CN101475673B - Transparent phenylethylene-dialkene star shaped copolymer and continuous preparation thereof - Google Patents
Transparent phenylethylene-dialkene star shaped copolymer and continuous preparation thereof Download PDFInfo
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- CN101475673B CN101475673B CN2009100954663A CN200910095466A CN101475673B CN 101475673 B CN101475673 B CN 101475673B CN 2009100954663 A CN2009100954663 A CN 2009100954663A CN 200910095466 A CN200910095466 A CN 200910095466A CN 101475673 B CN101475673 B CN 101475673B
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Abstract
The invention discloses a transparent styrene-diolefin star copolymer and a continuous preparation method thereof. The copolymer has the following structure: (PS-PB-PB/PS-PS) n-R or (PS-PB-PB/PS) n-R, wherein PS represents a polystyrene block, PB represents a polydiolefin block, PB/PS represents a styrene-diolefin random copolymer block, and R represents the core of the star structure. The invention also discloses the continuous preparation method for the copolymer. The preparation method has a high monomer conversion rate above 99.999 percent. The preparation method is characterized by low production cost, short reaction time, high yield, low operating cost, simple maintenance, no leakage of unconverted monomers and solvents during the production, reutilization, safety and environmental protection, and wide application range.
Description
Technical field
The present invention relates to a kind of transparent phenylethylene-dialkene star shaped copolymer and continuous preparation method thereof.
Background technology
Phenylethylene resin series is one of five big universal synthetic resins, generally is only second to PE, PVC and PP and occupies the 4th by output.PS (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), eps (EPS), styrene-butadiene copolymer (K-Resin) etc. is the huge phenylethylene resin series system of representative.
Nineteen fifty-two Amos etc. develops a kind of technology of new production toughness polystyrene resin; Its ultimate principle is in polymerization process, to stir; Thereby make rubber become dispersed particle rather than external phase; The toughness PS of producing like this is exactly so-called high-impact polystyrene (HIPS), and HIPS removes has the advantages such as rigidity, processing characteristics and tint permanence of general purpose polystyrene, and the introducing of rubber is risen its shock strength significantly; But performance index such as tensile strength, hardness, gloss descend, and have also lost certain transparency simultaneously.Because HIPS all adopts the radical polymerization mode to produce, and always has the small amounts of styrene monomer in the finished product, styrene monomer is poisonous, so its range of application just receives certain restriction.
K-Resin is by the breadboard chemist AlonzoKitchen invention of Phillips oil research and development; The pilot plant of first resin was built in 1967; Begin commodity production in the Borger of Texas SBC factory in October, 1972, and up to the present the yearly capacity in the world possibly surpass 500,000 tons.K-Resin is known as the transparent anti-impact resin of butylbenzene again; It is a butadiene-styrene block copolymer; Its main characteristic is high transparent, high impact properties and nontoxicity; It is the modified product of general purpose polystyrene, has not only kept the excellent transparency of general purpose polystyrene and good processibility, and has overcome the deadly defects such as fragility and environmental stress crack resistance difference of general purpose polystyrene.With some other shock proof transparent material: polycarbonate, rhodia, synthetic glass or modified organic glass are compared, though the shock strength of the transparent anti-impact resin of butylbenzene not as they, the very big advantage of tool on cost, processing characteristics.Therefore, it is widely used for fields such as food product pack, medical treatment product, toy for children, office appliance.The weight percentage of divinyl is generally 20-35% among the K-Resin; Though it has overcome shortcomings such as fragility and the environmental stress crack resistance of general purpose polystyrene; But compare its rigidity loss with general purpose polystyrene bigger; Application in some field is unsatisfactory, and therefore in the long-term inflexible Application Areas of needs, K-Resin can not replace general purpose polystyrene fully.
Summary of the invention
The object of the present invention is to provide a kind of transparent phenylethylene-dialkene star shaped copolymer and continuous preparation method thereof, monomer conversion of the present invention is very high, and＞99.999%, production cost is low; Be easy to accepted by market, the continuous processing production technique has the reaction times weak point, and output is big; Running cost is low, safeguards that simply unconverted monomer and solvent do not have leakage in the production process; Can recycle safety and environmental protection, the characteristics of applied range.
