CN1211405C - Continuous preparation method of thermoplastic resin polymer - Google Patents
Continuous preparation method of thermoplastic resin polymer Download PDFInfo
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- CN1211405C CN1211405C CN 02111011 CN02111011A CN1211405C CN 1211405 C CN1211405 C CN 1211405C CN 02111011 CN02111011 CN 02111011 CN 02111011 A CN02111011 A CN 02111011A CN 1211405 C CN1211405 C CN 1211405C
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Abstract
The present invention relates to a continuous preparation method for a thermoplastic resin polymer, which mainly solves the problems of complex technology, special raw materials and low productive efficiency when the polymer is prepared by a polymerization method in the past literature. In the present invention, a method in which double-kettle continuous main bodies are polymerized is adopted, and that is to say styrene, rubber, partial maleic anhydride, parts of a butanone solvent and parts of an initiation agent are inducted into a first reaction kettle with an anchor type stirring paddle after being prepared into a solution, and the first reaction kettle flows out after the materials react for 2.5 to 4.5 hours at the temperature of 75 to 100 DEG C; a solution prepared from the residual maleic anhydride, the residual solvent, the residual initiation agent and an anti-oxidant and first reaction kettle effluent together enter a second reaction kettle with a screw rod-guide barrel or a double screw rod-anchor stirring paddle, the second reaction kettle flows out after the materials react for 2.5 to 5.5 hours at the reaction temperature of 80 to 130 DEG C, and a thermoplastic resin polymer product can be obtained by devolatilization. The problems are well solved by the technical scheme, and the present invention can be used for industrial production of thermoplastic resin.
Description
Technical field
The present invention relates to the continuous preparation method of thermoplastic resin polymer, the continuous preparation method of the particularly good and thermoplastic resin polymer that shock resistance is good about resistance toheat.
Background technology
R-SMA (being called for short SMA) is the random copolymers of vinylbenzene (St) and maleic anhydride (MA), wherein anti-impact level SMA is a crucial kind in this series, it had both kept higher thermotolerance, consistency and the processing characteristics of transparent stage SMA (binary), carry out the fragility that graft copolymerization has overcome binary SMA owing to introducing rubber again, thereby have good market outlook.Anti-impact level SMA compares with binary SMA, owing to introduced rubber in the polymerization, has brought the new problems such as variation of transformation mutually, graft reaction and system viscosity, so reaction mechanism and polymerization technique are all more complex.
About the research work that changes mutually, be reported in 20th century 60, the seventies more, mainly be at HIPS synthetic in St-PB binary batchwise polymerization system, multicomponent system or the research work of transformation mutually that more approaches actual other feed way (as semicontinuous, the continuous) system of industry be report not almost.Research report or patent for anti-impact level SMA generally are to carry out body or solution polymerization under semicontinuous condition, study the relation between processing condition and the product performance.
Solution method has advantages such as steady, the easy control of polymerization, but owing to increased the recovery sepn process of solvent, the aftertreatment more complicated, usage ratio of equipment is low; And substance law has the plant factor height, advantages such as technology is simple, be the main flow technology of high-impact polystyrene (HIPS) and binary RSMA production of resins always, but because the copolymerization heat between St-MAH is bigger, and the adding of rubber will cause the increase of system viscosity, make the heat transfer of reaction and mix difficulty more, simultaneously because the solubleness of MAH in vinylbenzene is limited, the adding of rubber reduces the vinylbenzene of dissolving MAH, thereby causes the MAH content of product to reduce, and thermotolerance descends.For overcoming above shortcoming, improve product quality and production efficiency, the present invention will adopt few solvent bulk polymerization.
Successive polymerization has stable operation, characteristics that production efficiency is high, the most successive polymerization modes that adopt of the production of polymkeric substance at present, and therefore, the present invention adopts the continuous bulk polymerization process of few solvent, and being intended to provides foundation for scale operation.
Because graft copolymerization technology has a phase transition process, add that the polymerization system viscosity front and back alter a great deal, and should have staged reactor could satisfy these requirements.External relevant anti-impact level SMA continuous processing synthetic data seldom, be typically the USP3919354 (with the resemble process of PEP report description) of DOW company, this process using be typical low temperature slow reaction, SBR makes the toughness reinforcing glue of using, MEK (butanone) makes solvent, the series connection of three stills, temperature raises gradually, nearly 24 hours of total residence time, the structure of reactor is not described, if reaction efficiency is in kilogram/hour rise, have only 0.027 kilogram/hour and rise (calculating) by USP3919354,0.016 kilogram/hour rise (press the technology that PEP234 reports description).Idemitsu company has all adopted the placed in-line method of two stills at USP4732924 and Daicel company in JP60031514, but its patent main points all are the adding mode of outstanding rubber or the use of specialty elastomer and additive.
