CN1233674C - Continuous single-reactor prepn process of random styrene-cis-butenedioic anhydride copolymer - Google Patents
Continuous single-reactor prepn process of random styrene-cis-butenedioic anhydride copolymer Download PDFInfo
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- CN1233674C CN1233674C CN 02151174 CN02151174A CN1233674C CN 1233674 C CN1233674 C CN 1233674C CN 02151174 CN02151174 CN 02151174 CN 02151174 A CN02151174 A CN 02151174A CN 1233674 C CN1233674 C CN 1233674C
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Abstract
The present invention relates to a continuous single-reactor method for preparing styrene-maleic anhydride random polymers, which mainly solves the problems that when the content of maleic anhydride is low or high in styrene-maleic anhydride random polymers which are obtained in former technologies, the dispersion indexes of molecular weight are high, and flow is complicated and is hard to control. The present invention better solves the problems by adopting the technical scheme that at first, maleic anhydride is dissolved in part of styrene, then the dissolved maleic anhydride is added into a screw rod-diversion barrel type reactor where the rest of the styrene is thrown to polymerize for 1 to 10 hours, then the maleic anhydride solution which is dissolved in the styrene is added into the screw rod-diversion barrel type reactor with a certain speed, at the same time, the polymerization solution is led out with the same speed of charging, the stay time of raw material in the reactor is controlled for 1 to 20 hours, 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 continuous preparation method of single still of vinylbenzene-cis-butenedioic anhydride random copolymers.Particularly about the continuous preparation method of high molecular weight styrene-cis-butenedioic anhydride random copolymers.
Background technology
Vinylbenzene-cis-butenedioic anhydride multipolymer (SMA) is a kind of functional type multipolymer kind.Different along with cis-butenedioic anhydride in the multipolymer (MAH) content and molecular weight of copolymer and molecular weight distribution thereof, the performance of multipolymer is also different with purposes.Therefore, the control of cis-butenedioic anhydride content and molecular weight of copolymer and molecular weight distribution thereof is the critical technological point of vinylbenzene-cis-butenedioic anhydride copolymer in the multipolymer, and the stability of technological operation also is the prerequisite of multipolymer stability.
Yet the raising of cis-butenedioic anhydride content is subjected to the low and active higher restriction of multipolymer of cis-butenedioic anhydride solubleness in vinylbenzene in vinylbenzene-cis-butenedioic anhydride multipolymer; The control that molecular weight of copolymer distributes both had been subjected to the restriction of processing condition such as polymerization temperature or rate of polymerization and technology stability, also was subjected to the restriction of cis-butenedioic anhydride content in the multipolymer.Proposed a kind of continuous preparation technology of cis-butenedioic anhydride multipolymer among the EP27274, process characteristic is: adopt the vertical first still of band helical ribbon agitator to connect with the horizontal retort that needs the multiple spot continuous charging.Its technological 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 addition, the vertical first still of helical ribbon agitator is difficult to bear higher heat transfer load, thereby can only control lower rate of polymerization.
Introduced a kind of continous way operation bulk technique that contains the terpolymer of cis-butenedioic anhydride and vinyl aromatic monomer among the EP433711, process characteristic is: adopt the single vertical retort of band helical ribbon agitator, 104 ℃～127 ℃ of polymerization temperatures; Polymerization absolute pressure 50～90KPa.Cis-butenedioic anhydride adds reactor with molten state.The non-full still operation of this process using is removed heat by monomeric volatilization, and the problem that exists cis-butenedioic anhydride easily to enter vacuum system, corrosion and blocking pipeline is difficult to carry out mass-producing and moves continuously.
Adopt heterogeneous solution polymerization process synthetic vinylbenzene-cis-butenedioic anhydride alternating copolymer among the document CN91107516.X, though cis-butenedioic anhydride content can reach 30% (mole), the molecular weight dispersion index is wide to reach 5.0～10.0, and this method is periodical operation, polymerization temperature control inconvenience, polymerization efficiency is lower.
