CN102504119A - Method for producing high impact polystyrene - Google Patents
Method for producing high impact polystyrene Download PDFInfo
- Publication number
- CN102504119A CN102504119A CN2011103336006A CN201110333600A CN102504119A CN 102504119 A CN102504119 A CN 102504119A CN 2011103336006 A CN2011103336006 A CN 2011103336006A CN 201110333600 A CN201110333600 A CN 201110333600A CN 102504119 A CN102504119 A CN 102504119A
- Authority
- CN
- China
- Prior art keywords
- flow reactor
- linear flow
- reactor
- product stream
- polyblend
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005669 high impact polystyrene Polymers 0.000 title claims abstract description 46
- 239000004797 high-impact polystyrene Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title description 19
- 238000000034 method Methods 0.000 claims abstract description 74
- 229920001971 elastomer Polymers 0.000 claims abstract description 52
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- 239000011541 reaction mixture Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 239000005060 rubber Substances 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 23
- 239000004793 Polystyrene Substances 0.000 description 19
- 208000037516 chromosome inversion disease Diseases 0.000 description 18
- 239000002245 particle Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 238000010008 shearing Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 230000035882 stress Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 4
- 230000006353 environmental stress Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000021149 fatty food Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000013348 organic food Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical class OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
Images
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The abstract was not in accordance with PCT Rule 8.1 (b) because it was more than 150 words in length. The abstract has been established by this Authority to read as follows: A process for producing high impact polystyrene including feeding at least one vinyl aromatic monomer; an elastomer, and a free radical initiator to a first linear flow reactor to form a reaction mixture. Polymerizing the reaction mixture in the first linear flow reactor to a point below the point at which phase inversion occurs to produce a first polymerization mixture and feeding the first polymerization mixture from the first linear flow reactor to a second linear flow reactor. Polymerizing the reaction mixture in the second linear flow reactor to at least a phase inversion point of the mixture to produce a second polymerization mixture and feeding the second polymerization mixture from the second linear flow reactor to at least a third linear flow reactor for post.inversion polymerization of the second polymerization mixture.
Description
The cross reference of related application
Does not use
.
Technical field
Present invention relates in general to the manufacturing of PS.More specifically, the present invention relates to use continuous stirred tank reactor or plug flow reactor or its combination to make high-impact polystyrene.
Background technology
Monovinylidene aromatic compounds for example vinylbenzene, alpha-methyl styrene and nuclear substituted cinnamic elastomer reinforced polymer is widely used in the commercial applications of wide region.For example; The discrete elastomer particles for example cross-linked rubber elastomerics enhanced styrene polymer that disperses to spread all over the styrene polymer matrix can be used for wide range of applications, comprises food product pack, office appliance, trolley part, houseware and the consumer's goods, structural insulated body and cosmetic package.Such elastomer reinforced polymer is commonly referred to high-impact polystyrene (HIPS).
The polymkeric substance for example method of manufacture of HIPS can adopt the polymerization of using the continuous flow method.The continuous flow method relates to the equipment of the reactor drum that comprises a plurality of arranged in succession, wherein from a reactor drum to next reactor drum, extent of polymerization increases.The type of reactor of using in the manufacturing of HIPS can comprise continuous stirred tank reactor (CSTR) and/or plug flow reactor (PFR).The characteristic of the HIPS of the factor affecting manufacturing of the layout of reaction vessel and reaction conditions for example.The amount of extent of polymerization in each reactor drum (it causes different machinery and/or optical property) and elastomer content can determine the grade of the HIPS of manufacturing.
The physical property of HIPS and mechanical properties depend on the for example particle size of cross-linked rubbery particle of many factors.The important quality of HIPS material is the ability of such material resisting environmental stress and cracking.This ability must combine with the characteristic of high impact strength so that can be used for for example food product containers of goods.In addition, other critical nature of such goods comprises flexural strength and tensile strength.
