CN1228357C - Polymerization process of random styrene-cis-butenedioic anhydride copolymer - Google Patents
Polymerization process of random styrene-cis-butenedioic anhydride copolymer Download PDFInfo
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- CN1228357C CN1228357C CN 02151173 CN02151173A CN1228357C CN 1228357 C CN1228357 C CN 1228357C CN 02151173 CN02151173 CN 02151173 CN 02151173 A CN02151173 A CN 02151173A CN 1228357 C CN1228357 C CN 1228357C
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- butenedioic anhydride
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Abstract
The present invention relates to a polymerization method of styrene-maleic anhydride random copolymers, which mainly solves the problem existing in former technologies that the dispersion indexes of molecular weights are high when the content of maleic anhydride in the obtained styrene-maleic anhydride random copolymers through polymerization is low or high. The present invention better solves the problem by adopting the technical scheme that maleic anhydride is dissolved in a solution which is prepared from part of styrene and part of low activity polymerization monomers, and then the dissolved maleic anhydride is added into the rest of the styrene and the rest of the low activity polymerization monomers to react, wherein the low activity polymerization monomers are chosen from at least one of acrylonitrile, methyl acrylate, ethyl acrylate, acrylic acid ethyl ester or methyl methacrylate, and the present invention can be used in the industrial production of styrene-maleic anhydride random copolymers.
Description
Technical field
The present invention relates to the polymerization process of vinylbenzene-cis-butenedioic anhydride random copolymers, particularly about the polymerization process of high cis-butenedioic anhydride content lower molecular weight dispersion index vinylbenzene-cis-butenedioic anhydride random copolymers.
Background technology
In macromolecule product, mol ratio is formed the vinylbenzene-cis-butenedioic anhydride alternating copolymer near 1: 1, because it absorbs water easily and is difficult to forming process and can not be used as thermoplastic material.It is a kind of easy function of processing type thermoplastic macromolecule material that the cis-butenedioic anhydride molar content is lower than vinylbenzene-cis-butenedioic anhydride random copolymers (R-SMA) of 30%.Along with the difference of cis-butenedioic anhydride in the multipolymer (MAH) content, the performance of multipolymer is also different with purposes, and especially along with the rising of cis-butenedioic anhydride content in the multipolymer, the performance and the purposes of multipolymer improve.In addition, along with the variation of molecular weight of copolymer and distribution thereof, the physical properties of multipolymer also changes, especially as macromolecular material, the following general who has surrendered of molecular weight of copolymer causes the difficulty and the problem of aspects such as material processing, processing and application, is difficult to be cut into rule particle etc. when extruding as material.Therefore, the vinylbenzene-cis-butenedioic anhydride random copolymers of the high cis-butenedioic anhydride content of the narrow distribution of acquisition high molecular is the major objective during vinylbenzene-cis-butenedioic anhydride random copolymers synthesizes.
Yet the raising of cis-butenedioic anhydride content is subjected to the lower restriction of cis-butenedioic anhydride solubleness in vinylbenzene in vinylbenzene-cis-butenedioic anhydride random copolymers; The raising of vinylbenzene-cis-butenedioic anhydride random copolymers molecular weight not only is subjected to the restriction of polymerization temperature or rate of polymerization raising, also is subjected to the restriction of cis-butenedioic anhydride content in the multipolymer.In EP27274, introduced the bulk polymerisation process of vinyl aromatic monomer random copolymers, its process is: at first will charge into first reactor by vinylbenzene and the cis-butenedioic anhydride mix monomer that polymerization theory is calculated, the postheating reactor is to the temperature of reaction of setting (80 ℃～160 ℃), add a certain amount of cis-butenedioic anhydride then in per 40 minutes or shorter interval, the styrene conversion rate reaches the preset value among 30%～60% in system.After rate to be transformed reaches and stablizes, the mix monomer that adds certain metering proportion rapidly, simultaneously the copolymer solution of equivalent is caused second and subsequently the 3rd reactor with first reactors in series, and divide cis-butenedioic anhydride monomers that multiple spot adds different amounts in second reactor and the 3rd reactor.This shows, this complex process, complex operation, the control difficulty is difficult to obtain vinylbenzene-cis-butenedioic anhydride random copolymers that cis-butenedioic anhydride content is higher than 20% (mole).In the document (CN91107516.X), adopt heterogeneous solution polymerization process synthetic vinylbenzene-cis-butenedioic anhydride alternating copolymer, cis-butenedioic anhydride content is higher than 30% (mole), reach 5.0～10.0 but the molecular weight dispersion index is wide, and shortcomings such as this method exists batch operation and polymerization temperature control inconvenience, and polymerization efficiency is low.