In order to achieve the above object, technical scheme of the present invention is:
A kind of transparent phenylethylene-dialkene star shaped copolymer is characterized in that this multipolymer has following structure: (PS-PB-PB/PS-PS)
n-R or (PS-PB-PB/PS)
n-R.Wherein, PS is that polystyrene block, PB are that polydiolefin block, PB/PS are the phenylethylene-dialkene block of random copolymer, and R is " nuclear " of star structure.The molecular-weight average of phenylethylene-dialkene star shaped copolymer is 8 * 10
4-8 * 10
6, 3-10 bar " arm " is arranged, i.e. n=3-10.The weight percentage of diolefine is 0.1-19.9% in the phenylethylene-dialkene star shaped copolymer, and the weight ratio of vinylbenzene and diolefine is 99.9: 0.1-80.1: 19.9, and its mist degree is less than 3%, and transparency is greater than 85%.
Described diolefine is 1,3-butadiene and 2-methyl isophthalic acid, one or both in the 3-butadiene.
The phase farmland of described polymer P B block is of a size of 100-400nm; Phase farmland size is the size of system polydiolefin phase structure that block forms; That in the photo of electron microscope or AFM, can observe arrives; Its size also can be clear and definite measure, its size directly has influence on the transparency of polymkeric substance.
The continuous preparation method of described transparent phenylethylene-dialkene star shaped copolymer; Comprise the steps: that phenylethylene-dialkene star shaped copolymer adopts the negatively charged ion continuous polymerization method, 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; , added diolefine and cinnamic mix monomer and carry out polymerization greater than 95% o'clock at two sections monomer conversions, make it contain the PB/PS block; If need, can continue to add vinylbenzene and carry out polymerization; Add coupling agent at last, form the molecular structure of star.The weight percent that makes diolefine in the polymkeric substance in the polymerization process is 0.1-19.9%; Add catalyzer in the polymerization process, polymerization ends and adds terminator, and 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 finished, final reacting product directly got into recovery system and carries out MONOMER RECOVERY, and the polymkeric substance that obtains carries out obtaining phenylethylene-dialkene star shaped copolymer after the subsequent disposal.
Described negatively charged ion continuous polymerization method is a kind of in solution polymerization and the mass polymerization.
Described solution polymerization is meant that in monomer, adding a certain amount of solvent carries out premix, and solvent and monomeric volume ratio are 100: 1-1: 100, and reacted final product needs solvent is reclaimed after getting into recovery system.
The solvent that described and monomer carry out premix is one or more of ethylene dichloride, hexanaphthene, normal hexane, benzene,toluene,xylene, hexane, THF, acetone, heptane, sherwood oil, dioxolane, dioxane, dioxy seven rings and three oxygen, eight rings.
Catalyzer in the described polymerization process is a lithium alkylide.
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, the reverse conveying carries four screw extruder with Heterodromy double-screw extruder, forward in the same way and oppositely carries a kind of in the four screw extruder, and its length-to-diameter ratio is 10-200.