For HIPS or any other thermoplastic polymer of being used to prepare food product containers, the character of stress cracking resistance or environmental stress crack resistance (ESCR) is particularly important.The food contents of such polymer container can not make the polymeric material degrades of the HIPS that processes said container or any other type usually, but when thermoplastic polymer during by the extrusion sheet thermoforming, unrelieved stress is locked in the moulded parts.These stress make polymkeric substance begin to receive the invasion and attack of the common impregnable material of said polymkeric substance.By use modified rubber with such goods of the styrene polymer manufacturing that improves shock strength be present in Organic food in ordinary matter be easy to stress cracking when for example fat is with oily the contact.Equally, such product is also experiencing stress cracking with the organic blowing agent that contains fluorine and bromine when for example halohydrocarbon contacts.For example have these polymkeric substance usually in the refrigerator lining at the family expenses article, when filling the cavity in the refrigerator with polyurethane foam, because the whipping agent that adopts in the said foam, it can ftracture.
Past, prevent or the effort that alleviates environmental stress cracking by be usually directed to wherein between polystyrene layer and the whipping agent or the complicated process that the multilayer polymer structure of polymkeric substance intermediate protective layer is set between polystyrene layer and fatty food material form.Being used for said vinylbenzene and the isolated a kind of such material layer of these materials is the terpolymer material that is called ABS or acrylonitrile-butadiene-styrene (ABS).Other trial that improves the stress cracking resistance of high-impact mono-vinyl aromatic polymer comprises the amount that improves the rubber of sneaking in the said polymkeric substance.Yet higher rubber content can reduce stretching and flexural strength and typically will raise the cost.
The type of employed continuous flow method and the elastomeric amount of being utilized influence the HIPS manufacturing cost greatly.Therefore, expectation is developed to be used to make and is had enhanced mechanical properties for example equipment and the method for the HIPS of the elastomer content with reduction of shock strength, ductility and ESCR.Also the expectation exploitation is used to make equipment and the method for the HIPS of the environmental stress crack resistance with improvement.
Summary of the invention
An embodiment of the invention comprise at least a vi-ny l aromatic monomers, elastomerics and radical initiator are fed in first linear flow reactor to form reaction mixture for making the method for high-impact polystyrene.Make said reaction mixture in said first linear flow reactor be polymerized to point under the point that inversion of phases takes place to make first polyblend.To be fed to second linear flow reactor from said first polyblend of said first linear flow reactor, and in said second linear flow reactor, make phase inversion point that said first polyblend further is polymerized to said at least mixture to make second polyblend.To be fed to trilinear flow reactor and multiple reactor more randomly then from said second polyblend of said second linear flow reactor, to carry out the back conversion polymerization of said second polyblend.
An embodiment of the invention are for making the method for high-impact polystyrene; Comprise at least a vi-ny l aromatic monomers, elastomerics and radical initiator are fed to mixing tank to form reaction mixture, afterwards said reaction mixture is fed to first linear flow reactor and as the above-mentioned method, carries out from said mixing tank.
An alternate embodiments of the present invention comprises that the mixing tank that at least a vi-ny l aromatic monomers, elastomerics and radical initiator are fed to heating is to form reaction mixture; With the said reaction mixture in the mixing tank of said heating is heated, afterwards said reaction mixture is fed to first linear flow reactor and as the above-mentioned method, carries out from said mixing tank.
Further disclose among this paper through at least a vi-ny l aromatic monomers, elastomerics and radical initiator are fed to the continuation method that a series of polymerization reactors are made high-impact polystyrene.Said a series of polymerization reactor can comprise at least two linear flow reactor.After polymerization, can use the preheater that under the temperature that reduces, moves to make the product devolatilization.Said preheater can move the ESCR value to be improved under the temperature that is lower than 470 ° of F.
Embodiment of the present invention can be lower than the product that 10% rubber content manufacturing has the ESCR value of at least 10% remaining toughness (toughness retained).Embodiment of the present invention can be made the product with the rubber particle size (RPS) that is higher than 5 μ m.
Description of drawings
Fig. 1 is the synoptic diagram of the HIPS method of manufacture of prior art.
Fig. 2 is the synoptic diagram of the embodiment of HPFIR method of the present invention.
Fig. 3 is the synoptic diagram of embodiment that comprises the HPFIR method of the present invention of mixing tank.
Fig. 4 is the synoptic diagram of the art methods of use among the embodiment 1.
Fig. 5 is the synoptic diagram of the method for use during first of embodiment 2 tests.
Fig. 6 is the synoptic diagram of the method for use during second of embodiment 2 tests.
Fig. 7 is the synoptic diagram of the method used in the test of embodiment 3.
Fig. 8 is the figure that remaining toughness percentage ratio changes with RPS.