Summary of the invention
Technical problem to be solved by this invention is to overcome the high problem of molecular weight dispersion index when existing in vinylbenzene-cis-butenedioic anhydride multipolymer that polymerization obtains the lower or cis-butenedioic anhydride content of cis-butenedioic anhydride content high in the conventional art, and a kind of polymerization process of new vinylbenzene-cis-butenedioic anhydride random copolymers is provided.Vinylbenzene-cis-butenedioic anhydride the random copolymers that obtains with this method has cis-butenedioic anhydride content height, has the molecular weight height simultaneously, the characteristics that the molecular weight dispersion index is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the polymerization process of a kind of vinylbenzene-cis-butenedioic anhydride random copolymers may further comprise the steps:
A) cis-butenedioic anhydride of polymerization consumption is dissolved in the solution that the low activity polymerization single polymerization monomer of the vinylbenzene of polymerization consumption 10～80% and polymerization consumption 20～70% is made into and obtains mixed liquor A;
B) it is 110～160 ℃ in temperature of reaction, in the gauge pressure reaction pressure is under 50～450KPa condition, the mixed liquor A that obtains in a) step is joined the residue polymerization with weight phenylethylene with remain in the solution that polymerization consumption low activity polymerization single polymerization monomer is made into and carry out polyreaction, acquisition contains vinylbenzene 60～80% in molar percentage, the vinylbenzene of cis-butenedioic anhydride 19～30% and low activity polymerization single polymerization monomer 1～15%-cis-butenedioic anhydride random copolymers;
Wherein the low activity polymerization single polymerization monomer is selected from least a in vinyl cyanide, methyl acrylate, ethyl propenoate, n-butyl acrylate or the methyl methacrylate, and the molecular weight of vinylbenzene-cis-butenedioic anhydride random copolymers is 1.8 * 10
5～2.5 * 10
5, the molecular weight dispersion index is 1.8～3.0.
In the technique scheme, in molar percentage, low activity polymerization single polymerization monomer amount preferable range is 5～15% in vinylbenzene-cis-butenedioic anhydride random copolymers, and the temperature of reaction preferable range is 120～150 ℃, is 100～350KPa in gauge pressure reaction pressure preferable range.
The present invention introduces the 3rd component low activity polymerization single polymerization monomer by adopting in vinylbenzene and cis-butenedioic anhydride polymerization process, and cis-butenedioic anhydride is dissolved in earlier in the solution that part vinylbenzene and part low activity polymerization single polymerization monomer be made into, make cis-butenedioic anhydride can be fully, successfully be dissolved in the vinylbenzene, and above-mentioned mixed solution is added in residual styrene and the residue low activity polymerization single polymerization monomer.The inventor is unexpected to find that the vinylbenzene of acquisition-cis-butenedioic anhydride random copolymers has cis-butenedioic anhydride content height, can reach 19～30%, has the molecular weight of copolymer height simultaneously, can reach 1.8 * 10
5～2.5 * 10
5, and the molecular weight dispersion index is low, is 1.8～3.0 only, has obtained better technical effect.
The present invention adopts SA polymerization single polymerization monomer the 3rd component, and the technology controlling and process of polymerization process is become easily, has also brought convenience for the solids fraction cis-butenedioic anhydride under the normal temperature enters polymkeric substance.
The molecular weight of the multipolymer that the present invention mentioned and molecular weight distribution are measured by gel permeation chromatography (GPC) method.Cis-butenedioic anhydride content in the multipolymer is by the chemical titration analysis, utilizes the acid-base neutralisation reaction, is dissolved in anhydride group in the multipolymer of acetone with excessive alkali neutralization earlier, then with the sour alkali that comes the residual titration residual content.