Beneficial effect of the present invention is: transparent phenylethylene-dialkene star shaped copolymer of the present invention possesses the rigidity of general purpose polystyrene and the toughness of HIPS; Have low haze similar and high transparent again, filled up the blank of present phenylethylene resin series Application Areas with K-Resin; And employing anionoid polymerization, monomer conversion very high (＞99.999%), so residual styrene monomer is extremely low in the product; The more important thing is that production cost is low, be easy to accepted by market.What the present invention adopted is flow reactor continuous processing production technique, and this technological reaction time is short, and output is big, and running cost is low, safeguards that simply unconverted monomer and solvent do not have leakage in the production process, can recycle safety and environmental protection.Phenylethylene-dialkene star shaped copolymer applied range of the present invention 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
The working temperature that with length-to-diameter ratio is 200 reverse conveying four screw extruder is controlled at 200 ℃, and rotating speed is controlled to be 30r/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the reverse conveying four screw extruder; Treat that one section monomer conversion reaches 95% and adds 1,3-butadiene when above and carry out two sections polymerizations; Two sections monomer conversions added 1,3-butadiene greater than 95% o'clock and carry out three stage polymerization with cinnamic mix monomer, added vinylbenzene then and carried out four sections polymerizations, added coupling agent at last, the molecular structure of formation 3 " arm " star.The weight ratio of vinylbenzene and 1,3-butadiene is in the polymerization process: 80.1: 19.9.Then through adopt German Bruker NMR (
1H NMR) measure diene content, the weight percent that obtains 1,3-butadiene in the final polymkeric substance is 19.9%, and is as shown in table 1, and table 1 is the basic parameter table of polymkeric substance of the present invention; Add the catalyzer lithium alkylide in the polymerization process, total polymerization time is 60min.All added a certain amount of solvents tetrahydrofurane in above-mentioned arbitrary process monomer and carried out premix, solvent and monomeric volume ratio are 1: 100.Polymeric reaction temperature is 200 ℃.Polymerization ends and adds terminator water.Monomer solution exists with liquid state all the time in whole polymerization process, and polymkeric substance exists with solution state.What carried out this moment is solution anionoid polymerization.After polyreaction finishes; Final reacting product directly gets into the recovery that recovery system is carried out monomer and solvent; The polymkeric substance that obtains carries out obtaining transparent phenylethylene-dialkene star shaped copolymer after the subsequent disposal, adopts U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average to be: 8 * 10
4The phase farmland dimension measurement that adopts U.S. NanoScopeIII AFM (AFM, percussion mode) to carry out the PB block is: 400nm.
Embodiment 2
With length-to-diameter ratio is that 140 forward carries the working temperature of single screw extrusion machine to be controlled at-10 ℃, and rotating speed is controlled to be 30r/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the forward conveying single screw extrusion machine; 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; Two sections monomer conversions added the 2-methyl isophthalic acid greater than 95% o'clock, and 3-divinyl and cinnamic mix monomer carry out three stage polymerization, add coupling agent at last, form the molecular structure of 10 " arm " star.Vinylbenzene and 2-methyl isophthalic acid in the polymerization process, the weight ratio of 3-divinyl is: 88.0: 12.0.Then through adopt German Bruker NMR (
1H NMR) measure diene content, obtain 2-methyl isophthalic acid in the final polymkeric substance, the weight percent of 3-divinyl is 12%, and is as shown in table 1, and table 1 is the basic parameter table of polymkeric substance of the present invention; Add the catalyzer lithium alkylide in the polymerization process, total polymerization time is 20min.Polymeric reaction temperature is-10 ℃.Polymerization ends and adds terminator methyl alcohol.Monomer exists with liquid state all the time in whole polymerization process, and polymkeric substance exists with molten state.What carried out this moment is the body anionic polymerization.After polyreaction finishes; Final reacting product directly gets into the recovery that recovery system is carried out monomer and solvent; The polymkeric substance that obtains carries out obtaining transparent phenylethylene-dialkene star shaped copolymer after the subsequent disposal, adopts U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average to be: 2 * 10
5The phase farmland dimension measurement that adopts U.S. NanoScope III AFM (AFM, percussion mode) to carry out the PB block is: 200nm.
Embodiment 3
The working temperature that with length-to-diameter ratio is 10 the reciprocating type single screw extrusion machine of reverse conveying is controlled at 80 ℃, and rotating speed is controlled to be 30r/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the reciprocating type single screw extrusion machine of reverse conveying; Treat that one section monomer conversion reaches 95% and adds 1,3-butadiene when above and carry out two sections polymerizations; Two sections monomer conversions added 1,3-butadiene greater than 95% o'clock and carry out three stage polymerization with cinnamic mix monomer, added coupling agent at last, the molecular structure of formation 5 " arm " star.The weight ratio of vinylbenzene and 1,3-butadiene is in the polymerization process: 92.0: 8.0, then through adopt German Bruker NMR (
1HNMR) measure diene content, the weight percent that obtains 1,3-butadiene in the final polymkeric substance is 8%, and is as shown in table 1, and table 1 is the basic parameter table of polymkeric substance of the present invention; Add the catalyzer lithium alkylide in the polymerization process, total polymerization time is 75min.All added a certain amount of solvent dioxane in above-mentioned arbitrary process monomer and carried out premix, solvent and monomeric volume ratio are 20: 100.Polymeric reaction temperature is 80 ℃.Polymerization ends and adds terminator ethanol.Monomer solution exists with liquid state all the time in whole polymerization process, and newly-generated polymkeric substance and monomer and solvent can not mix when temperature is high, so polymkeric substance exists with slurry state.What carried out this moment is solution anionoid polymerization.After polyreaction finishes; Final reacting product directly gets into the recovery that recovery system is carried out monomer and solvent; The polymkeric substance that obtains carries out obtaining transparent phenylethylene-dialkene star shaped copolymer after the subsequent disposal, adopts U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average to be: 6 * 10
6The phase farmland dimension measurement that adopts U.S. NanoScopeIII AFM (AFM, percussion mode) to carry out the PB block is: 180nm.