Fig. 9 is the figure of the mean particle size distribution of reactor content and products therefrom pellet in the multiple reactor method.
Figure 10 is the figure of ESCR value (remaining toughness %) to devolatilizer preheater temperature.
Embodiment
Fig. 1 explains United States Patent(USP) No. 4,777, and 210 prior art high-impact polystyrene (HIPS) method of manufacture is introduced this paper as a reference fully with this patent.This method comprises: continuous stirred tank reactor (CSTR) pre-transform teactor R100 is CSTR conversion reactor R101 afterwards, is conversion reactor R-1 after at least one plug-flow afterwards.The output of R-1 is delivered to conventional heater H-1, conventional afterwards devolatilizer DV-1.
Fig. 2 describes to be used for to make continuously the synoptic diagram of the reactor assembly 200 of elastomer reinforced polymer.In one embodiment, reactor assembly 200 can be used for continuous HIPS method of manufacture.With reference to Fig. 2, can will comprise for example reaction mixture feed to the first linear flow reactor 210 of polybutadiene rubber and radical initiator of vinylbenzene, elastomerics through totally being expressed as one or more feeding lines of 205.In an alternate embodiments, reaction mixture comprise vinylbenzene, elastomerics for example polybutadiene rubber, chain-transfer agent and additional component for example in the HIPS manufacturing field known those.In another embodiment, reaction mixture comprises: vinylbenzene; Elastomerics is polybutadiene rubber for example; The combination of radical initiator and chain-transfer agent; And additional component for example in the HIPS manufacturing field known those.The selection and the amount that can as those of ordinary skills are known, comprise the radical initiator, chain-transfer agent and the additional component that are used to make HIPS.
In one embodiment, the reaction mixture that is fed to continuous HIPS method of manufacture can comprise about 75%～about 99% vinylbenzene, about 1%～about 15% polyhutadiene, about 0.001%～about 0.2% radical initiator and for giving the additional component that any required physical properties needs.The existence value is the weight percentage of all forming.
The term linear flow reactor comprises plug flow reactor (PFR).First linear flow reactor or PFR 210 can move allowing that polyreaction proceeds under the condition of any point of inversion of phases before taking place.In one embodiment, first linear flow reactor 210 is moved under the pre-inversion condition, that is, external phase wherein is that vinylbenzene-rubber solutions and discontinuous phase are vinylbenzene-PS.In one embodiment, the vinylbenzene thinner can comprise other thinner for example ethylbenzene, toluene, YLENE, with and combination.In one embodiment; First linear flow reactor 210 or pre-transform teactor (PIR) are located immediately at before the polymerization reactor, make vinylbenzene polyhutadiene, radical initiator and other component be fed to PIR210 and the mixture that leaves PIR is fed to polymerization reactor 220 subsequently.
In one embodiment, polymerization reactor 220 is second linear flow reactor.In one embodiment, said linear flow reactor comprises plug flow reactor (PFR).In one embodiment, polymerization reactor 220 or the 2nd PFR vertically arrange.In another embodiment, the 2nd PFR220 horizontal arrangement.
In one embodiment, the polymerization reactor 220 or second linear flow reactor can be moved under following condition: before reaction mixture being introduced into any extra polymerization reactor, allow that polyreaction proceeds to phase inversion point at least.Therefore, polymerization reactor 220 is called plug-flow conversion reactor (PFIR).In other words, the reactant in the polymerization reactor 220 experiences inversion of phases before leaving this reactor drum (being called PFIR 220 here).
Inversion of phases refers to that the form that during the HIPS preparation, takes place changes.The raw material that is used for the HIPS preparation generally includes polybutadiene rubber and styrene monomer.These two kinds of components are normally miscible.In the pre-inversion stage of making, the mixture of vinylbenzene and polyhutadiene formation PS and vinylbenzene are dispersed in the external phase of mixture wherein.Along with vinylbenzene increases to the carrying out of the reaction of PS and the amount of PS, inversion of phases takes place, and PS/styrene mixture forms rubber grain and is dispersed in external phase wherein afterwards.This inversion of phases causes rubber wherein to form with the compounded rubber particulate that the form of the film that surrounds the PS farmland of being contained exists.The size of rubber grain can influence physics and the mechanical properties of HIPS with distributing.
