CN101475674A - Preparation of phenylethylene-dialkene special copolymer - Google Patents
Preparation of phenylethylene-dialkene special copolymer Download PDFInfo
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- CN101475674A CN101475674A CNA2009100954678A CN200910095467A CN101475674A CN 101475674 A CN101475674 A CN 101475674A CN A2009100954678 A CNA2009100954678 A CN A2009100954678A CN 200910095467 A CN200910095467 A CN 200910095467A CN 101475674 A CN101475674 A CN 101475674A
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Abstract
The invention discloses a preparation method for a styrene-diolefin special copolymer. The preparation method comprises the following steps: taking a styrene-diolefin block random copolymer as PS-PB-PB/PS-PS; wherein PS representing a styrene copolymer block, PB representing a diolefin copolymer block, and PB/PS representing a styrene-diolefin random copolymer block; and adopting an anionic continuous polymerization method. The preparation method avoids the defects of a batch still and is characterized by low production cost, short production cycle, low operating cost, short reaction time and high yield.
Description
Technical field
The present invention relates to a kind of preparation method of phenylethylene-dialkene special copolymer.
Background technology
Phenylethylene resin series is one of five big universal synthetic resins, generally is only second to PE, PVC and PP by output and occupies the 4th.Polystyrene (PS), nineteen twenty-five, Germany I.G.Farben industrial took to cinnamic industrial production development, and nineteen thirty is realized suitability for industrialized production.China began to prepare production equipment in 1958, had started the industrial production of Chinese polystyrene resin.The phenylethylene resin series early stage of development, only produce general purpose polystyrene.Its matter is hard and crisp, physical strength is not high, thermotolerance is relatively poor, and inflammable.People have done a large amount of improvements for this reason, and having formed with high-impact polystyrene (HIPS), Expandable Polystyrene (EPS) (EPS), styrene-butadiene copolymer (K-Resin) etc. is the huge styrene resin resin system of representative.
The batch still formula that the is production technique that the phenylethylene-dialkene multipolymer adopts both at home and abroad at present in the phenylethylene resin series.This technological operation is flexible, be easy to adapt to different operating condition and range of product, be applicable to the products production that short run, many kinds, reaction times are long, but batch still formula production technique, non-productive operations such as charging and discharging need be arranged, and quality product also is difficult for stable, and facility investment is big, production cycle is long, overall operation cost height.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of phenylethylene-dialkene special copolymer, this method has been avoided the shortcoming of batch still, and it is low, with short production cycle to have a production cost, and running cost is low, and the reaction times is short, the characteristics that output is big.
In order to achieve the above object, technical scheme of the present invention is:
A kind of preparation method of phenylethylene-dialkene special copolymer, comprise the steps: that phenylethylene-dialkene special copolymer molecular structure is PS-PB-PB/PS-PS, wherein PS is a polystyrene block, and PB is the polydiolefin block, and PB/PS is the phenylethylene-dialkene block of random copolymer.The molecular weight of this kind polymkeric substance is 80000-800000, and the phase farmland that the PB block forms is of a size of 100-400nm (phase farmland size is meant that the polydiolefin block forms the size of microcosmic phase structure, and that can observe arrives) in the photo of atomic force microscope.The phenylethylene-dialkene special copolymer adopts the negatively charged ion continuous polymerization method, and at first the monomer styrene with liquid state carries out one-step polymerization with being pumped in the flow reactor; Treat that one section monomer conversion reaches 95% and adds diolefine when above and carry out two sections polymerizations, add diolefine and vinylbenzene blended monomer polymerization at two sections after finishing then, make it contain the PB/PS block, two sections monomer conversions added vinylbenzene greater than 95% o'clock and carry out the final stage polymerization.The weight percent of diolefine is 0.1-19.9% in the whole polymkeric substance, add lithium alkylide in the polymerization process as catalyzer, polymerization end to add a kind of in terminator water, methyl alcohol, the ethanol, monomer or monomer solution exist with liquid state all the time in whole polymerization process, and polymkeric substance exists with fusion, solution, slurry or solid state, after polyreaction finishes, final reacting product directly enters recovery system and carries out MONOMER RECOVERY, and the polymkeric substance that obtains carries out obtaining the phenylethylene-dialkene special copolymer after the subsequent disposal.