HIPS mostly adopts the production of many still series connection continuous processings.Generally, first reactor is the grafting still, and second reactor is the phase inversion still, and the 3rd (four) still further improves transformation efficiency, alleviating the devolatilization burden, and improves productivity ratio.To form uniform anti-impact level SMA resin in order preparing, must all to add MAH continuously at each still, this is the key difference of anti-impact type SMA production technique and traditional HIPS production technique.
Summary of the invention
Technical problem to be solved by this invention be the singularity of the complicacy that overcomes in the above-mentioned document technical process when adopting continuous processing to prepare anti-impact level SMA, toughner and production efficiency low problem, a kind of continuous preparation method of new thermoplastic resin polymer is provided.This method has that technical process is simple, and raw material is easy to get, and cost is low, the characteristics that production efficiency is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of continuous preparation method of thermoplastic resin polymer may further comprise the steps successively:
A) with rubber, single alkyl alkenyl arene monomer, account for 50～70% unsaturated dicarboxylic acid acid anhydrides of unsaturated dicarboxylic acid acid anhydrides gross weight, import first reactor that has anchor formula stirring rake after accounting for 70～90% butanone of solvent butanone gross weight and accounting for 35～65% initiator wiring solution-forming of initiator gross weight, under 75～100 ℃ of conditions of temperature of reaction, residence time of raw material is to flow out first reactor after 2.5～4.5 hours, wherein the consumption of rubber is thermoplastic resin amount's 5～25% by weight percentage, the consumption of single alkyl alkenyl arene is 60～90% of a thermoplastic resin consumption, the gross weight of unsaturated dicarboxylic acid acid anhydrides is 5～25% of a thermoplastic resin consumption, the gross weight of solvent butanone is 15～45% of single alkyl alkenyl arene monomer weight, initiator is 0.01～0.5% of single alkyl alkenyl arene monomer weight, and initiator is selected from superoxide or azo-compound;
B) with remaining unsaturated dicarboxylic acid acid anhydrides, remaining solvent butanone, remaining initiator and oxidation inhibitor 2,6-di-tert-butyl-4-methylphenol wiring solution-forming enters second reactor of band screw rod-guide shell or two ribbon-anchor stirring rake with the effluent of first reactor, in temperature of reaction is under 80～130 ℃ of conditions, residence time of raw material is to flow out second reactor after 2.5～5.5 hours, wherein oxidation inhibitor 2, and the consumption of 6-di-tert-butyl-4-methylphenol is 0.1～0.8% of single alkyl alkenyl arene monomer weight;
C) the second reactor effluent gets the thermoplastic resin polymer product after devolatilization.
The preferred version of single alkyl alkenyl arene is vinylbenzene or alpha-methyl styrene in the technique scheme, unsaturated dicarboxylic acid acid anhydrides preferred version is a maleic anhydride, the rubber preferred version is made up of cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR), and wherein cis-1,4-polybutadiene rubber is 20～80% of a rubber total amount by weight percentage.The raw material preferred version of first reactor is earlier rubber to be dissolved in the vinylbenzene, and maleic anhydride and initiator are dissolved in the solvent butanone, then these two portions is mixed the back and imports first reactor.The superoxide preferred version is for being selected from benzoyl peroxide or dicumyl peroxide, and the azo-compound preferred version is a Diisopropyl azodicarboxylate.
Used vinylbenzene, maleic anhydride, butanone etc. are technical grade product among the present invention, rubber can be cis-butadiene cement (high along glue, in along glue or low along glue), butadiene-styrene rubber (different styrene content) or its gum blend, initiator can be a peroxide, as dibenzoyl peroxide (BPO), dicumyl peroxide (DCP) etc., also can be the azo class, as Diisopropyl azodicarboxylate (AIBN) or their compound.Processing condition need be made less adjustment according to the kind or different of the content of rubber and initiator.
Except said components, additives such as oxidation inhibitor also are essential, and as 2,6-di-tert-butyl 4-methylphenol (264) etc. also can add processing fluidity, erosion-resisting characteristics and surface gloss etc. that white oil, silicone oil etc. increase product.