In one embodiment, polymerization reactor 220 can move allowing that polyreaction proceeds under the condition of any point of inversion of phases before taking place.In one embodiment, polymerization reactor 220 moves under the pre-inversion condition, and promptly wherein external phase is that vinylbenzene-rubber solutions and discontinuous phase are vinylbenzene-PS.In another embodiment, move under first linear flow reactor 210 and polymerization reactor 220 each comfortable pre-inversion condition.In further embodiment, move under first linear flow reactor 210, polymerization reactor 220 and any directly in succession each comfortable pre-inversion condition of PFR.In one aspect, move under first linear flow reactor 210 and each the comfortable pre-inversion condition of any other reactor drum before the PFIR.
PFIR can move under all temps scope.In one embodiment, PFIR moves under 230 ° of F or higher temperature.In another embodiment, PFIR moves under the temperature of 230 ° of F～300 ° F.In embodiment more specifically, PFIR moves under the temperature of 240 ° of F～280 ° F.In further embodiment, PFIR moves under the temperature of 260 ° of F～270 ° F.
The plug-flow characteristic can be used in the conversion reactor to optimize the formation of rubber grain.With reference to Fig. 2, PFIR 220 can comprise the whisking appliance 224 that is driven by phonomoter 222 once more.Such whisking appliance can promote the radial dispersion of reactant, but be not intended to axial mixing is provided, so that the back-mixing in the reactor drum minimizes.In one embodiment, can adjust propeller-blade configuration in the linear flow reactor to improve the plug-flow characteristic.
In one embodiment, the whisking appliance that moves this plug flow reactor is to obtain being lower than 175s
-1Shearing rate.In one embodiment, the whisking appliance of this plug flow reactor is with 8s
-1～150s
-1Shearing rate operation.In another embodiment, the whisking appliance of this plug flow reactor is with 8s
-1～90s
-1Shearing rate operation.In one embodiment, the whisking appliance of this plug flow reactor is with 25s
-1～75s
-1Shearing rate operation.In further embodiment, the whisking appliance of this plug flow reactor is with 8s
-1～50s
-1Shearing rate operation.In one aspect, the whisking appliance of this plug-flow conversion reactor PFIR is to be lower than 175s
-1Shearing rate operation.In another aspect, the whisking appliance of PFIR is with 35～90s
-1Shearing rate operation.In an alternative aspect, the whisking appliance of PFIR is with 50～70s
-1Shearing rate operation.The ability of the shearing rate at change system inherent point of inversion place can cause the product form improved.Reactor size, to make speed, agitator speed and whisking appliance configuration be can change with the shearing rate at the inherent point of inversion of system place and the factor of the product form that causes improving.
With reference to Fig. 2, show reactor process 200 once more, wherein from the export pipeline 215 of linear stream pre-transform teactor PIR 210 polymerization reactor 220 that can lead.Come the output of autoreactor 220 can be via pipeline 225 guiding second polymerization reactor 230.Come the output of autoreactor 230 can be via pipeline 235 guiding trimerization reactor drums 240.Come the output of autoreactor 240 can be via pipeline 245 guiding the 4th polymerization reactor 250.In one embodiment, the said polymerization reactor linear flow reactor of respectively doing for oneself.In another embodiment, first polymerization reactor 220 is a conversion reactor.In further embodiment, second polymerization reactor 230 is a conversion reactor.Respectively via pipeline 225,235 and 245 in the future the output of auto-polymerization reactor drums 220 be fed under the situation of extra polymerization reactor 230,240 and 250, vinylbenzene can continue to the polymerization of PS.In one embodiment, reactor drum 230,240 and 250 can be for example plug flow reactor of linear flow reactor, and it also can be equipped with through electric motor driven whisking appliance.In the embodiment shown in Fig. 2, desired like the user, three linear flow reactor 230,240 and 250 are location and be connected in series with polymerization reactor 220 flatly.Those skilled in the art can confirm quantity, location (for example, level or vertical) and the connectivity (for example, serial or parallel connection) of linear flow reactor based on the requirement of needed manufacturing capacity for example or required product transforming degree.Can via pipeline 255 from the end reaction device for example reactor drum 250 take out gained HIPS polymkeric substance and any other residue compound, and can collect the HIPS polymkeric substance afterwards and optional it further processed for example granulation.