Embodiment 4
The working temperature of continuous tubular reactor is controlled at 0 ℃, and material flow is controlled to be 3m/min.The monomer styrene of liquid state carries out one-step polymerization with being pumped in the continuous tubular reactor; Treat that one section monomer conversion reaches 95% and adds 1,3-butadiene when above and carry out two sections polymerizations; Two sections monomer conversions added 1,3-butadiene greater than 95% o'clock and carry out three stage polymerization with cinnamic mix monomer, added vinylbenzene then and carried out four sections polymerizations, added coupling agent at last, the molecular structure of formation 4 " arm " star.The weight ratio of vinylbenzene and 1,3-butadiene is in the polymerization process: 99.9: 0.1.Then through adopt German Bruker NMR (
1H NMR) measure diene content, the weight percent that obtains 1,3-butadiene in the final polymkeric substance is 0.1%, and is as shown in table 1, and table 1 is the basic parameter table of polymkeric substance of the present invention; Add the catalyzer lithium alkylide in the polymerization process, total polymerization time is 10min.Polymeric reaction temperature is 0 ℃.Polymerization ends and adds terminator water.Monomer exists with liquid state all the time in whole polymerization process, and polymkeric substance exists with molten state.What carried out this moment is the body anionic polymerization.After polyreaction finishes; Final reacting product directly gets into the recovery that recovery system is carried out monomer and solvent; The polymkeric substance that obtains carries out obtaining transparent phenylethylene-dialkene star shaped copolymer after the subsequent disposal, adopts U.S. Waters gel permeation chromatograph (GPC) to measure its molecular-weight average to be: 8 * 10
6The phase farmland dimension measurement that adopts U.S. NanoScope III AFM (AFM, percussion mode) to carry out the PB block is: 100nm.
Embodiment 5
The fundamental property of embodiment 1-4 and general PS, HIPS and K-Resin is compared.Wherein tensile yield strength and elongation at break all adopt American I nstra universal testing machine to measure, and the Izod shock strength adopts the Taiwan HK-5047 of remittance section type shock strength machine to measure.Shao's formula hardness adopts outstanding grace LX-D type duroplasts Shao formula sclerometer to measure.Transparence adopts DRK122 type photoelectricity haze meter to measure.As shown in table 2, table 2 is polymkeric substance of the present invention, PS, HIPS and K-Resin fundamental property test result; Can see that from table 2 transparent phenylethylene-dialkene star shaped copolymer tensile yield strength of the present invention all is higher than K-Resin, wherein high molecular weight products (6 * 10
6With 8 * 10
6) tensile yield strength in addition surpassed general PS and HIPS; Elongation at break and Izod shock strength are between general PS and K-Resin; Shao's formula hardness is a little less than general PS, and suitable in K-Resin; Transparence and general PS and K-Resin are suitable basically, and far above HIPS.This shows that transparent phenylethylene-dialkene star shaped copolymer of the present invention possesses the rigidity of general purpose polystyrene, have low haze similar and high transparent again, filled up the blank of present phenylethylene resin series Application Areas with K-Resin.