Described diolefine is 1,3-butadiene and 2-methyl isophthalic acid, one or both in the 3-butadiene.
Described negatively charged ion continuous polymerization method is a kind of in solution polymerization and the mass polymerization.
Described solution polymerization is meant that adding a certain amount of solvent in monomer carries out premix, and solvent and monomeric volume ratio are 100:1-1:100, need solvent is reclaimed after reacted final product enters recovery system; Wherein solvent is one or more of ethylene dichloride, hexanaphthene, normal hexane, benzene,toluene,xylene, hexane, tetrahydrofuran (THF), acetone, heptane, sherwood oil, dioxolane, dioxane, dioxy seven rings and three oxygen, eight rings.
The polymerization time of described polyreaction is 0.5-120min, polymeric reaction temperature is-and 20-200 ℃.
Described flow reactor adopts continuous tubular reactor, forward to carry single screw extrusion machine, oppositely carry single screw extrusion machine, forward to carry reciprocating type single screw extrusion machine, oppositely carry reciprocating type single screw extrusion machine, forward to carry in the same way with Heterodromy double-screw extruder, oppositely carry and carry four screw extruder with Heterodromy double-screw extruder, forward in the same way and oppositely carry a kind of in the four screw extruder, and its length-to-diameter ratio is 10-200.
Beneficial effect of the present invention is: the present invention adopts the method for negatively charged ion successive polymerization, and styrene monomer residual in the product is extremely low, the more important thing is that production cost is low, is easy to be accepted by market; Conventional phenylethylene-dialkene polymerization production method is an interrupter method, is flow reactor continuous processing production technique and the present invention adopts, and this technological reaction time is short, and output is big, and running cost is low, safeguards simple.The phenylethylene-dialkene special copolymer applied range of being produced can be widely used in stationery, clothes rack capable, vehicle lampshade, hard food holds and fields such as packing box, medical device, toy, artwork ornaments.
Embodiment
Embodiment 1
With length-to-diameter ratio is that 10 forward carries the working temperature of twin screw extruder to be controlled at-20 ℃, and rotating speed is controlled to be 200r/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the forward conveying twin screw extruder; Treat that one section monomer conversion reaches 95% and adds 1,3-butadiene when above and carry out two sections polymerizations, adding 1,3-butadiene and vinylbenzene blended monomer polymerization polymerization is finished after; Two sections monomer conversions added vinylbenzene greater than 95% o'clock and carry out the final stage polymerization, and the weight percent of 1,3-butadiene is 0.1% in the final polymkeric substance, adds lithium alkylide in the polymerization process as catalyzer, and total polymerization time is 0.5min.Polymeric reaction temperature is-20 ℃.Polymerization ends and adds terminator water.Monomer exists with liquid state all the time in whole polymerization process, and polymkeric substance exists with solid state.What carried out this moment is the body anionic polymerization.After polyreaction finished, final reacting product directly entered the recovery that recovery system is carried out monomer and solvent, and the polymkeric substance that obtains carries out obtaining the phenylethylene-dialkene special copolymer after the subsequent disposal.Adopt German Bruker nuclear magnetic resonance analyser (
1H NMR) measure diene content, the weight percent that obtains 1,3-butadiene in the final polymkeric substance is 0.1%; Adopting U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average is 80000.The phase farmland of adopting U.S. NanoScope III atomic force microscope (percussion mode) to measure the PB block is of a size of 100nm.