In one embodiment, said linear flow reactor comprises the reactor drum that is located immediately at pre-transform teactor at least 2 arranged in series afterwards.In another embodiment, the reactor drum of 2～10 arranged in series is located immediately at after the pre-transform teactor.In further embodiment, the reactor drum of 4 arranged in series is located immediately at after the pre-transform teactor.But said linear flow reactor serial or parallel connection is arranged.In one embodiment, arrange with parallel way at least 2 of said linear flow reactor.In an alternate embodiments, with reference to Fig. 2, one or more reactor drums of representing parallel connection of reactor drum 210,220,230,240,250 above one.For example, on behalf of two reactor drums of parallel connection and reactor drum 240, reactor drum 230 can represent three parallelly connected reactor drums.
Fig. 3 describes to be used for to make continuously the synoptic diagram of the reactor assembly 300 of elastomer reinforced polymer, wherein before the reactor drum scheme of Fig. 2, adds mixing tank 306.In one embodiment, reactor assembly 300 can be used for continuous HIPS method of manufacture.With reference to Fig. 3; Comprise vinylbenzene, elastomerics for example the reaction mixture of polybutadiene rubber and radical initiator can be fed to mixing tank 306 through totally being expressed as one or more feeding lines of 305, and can comprise the whisking appliance 318 that drives through phonomoter 316.
In one embodiment, mixing tank 306 is before the linear flow reactor system of Fig. 2.In Fig. 3, from the export pipeline 307 entering linear stream pre-transform teactor PIR 310 of this mixing tank.Output from PIR 310 can be via pipeline 315 guiding polymer reactors 302 (conversion reactor), and it can comprise the whisking appliance 324 that drives through phonomoter 322.Come the output of autoreactor 320 can be via pipeline 325 guiding second polymerization reactor 330.Come the output of autoreactor 330 can be via pipeline 335 guiding trimerization reactor drums 340.Come the output of autoreactor 340 can be via pipeline 345 guiding the 4th polymerization reactor 350.Come the output of autoreactor 350 to leave said method via pipeline 355.In one embodiment, the said polymerization reactor linear flow reactor of respectively doing for oneself.In another embodiment, first polymerization reactor 320 is a conversion reactor.In further embodiment, second polymerization reactor 330 is a conversion reactor.Respectively via pipeline 325,335 and 345 in the future the output of auto-polymerization reactor drums 320 be fed under the situation of extra polymerization reactor 330,340 and 350, vinylbenzene can continue to the polymerization of PS.In one embodiment, reactor drum 330,340 and 350 can be for example plug flow reactor of linear flow reactor, and it also can be equipped with through electric motor driven whisking appliance.In the embodiment shown in Fig. 3, three linear flow reactor 330,340 and 350 are location and be connected in series with polymerization reactor 320 flatly.Those skilled in the art can confirm quantity, location (for example, level or vertical) and the connectivity (for example, serial or parallel connection) of linear flow reactor based on the requirement of needed manufacturing capacity for example or required product transforming degree.Can via pipeline 355 from the end reaction device for example reactor drum 350 take out gained HIPS polymkeric substance and any other residue compound, and can collect the HIPS polymkeric substance afterwards and optional it further processed for example granulation.
In one embodiment, mixing tank 306 is for example CSTR of stirred tank.In one embodiment, the internal capacity of this mixing tank is 1: 4～8: 1 with the ratio of linear flow reactor.In an alternate embodiments, the volume of this mixing tank is 1: 2～4: 1 with the ratio of linear flow reactor.In further embodiment, the volume of this mixing tank is 1: 2～2: 1 with the ratio of linear flow reactor.In one embodiment, the liquid level percentage ratio of this mixing tank is at 100% place of this tank volume.In another embodiment, the liquid level percentage ratio of this mixing tank is 5～99.9%.In an alternate embodiments, the liquid level of this mixing tank is 10～95%.In further embodiment, the liquid level of this mixing tank is 25～90%.This mixing tank is in another embodiment of CSTR therein, and said liquid level is at the minimum level place of the whisking appliance that is enough to complete this CSTR of submergence.
In one embodiment, mixing tank 306 is without undergoing the warm from external source.In such embodiment, the only heat that is supplied to this mixing tank is from feed stream.In another embodiment, apply heat via external source to this mixing tank.In one aspect, external heat source comprises steam sleeve and any other known device that is used to heat mixing tank.In one embodiment, with the mixture heating up in this mixing tank to the temperature that is lower than 230 ° of F.In another embodiment, with the temperature of this mixture heating up to 150 ° F～225 ° of F.In further embodiment, with the temperature of this mixture heating up to 175 ° F～220 ° of F.