Table 1
| Basic parameter | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Molecular-weight average | 80,000 | 20,0000 | 600,0000 | 800,0000 |
| Diene content (wt) % | 19.9 | 12.0 | 8.0 | 0.1 |
| The diolefine kind | 1,3-butadiene | The 2-methyl isophthalic acid, the 3-divinyl | 1,3-butadiene | 1,3-butadiene |
| The bar number of " arm " in the molecule | 3 | 10 | 5 | 4 |
| Synthetic catalyst | Lithium alkylide | Lithium alkylide | Lithium alkylide | Lithium alkylide |
Table 2
| Test event | Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | General PS | HIPS | K-Resin |
| Tensile yield strength (MPa) | ASTM-D638 | 26 | 30 | 50 | 70 | 46 | 31 | 23.7 |
| Elongation at break (%) | ASTM-D638 | 25 | 20 | 8 | 2 | 2 | 23 | 30 |
| Izod shock strength (J/m) | ASTM-D256 | 31 | 27 | 25 | 23 | 19.7 | 64 | 30 |
| Shao's formula hardness (D) | ASTM-D2440 | 65 | 65 | 67 | 72 | 72 | 70 | 64 |
| Transparence (%) | ASTM-D1003 | 87 | 90 | 91 | 93 | 92 | 65 | 90 |
Claims (9)
1. a transparent phenylethylene-dialkene star shaped copolymer is characterized in that this multipolymer has following structure: (PS-PB-PB/PS-PS)
n-R or (PS-PB-PB/PS)
n-R; Wherein, PS is that polystyrene block, PB are that polydiolefin block, PB/PS are the phenylethylene-dialkene block of random copolymer, and R is " nuclear " of star structure; The molecular-weight average of phenylethylene-dialkene star shaped copolymer is 8 * 10
4-8 * 10
6, 3-10 bar " arm " is arranged, i.e. n=3-10; The weight percentage of diolefine is 0.1-19.9% in the phenylethylene-dialkene star shaped copolymer, and the weight ratio of vinylbenzene and diolefine is 99.9: 0.1-80.1: 19.9, and its mist degree is less than 3%, and transparency is greater than 85%; The phase farmland of described polymer P B block is of a size of 100-400nm.
2. transparent phenylethylene-dialkene star shaped 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-divinyl.
3. the continuous preparation method of a transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 1; It is characterized in that: phenylethylene-dialkene star shaped 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; , added diolefine and cinnamic mix monomer and carry out polymerization greater than 95% o'clock at two sections monomer conversions, make it contain the PB/PS block; If need, can continue to add vinylbenzene and carry out polymerization; Add coupling agent at last, form the molecular structure of star; The weight percent that makes diolefine in the polymkeric substance in the polymerization process is 0.1-19.9%; Add catalyzer in the polymerization process, polymerization ends and adds terminator, and 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 finished, final reacting product directly got into recovery system and carries out MONOMER RECOVERY, and the polymkeric substance that obtains carries out obtaining phenylethylene-dialkene star shaped copolymer after the subsequent disposal.
4. the continuous preparation method of transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 3 is characterized in that: described negatively charged ion continuous polymerization method is a kind of in solution polymerization and the mass polymerization.
5. the continuous preparation method of transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 4; It is characterized in that: described solution polymerization is meant that in monomer, adding a certain amount of solvent carries out premix; Solvent and monomeric volume ratio are 100: 1-1: 100, and, reacted final product needs solvent is reclaimed after getting into recovery system.
6. the continuous preparation method of transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 5 is characterized in that: the solvent that described and monomer carry out premix is one or more of ethylene dichloride, hexanaphthene, normal hexane, benzene,toluene,xylene, THF, acetone, heptane, sherwood oil, dioxolane, dioxane, dioxy seven rings and three oxygen, eight rings.
7. the continuous preparation method of transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 3, it is characterized in that: the catalyzer in the described polymerization process is a lithium alkylide.
8. the continuous preparation method of transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 3, it is characterized in that: the polymerization time of described polyreaction is 0.5-120min, polymeric reaction temperature is-20～200 ℃.
9. the continuous preparation method of transparent phenylethylene-dialkene star shaped copolymer as claimed in claim 3; 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, the reverse conveying carries four screw extruder with Heterodromy double-screw extruder, forward in the same way and oppositely carries a kind of in the four screw extruder, and its length-to-diameter ratio is 10-200.
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