Summary of the invention
Technical problem to be solved by this invention is that the lower or cis-butenedioic anhydride content of vinylbenzene-cis-butenedioic anhydride multipolymer cis-butenedioic anhydride content of obtaining of conventional art is when high, the problem of molecular weight dispersion index height and flow process complexity, control difficulty provides a kind of continuous preparation method of single still of new vinylbenzene-cis-butenedioic anhydride multipolymer.The vinylbenzene that this method makes-cis-butenedioic anhydride multipolymer has cis-butenedioic anhydride content height, and molecular weight can reach high value simultaneously, and the molecular weight dispersion index is low, and technical process is simple, the characteristics of convenient operation and control.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the continuous preparation method of single still of a kind of vinylbenzene-cis-butenedioic anhydride random copolymers may further comprise the steps successively:
A) at first the cis-butenedioic anhydride of polymerization total monomer weight 5～15% is dissolved in polymerization by weight percentage with the vinylbenzene amount 20～90% in wiring solution-forming, then this solution is joined equably pre-the throwing in 10～80% the screw rod-water conservancy diversion cartridge reactor of polymerization by weight percentage with the vinylbenzene amount, in temperature of reaction is 80～150 ℃, is to carry out polymerization under 150～450KPa condition 1～10 hour with the absolute manometer reaction pressure;
B) then will be in advance the solution of the vinylbenzene of vinylbenzene 85～95% and cis-butenedioic anhydride 5～15% preparations by weight percentage and cis-butenedioic anhydride add equably in screw rod-water conservancy diversion cartridge reactor in the step a), draw polymer fluid with the identical flow of feed rate simultaneously and carry out the devolatilization separation, obtain even, transparent, slick vinylbenzene-cis-butenedioic anhydride random copolymerization composition granule, the residence time of raw material in screw rod-water conservancy diversion cartridge reactor is 1～20 hour.
In the technique scheme, the temperature of reaction preferable range is 110～140 ℃, is 250～450KPa with absolute manometer reaction pressure preferable range, and the residence time preferable range of raw material in screw rod-water conservancy diversion cartridge reactor is 1～5 hour.
The present invention finishes polymerization with single still technique of continuous bulk polymerization, and wherein crucial polymerization unit adopts band mixing, all good screw rod-water conservancy diversion cartridge type reactors of heat-transfer capability, band malleation, full still operation.Adopt semicontinuous start-up course and successive processes to finish polymerization, finish the separation of polymkeric substance with the vacuum process for devolatilization.
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 is owing to be dissolved in cis-butenedioic anhydride earlier in the part vinylbenzene, and then in the adding reactor with the residual styrene polymerization, make that cis-butenedioic anhydride content can reach 25% in the vinylbenzene-cis-butenedioic anhydride random copolymers that makes, molecular weight also can reach high value, can reach 250,000, and the molecular weight dispersion index is lower, only is 1.6～2.8.Because the present invention adopts screw rod-water conservancy diversion cartridge reactor list still operate continuously, can satisfy on the one hand the needs of mixings, heat transfer in addition, simplify operating process simultaneously, and operate more conveniently, obtain better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
Press at screw rod-10 liters of bands of water conservancy diversion cartridge type earlier and drop into 1870 gram vinylbenzene in (absolute pressure is 150KPa) reactor, be warming up to 110 ℃, the solution that will be made into by 1870 gram vinylbenzene and 375 gram cis-butenedioic anhydrides adds in the reactor equably with the flow of 675 Grams Per Hours again.After this solution feeds in raw material and finishes, switch to the solution that is made into than 1 gram cis-butenedioic anhydride by 10 gram vinylbenzene, and add reactor equably with the flow of 1500 Grams Per Hours, simultaneously the polymer fluid in the reactor is drawn 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 25.0% (mole), molecular weight are that 20.0 ten thousand (weight averages), molecular weight dispersion index are 2.6 in the gained multipolymer.
[embodiment 2]
Press at 10 liters of bands of screw rod-water conservancy diversion cartridge type and to drop into 3750 gram vinylbenzene in (absolute pressure is 200KPa) reactor earlier, be warming up to 80 ℃, the solution that will be made into by 3750 gram vinylbenzene and 750 gram cis-butenedioic anhydrides adds in the reactor equably with the flow of 1350 Grams Per Hours again.After this solution feeds in raw material and finishes, switch to the solution that is made into than 1 gram cis-butenedioic anhydride by 10 gram vinylbenzene, and add reactor equably with the flow of 500 Grams Per Hours, simultaneously the polymer fluid in the reactor is drawn 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 21.0% (mole), molecular weight are that 25.0 ten thousand (weight averages), molecular weight dispersion index are 2.8 in the gained multipolymer.