In one embodiment, the product stream that leaves final polymerization reactor is delivered to devolatilizer, before extrusion step, to remove volatile constituent from molten polymer product.Said devolatilizer can comprise preheater.Said devolatilizer and/or preheater can be selected from any suitable devolatilizer design and the design of devolatilizer preheater, for example shell-tube type devolatilizer and board-like devolatilizer.In one embodiment, said devolatilizer is moved under the temperature of 390 ° of F～470 ° F.In further embodiment, said devolatilizer is moved under the temperature of 400 ° of F～450 ° F.Have been found that lower devolatilizer temperature can cause the product form of improving.
Embodiment
Embodiment has been carried out general description, provided embodiment and demonstration its practical and the advantage of following examples as present disclosure.Understand, said embodiment provides as explanation and is not intended to and by any way specification sheets or claim limited.
In one embodiment, the container V-1 shown in Figure 4 and 5 is for example CSTR of stirred vessel.In one embodiment, the internal capacity of V-1 is 1: 4～2: 1 with the ratio of linear flow reactor.In an alternate embodiments, the volume of this mixing tank is 1: 2～2: 1 with the ratio of linear flow reactor.In further embodiment, the volume of this mixing tank is 1: 1～2: 1 with the ratio of linear flow reactor.
In one embodiment, be for example CSTR of stirred vessel like Fig. 4, the container V-2 shown in 5 and 6.In one embodiment, the internal capacity of V-2 is 1: 1～8: 1 with the ratio of linear flow reactor.In an alternate embodiments, the volume of this mixing tank is 2: 1～6: 1 with the ratio of linear flow reactor.In further embodiment, the volume of this mixing tank is 3: 1～5: 1 with the ratio of linear flow reactor.
Use first horizontal piston conversion reactor (HPFIR) method that flows to make high-impact polystyrene.As shown in Figure 4, baseline (baseline) method begins with two CSTR, is 3 or 4 HPFIR afterwards.Employed rubber is Texas, the Firestone Diene 55 (D55) of Orange and the Tactene (1202) of Lanxess Corp.
Table 1 is included in the result who uses the test of Lacqrene 7240 (can derive from the commercial HIPS PS grade of Total Petrochemicals Europe) in the configuration of baseline method:
Use the new configuration shown in Fig. 5 and 6 to make an experiment then.Fig. 5 is depicted as has a CSTR (V-1), is first and second HPFIR (R-1 and R-2) afterwards, is the 2nd CSTR (V-2) afterwards, is third and fourth HPFIR (R-3 and R-4) afterwards.For these tests, selection can derive from the two kinds of grade 825E PS and the 7240PS of the commercial HIPS PS grade of TotalPetrochemicals Europe.
Use 7240 grades to carry out 2 kinds of tests.The method of configuration is as shown in Figure 5 used in test 8.Test 9 is identical with 8, but removing V-1 makes charging be transported to R-1, as shown in Figure 6.
Table 2 shows crucial processing condition and gained character.
Embodiment 3
In embodiment 3, remove reactor drum V-1 and V-2, cause not having in the method CSTR, as shown in Figure 7.This changes the generation gel: rubber is than the improvement of aspect.Carry out 2 kinds of tests.This new method configuration is used in test 12, but removes V-1 and V-2, as shown in Figure 7.Test 13 is identical with test 12, but causes with Lupersol L233.
Table 3 shows the result of embodiment 3.Table 3 also shows, compares with the method for embodiment 2 in art methods in the table 1 and the table 2, and the method for embodiment 3 realizes higher gel: the rubber ratio.
| Test number | 12 | 13 |
| Describe | 7240 heat | 7240w/L233 |
| Initiator | L233 | |
| Initiator concentration, |
100 | |
| Make speed, Pounds Per Hour | 56 | 63 |
| Melt flow rate(MFR) | 3.6 | 4.3 |
| Pellet RPS | 4.1 | 4 |
| Tensile modulus, psi | 258000 | 251200 |
| Elongation at break, % | 49.3 | 58.4 |
| Modulus in flexure, psi | 288400 | 283100 |
| Swelling index | 12 | 12 |
| Gel content | 24.87 | 24.88 |
| Grafting | 182 | 203.5 |
| Gel: rubber | 2.8 | 3.03 |
| RPVF | 21.3 | 26.7 |
Embodiment 4
Use first vertical piston conversion reactor (VPFIR) method that flows to make high-impact polystyrene.Make an experiment with the ESCR value of the product of confirming this VPFIR method.The result is shown in the following table 5:
Utilize the test of the mobile conversion reactor of first vertical piston to cause poor ESCR value.