The present invention only adopts single polymeric kettle to finish polymerization, and technical process is simple, and is easy to operate.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
In having 10 liters of reactors of helix agitator, drop into 1875 gram vinylbenzene and 125 gram n-butyl acrylates (BA) earlier, be warming up to 110 ℃, again will be by 1875 gram vinylbenzene, the solution that 300 gram cis-butenedioic anhydrides and 125 gram n-butyl acrylates are made into adds reactor equably with the flow of 675 Grams Per Hours, after solution feeds in raw material and finishes, the reaction terminating agent Resorcinol that adds 50 milliliter of 1% (weight) concentration finishes reaction, carrying out devolatilization then separates and extrudes, cooling, aftertreatments such as pelletizing, obtain evenly, transparent copolymer pellet, measure by analysis, cis-butenedioic anhydride content is 21.0% (mole) in the gained multipolymer, molecular weight is 23.0 ten thousand (weight averages), the molecular weight dispersion index is 2.7.
[embodiment 2]
In having 10 liters of reactors of helix agitator, drop into 3750 gram vinylbenzene and 250 gram n-butyl acrylates earlier, be warming up to 110 ℃, again will be by 3750 gram vinylbenzene, the solution that 750 gram cis-butenedioic anhydrides and 250 gram n-butyl acrylates are made into adds reactor equably with the flow of 1350 Grams Per Hours, after this solution feeds in raw material and finishes, polymer fluid in the reactor drawn carry out devolatilization and separate and extrude, cooling, aftertreatments such as pelletizing, obtain evenly, transparent copolymer pellet, measure by analysis, cis-butenedioic anhydride content is 26.0% (mole) in the gained multipolymer, molecular weight is 23.0 ten thousand (weight averages), the molecular weight dispersion index is 2.7.
[comparative example 1]
In having 10 liters of reactors of helix agitator, drop into 1875 gram vinylbenzene earlier, be warming up to 110 ℃, again will be by 1875 gram vinylbenzene, the solution that 300 gram cis-butenedioic anhydrides are made into adds reactor equably with the flow of 675 Grams Per Hours, after solution feeds in raw material and finishes, the reaction terminating agent Resorcinol that adds 50 milliliter of 1% (weight) concentration finishes reaction, carrying out devolatilization then separates and extrudes, cooling, aftertreatments such as pelletizing, obtain evenly, transparent copolymer pellet, measure by analysis, cis-butenedioic anhydride content is 19.0% (mole) in the gained multipolymer, molecular weight is 16.0 ten thousand (weight averages), the molecular weight dispersion index is 2.5.
[comparative example 2]
In having 10 liters of reactors of helix agitator, drop into 3750 gram vinylbenzene earlier, be warming up to 110 ℃, to add reactor equably with the flow of 1350 Grams Per Hours by 3750 gram vinylbenzene and 750 solution that are made into of gram cis-butenedioic anhydrides again, reaction is finished in the reinforced back that finishes of this solution, with the polymer fluid in the reactor draw carry out devolatilization separate and extrude, aftertreatments such as cooling, pelletizing, obtain even, transparent copolymer pellet, measure by analysis, cis-butenedioic anhydride content is that 19.0% (mole), molecular weight are that 16.0 ten thousand (weight averages), molecular weight dispersion index are 2.5 in the gained multipolymer.
[embodiment 3～12]
Press each step of embodiment 1, just change raw material weight and form and low activity polymerization single polymerization monomer kind, and processing condition, the results are shown in following table, wherein among the embodiment 11, the weight ratio of AN and BA is 1: 1, among the embodiment 12, the weight ratio of AN and MMA is 1: 1.