Embodiment 2
The working temperature that with length-to-diameter ratio is 40 reverse conveying twin screw extruder is controlled at 200 ℃, and rotating speed is controlled to be 50r/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the reverse conveying twin screw extruder; Treat that one section monomer conversion reaches 95% and adds the 2-methyl isophthalic acid when above, the 3-divinyl carries out two sections polymerizations, adding 2-methyl isophthalic acid polymerization is finished after, 3-divinyl and vinylbenzene blended monomer polymerization; Two sections monomer conversions added vinylbenzene greater than 95% o'clock and carry out the final stage polymerization, 2-methyl isophthalic acid in the final polymkeric substance, and the weight percent of 3-divinyl is 19.9%, adds lithium alkylide in the polymerization process as catalyzer, total polymerization time is 120min.All added a certain amount of solvent toluene in above-mentioned arbitrary process monomer and carried out premix, solvent and monomeric volume ratio are 100:1.Polymeric reaction temperature is 200 ℃.Polymerization ends and adds terminator methyl alcohol.Monomer solution exists with liquid state all the time in whole polymerization process, and polymkeric substance exists with slurry state.What carried out this moment is solution anionoid polymerization.After polyreaction finished, final reacting product directly entered the recovery that recovery system is carried out monomer and solvent, and the polymkeric substance that obtains carries out obtaining the phenylethylene-dialkene special copolymer after the subsequent disposal.Adopt German Bruker nuclear magnetic resonance analyser (
1H NMR) measure diene content, obtain 2-methyl isophthalic acid in the final polymkeric substance, the weight percent of 3-divinyl is 19.9%; Adopting U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average is 100000.The phase farmland of adopting U.S. NanoScope III atomic force microscope (percussion mode) to measure the PB block is of a size of 400nm.
Embodiment 3
With length-to-diameter ratio is that 200 forward carries the working temperature of four screw extruder to be controlled at 100 ℃, and rotating speed is controlled to be 50r/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the reverse conveying twin screw extruder; Treat that one section monomer conversion reaches 95% and adds the 2-methyl isophthalic acid when above, the 3-divinyl carries out two sections polymerizations, adding 2-methyl isophthalic acid polymerization is finished after, 3-divinyl and vinylbenzene blended monomer polymerization; Two sections monomer conversions added vinylbenzene greater than 95% o'clock and carry out the final stage polymerization, 2-methyl isophthalic acid in the final polymkeric substance, and the weight percent of 3-divinyl is 9.8%, adds lithium alkylide in the polymerization process as catalyzer, total polymerization time is 100min.All added a certain amount of solvent toluene in above-mentioned arbitrary process monomer and carried out premix, solvent and monomeric volume ratio are 20:100.Polymeric reaction temperature is 100 ℃.Polymerization ends and adds terminator ethanol.Monomer solution exists with liquid state all the time in whole polymerization process, and polymkeric substance exists with slurry state.What carried out this moment is solution anionoid polymerization.After polyreaction finished, final reacting product directly entered the recovery that recovery system is carried out monomer and solvent, and the polymkeric substance that obtains carries out obtaining the phenylethylene-dialkene special copolymer after the subsequent disposal.Adopt German Bruker nuclear magnetic resonance analyser (
1H NMR) measure diene content, obtain 2-methyl isophthalic acid in the final polymkeric substance, the weight percent of 3-divinyl is 9.8%; Adopting U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average is 800000.The phase farmland of adopting U.S. NanoScope III atomic force microscope (percussion mode) to measure the PB block is of a size of 200nm.
Claims (6)
1, a kind of preparation method of phenylethylene-dialkene special copolymer, it is characterized in that comprising the steps: that phenylethylene-dialkene special copolymer molecular structure is PS-PB-PB/PS-PS, wherein PS is a polystyrene block, PB is the polydiolefin block, and PB/PS is the phenylethylene-dialkene block of random copolymer; The molecular weight of this kind polymkeric substance is 80000-800000, and the phase farmland that the PB block forms is of a size of 100-400nm; The phenylethylene-dialkene special copolymer adopts the negatively charged ion continuous polymerization method, and at first the monomer styrene with liquid state carries out one-step polymerization with being pumped in the flow reactor; Treat that one section monomer conversion reaches 95% and adds diolefine when above and carry out two sections polymerizations, add diolefine and vinylbenzene blended monomer polymerization at two sections after finishing then, make it contain the PB/PS block, two sections monomer conversions added vinylbenzene greater than 95% o'clock and carry out the final stage polymerization; The weight percent of diolefine is 0.1-19.9% in the whole polymkeric substance, add lithium alkylide in the polymerization process as catalyzer, polymerization end to add a kind of in terminator water, methyl alcohol, the ethanol, monomer or monomer solution exist with liquid state all the time in whole polymerization process, and polymkeric substance exists with fusion, solution, slurry or solid state, after polyreaction finishes, final reacting product directly enters recovery system and carries out MONOMER RECOVERY, and the polymkeric substance that obtains carries out obtaining the phenylethylene-dialkene special copolymer after the subsequent disposal.