Use the HPFIR method with four horizontal piston flow reactors as shown in Figure 7 to make high-impact polystyrene, wherein second horizontal reactor is a conversion reactor.The product that leaves the 4th reactor drum is delivered to two devolatilizer and will be recycled to charging from the volatile constituent of removing of said devolatilizer.Make an experiment 31 in the method.
The ESCR performance of the product of this method is very high, has about 26.5% value.RPS distribute obviously than typically under CSTR transforms those of acquisition narrow.
Table 6A
| |
35 | 36 |
| Flow arrangement | HPFIR | HPFIR |
| Product/evaluation | ||
| Feed composition | ||
| The recycling flow velocity, Pounds Per Hour | 21.1 | 21.0 |
| Make speed, Pounds Per Hour | 68 | 67 |
| Product characterizes | ||
| Melt flow, dg/10min | 3.76 | 4.05 |
| Rubber content, % | 8.53 | 8.41 |
| Pellet RPS, μ m | 7.07 | 8.82 |
| Swelling index | 11 | 11 |
| Gel content | 31 | 30.8 |
| Mn | 65753 | 66589 |
| Mw | 177539 | 172753 |
| Polymolecularity | 2.7 | 2.6 |
| RPVF | 40.7 | 40.9 |
| The fracture of breach type socle girder | 1.63 | 1.76 |
| Tensile modulus | 211718 | 210802 |
| Yield tensile strength | 2348 | 2329 |
| Fracture tensile strength | 3348 | 3371 |
| Elongation at break | 62.3 | 63 |
| Modulus in flexure | 235965 | 231541 |
| Flexural strength | 5413 | 5386 |
| ESCR toughness is untreated | 1219 | 1036 |
| ESCR toughness, treated | 139 | 113 |
| ESCR, remaining toughness % | 11.4 | 10.9 |
Embodiment 7
Use has the HPFIR method of 4 horizontal piston flow reactors and makes high-impact polystyrene, and wherein second horizontal reactor is a conversion reactor.The product that leaves the 4th reactor drum is delivered to two devolatilizer and will be recycled to charging from the volatile constituent of removing of said devolatilizer.Sample 38 from embodiment 5 is realized excellent rubber utilization and ESCR performance.Sample 38 is to make at the temperature of reactor that said conversion reactor is sentenced the rising of 300 ° of F.This high temperature causes solids content very high in this reactor drum (34.8%), and therefore causes the high relatively average RPS of pellet of 6.81 μ m.In this embodiment, under lower temperature, sample 38 is reproduced.Five kinds of tests of operation under new lesser temps.In table 8, the condition of said test and the test 38 of result and embodiment 5 are compared.
Under lower temperature, the reproduction from the sample 38 of embodiment 5 is realized lower a little, still gratifying rubber utilization.Compare with single low temperature catalyst system, the low temperature catalyst of 1: 1 ratio and the mixture of high temperature catalyst do not cause better or worse result.
In sample 52, utilize the conversion reaction actuator temperature and the charging of rising of 290 ° of F identical, except in sample 52, not using the PIB with the charging in 38.The narrow particle size distribution of sample 52 realization response device contents and 7.76 rubber particle size; Yet in the product pellet, particle size distribution is wide, is illustrated in the degeneration of form in the final manufacturing stage.The result of sample 52 is shown among the figure of Fig. 9.
The Lacqrene 8260 that can derive from Total Petrochemicals Europe is used among this embodiment and the embodiment 5.For test 33-39,48,50 and 51, the residual toughness percent value that in Fig. 8, will fill a prescription is mapped to RPS.