The present invention is owing to only adopt two still continuous processings, so technical process is simple, and equipment cost is low.Used raw material is technical grade product, and is product commonly used, inexpensive, so production cost is lower, and raw material is easy to get.In the bulk polymerization of two still series connection improvement that the present invention adopts, first reactor adopts anchor formula stirring rake, as grafting phase inversion still, second reactor is selected screw rod-guide shell or two ribbon-anchor agitator respectively for use according to the requirement of mass transfer and heat transfer, established rubber particles can be stablized on the one hand, transformation efficiency can be improved on the other hand.Adopt rubber and vinylbenzene all to add from first reactor, the mode that maleic anhydride, butanone solvent and initiator two stills add respectively can further improve transformation efficiency, helps the carrying out that reacts, thereby improve polymerization efficiency and enhance productivity, obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
The unloading phase of semicontinuous:
Earlier the high suitable glue PB (Yanshan Mountain BR9004) of 425 grams is dissolved in 3825 gram vinylbenzene and the 1200 gram butanone, glue after the dissolving adds in first reactor, add initiator B PO 0.61 gram that is dissolved in 100 gram butanone after waiting to rise to temperature of reaction, carry out adding of maleic anhydride solution then, 720 gram maleic anhydrides+1080 gram butanone+1.9 that are formulated as of adding liquid restrain BPO, reaction was carried out 6 hours altogether, temperature of reaction remains on 91 ℃, the speed of adding is 240 Grams Per Hours, mixing speed was 220 rev/mins in preceding 3 hours, and mixing speed was 90 rev/mins in back 3 hours.
Two still successive stage:
First still adopts anchor formula stirring rake, and volume is 7.65 liters, and second still adopts two ribbons-anchor agitator, and volume is 9.33 liters.First still feed composition comprises following component: PB 7.35% by weight percentage, St (vinylbenzene) 66.15%, and MA 5.25%, MEK (butanone) 21.25%, BPO 0.035%, and the speed of adding is 2000 Grams Per Hours, temperature of reaction is 92 ℃, and stirring velocity is 160 rev/mins; The second still feed composition comprises following component: MA (maleic anhydride) 33.33% by weight percentage, MEK66.67%, BPO 0.298%, antioxidant 264 (2,6-di-tert-butyl 4-methylphenol) 1.12%, the speed of adding is 285 Grams Per Hours, and temperature of reaction is 100 ℃, and stirring velocity is 70 rev/mins.Online mode is adopted in devolatilization, carries out continuous devolatilization granulation with the exhaust twin screw extruder.The gained resin property sees Table 1.
[embodiment 2]
The unloading phase of semicontinuous:
Earlier high suitable glue PB (Yanshan Mountain BR9004) of 384 grams and 16 gram maleic anhydrides are dissolved in the 4800 gram vinylbenzene, glue after the dissolving adds in first reactor, carry out adding of maleic anhydride solution after waiting to rise to temperature of reaction, 196 gram maleic anhydrides+549 gram butanone+1.03 that are formulated as of adding liquid restrain BPO, reaction was carried out 4 hours altogether, and temperature of reaction remains on 97 ℃, and the speed of adding is 750 Grams Per Hours, mixing speed was 220 rev/mins in preceding 2 hours, and mixing speed was 90 rev/mins in back 2 hours.
Two still successive stage:
First still adopts anchor formula stirring rake, and volume is 8.50 liters, and second still adopts screw rod-guide shell to stir, and volume is 8.86 liters.First still feed composition comprises following component PB 6.87% by weight percentage, and St 55.2%, and MA 5.31%, and MEK 32.8%, and BPO 0.0706%, and the speed of adding is 3000 Grams Per Hours, and temperature of reaction is 90 ℃, and stirring velocity is 220 rev/mins; The second still feed composition comprises following component MA 33.33% by weight percentage, and MEK 66.67%, and BPO 0.298%, oxidation inhibitor 1.42%, form and to comprise following component by weight percentage to add speed be 450 Grams Per Hours, temperature of reaction is 85 ℃, and stirring velocity is 70 rev/mins.Devolatilization and properties of sample are measured with embodiment 1.The gained resin property sees Table 1.
[comparative example 1]
The reactor condition is identical with embodiment 2 with input speed and composition etc., and first still temperature of reaction is 90 ℃, and mixing speed is 180 rev/mins, and the second still temperature of reaction is 88 ℃, and mixing speed is 70 rev/mins, and devolatilization and properties of sample are measured with embodiment 1.The gained resin property sees Table 1.