2, the preparation method of a kind of phenylethylene-dialkene special copolymer as claimed in claim 1 is characterized in that: described diolefine is 1,3-butadiene and 2-methyl isophthalic acid, one or both in the 3-butadiene.
3, the preparation method of a kind of phenylethylene-dialkene special copolymer as claimed in claim 1 is characterized in that: described negatively charged ion continuous polymerization method is a kind of in solution polymerization and the mass polymerization.
4, the preparation method of a kind of phenylethylene-dialkene special copolymer as claimed in claim 1, it is characterized in that: described solution polymerization is meant that adding a certain amount of solvent in monomer carries out premix, solvent and monomeric volume ratio are 100:1-1:100, need solvent is reclaimed after reacted final product enters recovery system; Wherein solvent is one or more of ethylene dichloride, hexanaphthene, normal hexane, benzene,toluene,xylene, hexane, tetrahydrofuran (THF), acetone, heptane, sherwood oil, dioxolane, dioxane, dioxy seven rings and three oxygen, eight rings.
5, the preparation method of a kind of phenylethylene-dialkene special copolymer as claimed in claim 1 is characterized in that: the polymerization time of described polyreaction is 0.5-120min, polymeric reaction temperature is-and 20-200 ℃.
6, the preparation method of a kind of phenylethylene-dialkene special copolymer as claimed in claim 1, it is characterized in that: described flow reactor adopts continuous tubular reactor, forward to carry single screw extrusion machine, oppositely carry single screw extrusion machine, forward to carry reciprocating type single screw extrusion machine, oppositely carry reciprocating type single screw extrusion machine, forward to carry in the same way with Heterodromy double-screw extruder, oppositely carry and carry four screw extruder with Heterodromy double-screw extruder, forward in the same way and oppositely carry a kind of in the four screw extruder, and its length-to-diameter ratio is 10-200.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628954A (en) * | 2015-02-04 | 2015-05-20 | 张乃然 | Preparation method of food-grade butylbenzene or butadiene solution polymerized rubber |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN106397696A (en) * | 2016-08-31 | 2017-02-15 | 广东众和化塑有限公司 | SBS elastomer simultaneously having high transmittance, high twisting resistance and high foaming efficiency, and production method thereof |
-
2009
- 2009-01-15 CN CN2009100954678A patent/CN101475674B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628954A (en) * | 2015-02-04 | 2015-05-20 | 张乃然 | Preparation method of food-grade butylbenzene or butadiene solution polymerized rubber |
| CN111019045A (en) * | 2015-02-04 | 2020-04-17 | 张乃然 | Method for preparing food-grade butylbenzene or butadiene solution polymerized rubber |
| CN105175659A (en) * | 2015-07-23 | 2015-12-23 | 湖南博瑞康新材料有限公司 | Transparent hydrogenated polystyrene-b-random copolymerized conjugated diene/styrene resin and preparation method therefor |
| CN105175659B (en) * | 2015-07-23 | 2017-11-03 | 湖南博瑞康新材料有限公司 | A kind of transparent type hydrogenated polystyrene b random copolymerizations conjugated diene/styrene resin and preparation method thereof |
| CN106397696A (en) * | 2016-08-31 | 2017-02-15 | 广东众和化塑有限公司 | SBS elastomer simultaneously having high transmittance, high twisting resistance and high foaming efficiency, and production method thereof |
| CN106397696B (en) * | 2016-08-31 | 2019-03-22 | 广东众和化塑有限公司 | It is a kind of to be provided simultaneously with high saturating, highly resistance tortuosity and SBS elastomer of high-foaming efficiency and preparation method thereof |
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