| Embodiment number | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 |
| Vinylbenzene consumption % (weight) | 88 | 81 | 65 | 89 | 75 | 75 | 89 | 65 | 75 | 75 |
| Cis-butenedioic anhydride consumption % (weight) | 10 | 10 | 10 | 10 | 15 | 15 | 10 | 20 | 10 | 10 |
| The 3rd amounts of components % (weight) | 2 | 9 | 15 | 1 | 10 | 0 | 1 | 15 | 15 | 15 |
| The 3rd component kind | AN | AN | AN | BA | BA | / | MMA | MMA | AN+BA | AN+MMA |
| Polymerization temperature (℃) | 115 | 115 | 115 | 120 | 110 | 110 | 115 | 110 | 110 | 110 |
| Polymerization time (hour) | 3.5 | 4.5 | 5.5 | 4.5 | 3.5 | 3.5 | 3.5 | 4.5 | 3.5 | 3.5 |
| MAH content % (mole) among the SMA | 21 | 21 | 21 | 19 | 26 | 19 | 20 | 30 | 23 | 24 |
| SMA molecular weight (ten thousand) | 19 | 23 | 26 | 19 | 23 | 16 | 18 | 25 | 22 | 23 |
| The molecular weight dispersion index | 2.5 | 2.5 | 3.0 | 2.5 | 2.7 | 2.5 | 2.7 | 2.8 | 2.7 | 2.5 |
Annotate: AN is a vinyl cyanide, and BA is a n-butyl acrylate, and MMA is a methyl methacrylate.
Claims (4)
1, the polymerization process of a kind of vinylbenzene-cis-butenedioic anhydride random copolymers may further comprise the steps:
A) cis-butenedioic anhydride of polymerization consumption is dissolved in the solution that the low activity polymerization single polymerization monomer of the vinylbenzene of polymerization consumption 10～80% and polymerization consumption 20～70% is made into and obtains mixed liquor A;
B) it is 110～160 ℃ in temperature of reaction, in the gauge pressure reaction pressure is under 50～450KPa condition, the mixed liquor A that obtains in a) step is joined the residue polymerization with weight phenylethylene with remain in the solution that polymerization consumption low activity polymerization single polymerization monomer is made into and carry out polyreaction, acquisition contains vinylbenzene 60～80% in molar percentage, the vinylbenzene of cis-butenedioic anhydride 19～30% and low activity polymerization single polymerization monomer 1～15%-cis-butenedioic anhydride random copolymers;
Wherein the low activity polymerization single polymerization monomer is selected from least a in vinyl cyanide, methyl acrylate, ethyl propenoate, n-butyl acrylate or the methyl methacrylate, and the molecular weight of vinylbenzene-cis-butenedioic anhydride random copolymers is 1.8 * 10
5～2.5 * 10
5, the molecular weight dispersion index is 1.8～3.0.
According to the polymerization process of the described vinylbenzene of claim 1-cis-butenedioic anhydride random copolymers, it is characterized in that 2, low activity polymerization single polymerization monomer amount is 5～15% in vinylbenzene-cis-butenedioic anhydride random copolymers in molar percentage.
3,, it is characterized in that temperature of reaction is 120～150 ℃ according to the polymerization process of the described vinylbenzene of claim 1-cis-butenedioic anhydride random copolymers.
4,, it is characterized in that in the gauge pressure reaction pressure be 100～350KPa according to the polymerization process of the described vinylbenzene of claim 1-cis-butenedioic anhydride random copolymers.
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| CN 02151173 CN1228357C (en) | 2002-12-11 | 2002-12-11 | Polymerization process of random styrene-cis-butenedioic anhydride copolymer |
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| CN1228357C true CN1228357C (en) | 2005-11-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4742647B2 (en) * | 2005-03-31 | 2011-08-10 | 住友化学株式会社 | Method for producing polar monomer-olefin copolymer |
| CN101220122B (en) * | 2008-01-30 | 2010-06-02 | 上海华明高技术（集团）有限公司 | Plastics toughening agent containing nano-calcium carbonate and polyalcohol, and method for producing the same |
| CN109021156A (en) * | 2018-07-25 | 2018-12-18 | 嘉兴华雯化工有限公司 | A kind of low yellowing styrene-acrylonitrile-copolymer-maleic anhydride and preparation method thereof |
| CN110724220A (en) * | 2019-10-15 | 2020-01-24 | 江苏科技大学 | Needle-shaped control agent and preparation method and application thereof |
| CN114085308B (en) * | 2021-12-24 | 2024-04-26 | 常熟世名化工科技有限公司 | Oleophylic styrene-maleic anhydride copolymer and preparation method and application thereof |
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