[embodiment 3]
Press at 10 liters of bands of screw rod-water conservancy diversion cartridge type and to drop into 3500 gram vinylbenzene in (absolute pressure is 250KPa) reactor earlier, be warming up to 140 ℃, the solution that will be made into by 4500 gram vinylbenzene and 300 gram cis-butenedioic anhydrides adds in the reactor equably with the flow of 4500 Grams Per Hours again.After this solution feeds in raw material and finishes, switch to the solution that is made into than 4.3 gram cis-butenedioic anhydrides by 80 gram vinylbenzene, and add reactor equably with the flow of 7500 Grams Per Hours, to answer polymer fluid in the still to draw simultaneously to carry out devolatilization to separate and extrude, aftertreatments such as cooling, pelletizing, obtain even, transparent copolymer pellet, measure by analysis, cis-butenedioic anhydride content is that 8.0% (mole), molecular weight are that 10.0 ten thousand (weight averages), molecular weight dispersion index are 1.6 in the gained multipolymer.
[embodiment 4]
Press 750 kilograms of vinylbenzene of elder generation's input in (absolute pressure is 350KPa) reactor at screw rod-2000 liters of bands of water conservancy diversion skeleton symbol, be warming up to 140 ℃, the solution that will be made into by 750 kilograms of vinylbenzene and 50 kilograms of cis-butenedioic anhydrides adds reactor equably with 300 kilograms/hour flow again, after this solution feeds in raw material and finishes, switch to the solution that is made into than 1 kilogram of cis-butenedioic anhydride by 15 kilograms of vinylbenzene, and add reactor equably with 650 kilograms/hour flow, to answer polymer fluid in the still to draw simultaneously to carry out devolatilization to separate and extrude, cooling, aftertreatments such as pelletizing, obtain evenly, transparent copolymer pellet, measure by analysis, cis-butenedioic anhydride content is 11.0% (mole) in the gained multipolymer, molecular weight is 14.0 ten thousand (weight averages), the molecular weight dispersion index is 2.0.
[embodiment 5]
Press 750 kilograms of vinylbenzene of elder generation's input in (absolute pressure is 450KPa) reactor at screw rod-2000 liters of bands of water conservancy diversion cartridge type, be warming up to 120 ℃, the solution that will be made into by 750 kilograms of vinylbenzene and 150 kilograms of cis-butenedioic anhydrides adds reactor equably with 350 kilograms/hour flow again, after this solution feeds in raw material and finishes, switch to the solution that is made into than 1 kilogram of cis-butenedioic anhydride by 10 kilograms of vinylbenzene, and add reactor equably with 650 kilograms/hour flow, to answer polymer fluid in the still to draw simultaneously to carry out devolatilization to separate and extrude, 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 15.0 ten thousand (weight averages), the molecular weight dispersion index is 2.0.
[comparative example 1]
In having 10 liters of reactors of helix agitator, drop into 1870 gram vinylbenzene, be warming up to 110 ℃, to add reactor equably with the flow of 675 Grams Per Hours by 1870 gram vinylbenzene and 375 solution that are made into of gram cis-butenedioic anhydrides again, 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 18.0 ten thousand (weight averages), the molecular weight dispersion index is 2.9.
[comparative example 2]
In having 10 liters of reactors of helix agitator, drop into 3750 gram vinylbenzene earlier, be warming up to 80 ℃, 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, after this solution feeds in raw material and finishes, switch to the solution that is made into than 1 gram cis-butenedioic anhydride by 10 gram vinylbenzene, and add reactor equably with the flow of 1500 Grams Per Hours, simultaneously the polymer fluid in the reactor is drawn and 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 17.0% (mole) in the gained multipolymer, molecular weight is 18.0 ten thousand (weight averages), the molecular weight dispersion index is 3.2.
[comparative example 3]
In having 10 liters of reactors of helix agitator, drop into 3500 gram vinylbenzene earlier, be warming up to 140 ℃, to add reactor equably with the flow of 4500 Grams Per Hours by 4500 gram vinylbenzene and 300 solution that are made into of gram cis-butenedioic anhydrides again, after this solution feeds in raw material and finishes, switch to the solution that is made into than 3 gram cis-butenedioic anhydrides by 80 gram vinylbenzene, and add reactor equably with the flow of 7500 Grams Per Hours, but reactor temperature runaway phenomenon appears, polymerization process is difficult to continue.Polymer fluid in the reactor can only be drawn carry out devolatilization separate and extrude, aftertreatments such as cooling, pelletizing, the copolymer pellet homogeneity, the transparency that obtain are all undesirable, measure by analysis, cis-butenedioic anhydride content is that 6.0% (mole), molecular weight are that 9.0 ten thousand (weight averages), molecular weight dispersion index are 2.6 in the gained multipolymer.