Table 1 couple still long run test result
| Sequence number | Temperature of reaction ℃ | Mixing speed rev/min | Add the speed Grams Per Hour | Residence time hour | Tensile strength MPa | Modulus in flexure MPa | Shock strength Jiao/rice | Vicat ℃ | Final solid content % | The polymerization efficiency kilogram/hour. rise | ||||
| Embodiment 1 | 92 | 100 | 160 | 70 | 2000 | 285 | 3.6 | 3.8 | 36.2 | 2117 | 114.1 | 131 | 52.77 | 7.10 |
| Embodiment 2 | 90 | 85 | 220 | 70 | 3000 | 450 | 2.7 | 2.4 | 34.9 | 2020 | 72.2 | 143.6 | 49.12 | 9.76 |
| Comparative example 1 | 90 | 88 | 180 | 70 | 3000 | 450 | 2.7 | 2.4 | 33.8 | 1712 | 70.6 | 141 | 50.67 | 10.37 |
| Testing standard | GB/T1040 | GB/T9341 | GB/T1843 | GB/T1633 | ||||||||||
Claims (6)
1, a kind of continuous preparation method of thermoplastic resin polymer may further comprise the steps successively:
A) with rubber, single alkyl alkenyl arene monomer, account for 50～70% unsaturated dicarboxylic acid acid anhydrides of unsaturated dicarboxylic acid acid anhydrides gross weight, import first reactor that has anchor formula stirring rake after accounting for 70～90% butanone of solvent butanone gross weight and accounting for 35～65% initiator wiring solution-forming of initiator gross weight, under 75～100 ℃ of conditions of temperature of reaction, residence time of raw material is to flow out first reactor after 2.5～4.5 hours, wherein the consumption of rubber is thermoplastic resin amount's 5～25% by weight percentage, the consumption of single alkyl alkenyl arene is 60～90% of a thermoplastic resin consumption, the gross weight of unsaturated dicarboxylic acid acid anhydrides is 5～25% of a thermoplastic resin consumption, the gross weight of solvent butanone is 15～45% of single alkyl alkenyl arene monomer weight, initiator is 0.01～0.5% of single alkyl alkenyl arene monomer weight, and initiator is selected from superoxide or azo-compound;
B) with remaining unsaturated dicarboxylic acid acid anhydrides, remaining solvent butanone, remaining initiator and oxidation inhibitor 2,6-di-tert-butyl-4-methylphenol wiring solution-forming enters second reactor of band screw rod-guide shell or two ribbon-anchor stirring rake with the effluent of first reactor, in temperature of reaction is under 80～130 ℃ of conditions, residence time of raw material is to flow out second reactor after 2.5～5.5 hours, wherein oxidation inhibitor 2, and the consumption of 6-di-tert-butyl-4-methylphenol is 0.1～0.8% of single alkyl alkenyl arene monomer weight;
C) the second reactor effluent gets the thermoplastic resin polymer product after devolatilization.
2,, it is characterized in that single alkyl alkenyl arene is vinylbenzene or alpha-methyl styrene according to the continuous preparation method of the described thermoplastic resin polymer of claim 1.
3,, it is characterized in that the unsaturated dicarboxylic acid acid anhydrides is a maleic anhydride according to the continuous preparation method of the described thermoplastic resin polymer of claim 1.
4, according to the continuous preparation method of the described thermoplastic resin polymer of claim 1, it is characterized in that rubber is made up of cis-1,4-polybutadiene rubber and styrene-butadiene rubber(SBR), wherein cis-1,4-polybutadiene rubber is 20～80% of a rubber total amount by weight percentage.
5, according to the continuous preparation method of the described thermoplastic resin polymer of claim 1, the raw material that it is characterized in that first reactor is earlier rubber to be dissolved in the vinylbenzene, maleic anhydride and initiator are dissolved in the solvent butanone, then these two portions are mixed the back and import first reactor.
6, according to the continuous preparation method of the described thermoplastic resin polymer of claim 1, it is characterized in that superoxide is benzoyl peroxide or dicumyl peroxide, azo-compound is a Diisopropyl azodicarboxylate.
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| CN 02111011 CN1211405C (en) | 2002-03-13 | 2002-03-13 | Continuous preparation method of thermoplastic resin polymer |
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| CN 02111011 CN1211405C (en) | 2002-03-13 | 2002-03-13 | Continuous preparation method of thermoplastic resin polymer |
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| CN1211405C true CN1211405C (en) | 2005-07-20 |
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