonomer is ethyl propenoate in the composition of stock liquid, and multifunctional initiator is that 2,2-pair of (4,4-, two tert-pentyl peroxide cyclohexyl) propane add-ons are 0.005 part, and other is identical with embodiment 1.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in the table 1.
Embodiment 4
Use the method identical with embodiment 1, in the composition of stock liquid, except multifunctional initiator is that 2,2-pair of (4,4-, two uncle's octyl group peroxide cyclohexyl) propane add-ons are identical with embodiment 1 outside 0.005 part.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in the table 1.
Embodiment 5
Use the method identical with embodiment 1, in the composition of stock liquid, the initiator that adds is 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) mixture of two (4,4-, the two 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 the table 1.
Comparative example 1
Use the method identical with embodiment 1, in the composition of stock liquid, except initiator is that 1,1-pair of (t-butyl peroxy) hexanaphthene add-ons are identical with embodiment 1 outside 0.03 part.Concrete converging operationJu Hecaozuo condition and polymkeric substance test result are listed in the table 1.The 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, comonomer is ethyl propenoate in the composition of stock liquid, and initiator is that the 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 the table 1.The 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 multifunctional initiator of seldom measuring within the desirable time, to finish polyreaction, the polymkeric substance that acquisition has better performance, the product transmittance is high, and glossiness is good, and has good processing fluidity.Because dendritic polymer is less than the value that the linear pattern polymkeric substance with molecular mass records by the relative average molecular mass that GPC records, absolute molecular mass and the multiple angle laser light scattering instrument is measured, so Mw*/Mw has generated dendritic polymer much larger than 1 explanation.
Table 1
Wherein, the I reactor is all mixed-type reactor
The II reactor is straight tubular reactor
A:2, two (4, the 4-di-t-butyl peroxide cyclohexyl) butane of 2-
B:2, two (4,4-, the two tert-pentyl peroxide cyclohexyl) propane of 2-
C:2, two (4,4-, two uncle's octyl group peroxide cyclohexyl) the propane D:2 of 2-, two (4,4-, the two α-cumyl peroxide cyclohexyl) propane of 2-
E:1, two (t-butyl peroxy) hexanaphthenes of 1-
F: peroxidized t-butyl perbenzoate
Claims (1)
1. the preparation method of a branched structure (methyl) acrylic polymer is characterized in that: by nitrogen system the oxygen level of dissolving in comonomer and the agent mixture is down to below the 2ppm; Supply with comonomer and agent mixture, initiator and chain-transfer agent continuously in all mixed-type reactor, polymerization temperature is controlled in the 130-150 ℃ of scope, and the control polymerisation conversion is 45-75%; The reaction mixture that obtains in all mixed-type reactor is sent into further polymerization in the straight tubular reactor continuously, and temperature of reaction is controlled in the 140-160 ℃ of scope, and the final transformation efficiency of control polymerization is 60-90%; With the polymkeric substance that finally obtains, deliver in the vented twin-screw extruder, separate continuously and remove volatile matter, make the moulding compound particle by tablets press at last;
Described comonomer and agent mixture are made of alkyl methacrylate 90～98 weight parts and alkyl acrylate 2～10 weight parts;
Described initiator is 2,2-two (4,4-two tert-pentyl peroxide cyclohexyl) propane, 2, two (4,4-, the two uncle's octyl group peroxide cyclohexyl) propane, 2 of 2-, 2-two (4,4-two α-cumyl peroxide cyclohexyl) propane, 2, two (4, the 4-di-t-butyl peroxide cyclohexyl) butane or 2 of 2-, two (4,4-, the two uncle's octyl group peroxide cyclohexyl) butane of 2-; Take monomer mixture as 100 weight parts, the weight of initiator is 0.0005～0.01 part;
Described chain-transfer agent is uncle's lauryl mercaptan, and weight is 0.2 part.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311726A (en) * | 2014-10-30 | 2015-01-28 | 中国科学院化学研究所 | Method for preparing solid acrylic resin |
| CN112707993A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Styrene- (methyl) acrylate copolymer, preparation method and application |
| 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 |
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| 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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Patent Citations (4)
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| US5254650A (en) * | 1988-07-22 | 1993-10-19 | Kayaku Akzo Corporation | Process for the preparation of styrene or styrene derivative-containing copolymers |
| JPH0675435A (en) * | 1992-08-26 | 1994-03-18 | Canon Inc | Electrophotographic carrier |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104311726A (en) * | 2014-10-30 | 2015-01-28 | 中国科学院化学研究所 | Method for preparing solid acrylic resin |
| CN112707993A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Styrene- (methyl) acrylate copolymer, preparation method and application |
| 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 |
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