[embodiment 6～15]
Press each step of embodiment 1, just change raw material weight and form and reaction conditions, the results are shown in following table.
| Embodiment number | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| The reactor volume | 10 | 10 | 10 | 10 | 10 | 10 | 2000 | 2000 | 200 | 2000 |
| Vinylbenzene consumption % (weight) | 95 | 93 | 91 | 89 | 87 | 85 | 89 | 91 | 93 | 95 |
| Cis-butenedioic anhydride consumption % (weight) | 5 | 7 | 9 | 11 | 13 | 15 | 11 | 9 | 7 | 5 |
| Polymerization temperature (℃) | 90 | 115 | 100 | 80 | 110 | 150 | 115 | 120 | 130 | 140 |
| Polymerization time (hour) | 9.5 | 5.0 | 5.5 | 8.5 | 3.5 | 1.0 | 3.5 | 4.0 | 3.5 | 1.5 |
| Polymerization pressure (KPa) * 10 2 | 1.5 | 2.0 | 2.5 | 3.5 | 3.0 | 3.5 | 3.5 | 4.0 | 4.5 | 2.5 |
| MAH content (mole) among the SMA | 8 | 14 | 21 | 19 | 21 | 25 | 20 | 18 | 15 | 10 |
| SMA molecular weight (ten thousand) | 24 | 18 | 20 | 21 | 20 | 10 | 16 | 20 | 17 | 11 |
| The molecular weight dispersion index | 2.7 | 2.5 | 2.8 | 2.5 | 2.4 | 1.6 | 2.0 | 2.4 | 2.1 | 1.8 |
Claims (4)
1, the continuous preparation method of single still of a kind of vinylbenzene-cis-butenedioic anhydride random copolymers may further comprise the steps successively:
A) at first the cis-butenedioic anhydride of polymerization total monomer weight 5～15% is dissolved in polymerization by weight percentage with the vinylbenzene amount 20～90% in wiring solution-forming, then this solution is joined equably pre-the throwing in 10～80% the screw rod-water conservancy diversion cartridge reactor of polymerization by weight percentage with the vinylbenzene amount, in temperature of reaction is 80～150 ℃, is to carry out polymerization under 150～450KPa condition 1～10 hour with the absolute manometer reaction pressure;
B) then will be in advance the solution of the vinylbenzene of vinylbenzene 85～95% and cis-butenedioic anhydride 5～15% preparations by weight percentage and cis-butenedioic anhydride add equably in screw rod-water conservancy diversion cartridge reactor in the step a), draw polymer fluid with the identical flow of feed rate simultaneously and carry out the devolatilization separation, obtain even, transparent, slick vinylbenzene-cis-butenedioic anhydride random copolymerization composition granule, the residence time of raw material in screw rod-water conservancy diversion cartridge reactor is 1～20 hour.
2,, it is characterized in that temperature of reaction is 110～140 ℃ according to the continuous preparation method of single still of the described vinylbenzene of claim 1-cis-butenedioic anhydride random copolymers.
3,, it is characterized in that with the absolute manometer reaction pressure be 250～450KPa according to the continuous preparation method of single still of the described vinylbenzene of claim 1-cis-butenedioic anhydride random copolymers.
4,, it is characterized in that the residence time of raw material in screw rod-water conservancy diversion cartridge reactor is 1～5 hour according to the continuous preparation method of single still of the described vinylbenzene of claim 1-cis-butenedioic anhydride random copolymers.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02151174 CN1233674C (en) | 2002-12-11 | 2002-12-11 | Continuous single-reactor prepn process of random styrene-cis-butenedioic anhydride copolymer |
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| CN 02151174 CN1233674C (en) | 2002-12-11 | 2002-12-11 | Continuous single-reactor prepn process of random styrene-cis-butenedioic anhydride copolymer |
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| CN1233674C true CN1233674C (en) | 2005-12-28 |
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| CN 02151174 Expired - Lifetime CN1233674C (en) | 2002-12-11 | 2002-12-11 | Continuous single-reactor prepn process of random styrene-cis-butenedioic anhydride copolymer |
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Granted publication date: 20051228 |