Table 8A
| Test number | 38 | 48 | 49 |
| Product/description/evaluation | |||
| Make speed, Pounds Per Hour | 67 | 65 | 58 |
| Melt flow rate(MFR) | 4.2 | 5.8 | 4 |
| Rubber particle size | 6.81 | 5.57 | 4.87 |
| Tensile modulus | 206590 | 211850 | 229730 |
| Yield tensile strength | 2370 | 2450 | 2620 |
| Fracture tensile strength | 3170 | 2880 | 3020 |
| Elongation at break | 70.5 | 58.1 | 65.6 |
| Modulus in flexure | 228700 | 233770 | 2470040 |
| Flexural strength | 5130 | 5020 | 5380 |
| Swelling index | 11 | 12 | 12 |
| Gel: rubber | 3.41 | 3.24 | 3.10 |
| RPVF | 39.9 | 35.5 | 33.8 |
| ESCR toughness is untreated | 1125 | 954 | |
| ESCR toughness, treated | 288 | 154 | |
| ESCR, remaining toughness % | 25.6 | 16.1 |
Table 8B
| Test number | 50 | 51 | 52 |
| Product/description/evaluation | Ref48 | ||
| Make speed, Pounds Per Hour | 66 | 61 | 61 |
| Melt flow rate(MFR) | 3.6 | 3.7 | 3.6 |
| Rubber particle size | 5.54 | 6.2 | 7.76 |
| Tensile modulus | 211040 | 221570 | 211820 |
| Yield tensile strength | 2430 | 2510 | 2380 |
| Fracture tensile strength | 3020 | 3100 | 3130 |
| Elongation at break | 64.1 | 44.1 | 44.7 |
| Modulus in flexure | 224000 | 240550 | 230200 |
| Flexural strength | 5070 | 5390 | 5340 |
| Swelling index | 11 | 10 | 10 |
| Gel: rubber | 3.26 | 3.47 | 3.61 |
| RPVF | 36.4 | 36.7 | 40.2 |
| ESCR toughness is untreated | 1128 | 1016 | |
| ESCR toughness, treated | 246 | 50 | |
| ESCR, remaining toughness % | 21.8 | 4.9 |
Embodiment 9
Use has RPVF and the rubber utilization that the method for three or more a plurality of horizontal piston flow reactor (wherein conversion reactor is one of said horizontal piston flow reactor) can realize improving.Make said conversion reactor isolation and its ability of under controlled agitation speed, moving can be improved the control of rubber particle size with the expectation form.Less and be the ability that is controlled at the stir speed (S.S.) of conversion place than the advantage of multiple reactor.The use of a plurality of HPF reactor drums can realize more controlled method; Wherein can be in the amount of controlling pre-inversion, conversion and back conversion reaction to a greater extent, thus can realize bigger control to rubber particle size, rubber utilization and gained form and physical properties.With the method for describing among this paper, use to be in the devolatilizer preheater that reduces under the temperature, can further improve the ESCR value.In one embodiment,, use, can improve the ESCR value at 480 ° of F or the devolatilizer preheater under the low temperature more with the method for describing among this paper.Embodiment can comprise that use is at 460 ° of F or lower, randomly 440 ° of F or lower, randomly 430 ° of F or lower, the devolatilizer preheater under 420 ° of F or the lower temperature randomly.The mensuration of gel percentage ratio and swelling index
The swelling index of high-impact polystyrene is measured as the weight of (using methylbenzene extraction) swollen gel and the ratio of the weight of xerogel.Gel content is divided by the gross weight mensuration of sample as the dry weight of (the methylbenzene extraction of polystyrene sample after) gel.It is normally reported as percentage ratio.The mensuration of percentage graft and rubber percentage ratio
Through methylethylketone (MEK) extraction free PS (not grafted, uncrosslinked) and " insolubles " (that is, rubber, grafting and crosslinked PS) are separated.Be dissolved in the methylene dichloride gained residue and mensuration rubber percentage ratio.
Grafting: the weight that the ratio percentage ratio of rubber is defined as the grafted PS multiply by 100 divided by the weight of rubber.
Rubber percentage ratio among the HIPS is through making two keys and excessive iodine monochloride (ICl) reaction assay in the rubber.The amount that experiences the rubber of this reaction is through carrying out residual titration with the excessive ICl of standardized thiosulfuric acid salt pair and with the comparison of the blank titration of ICl and definite.
The test determination of ESCR
Explain: in the baking oven of 65 ℃ (149 ± 2 ° of F), tensile bars is exposed to oleomargarine (salt-free) different time.Confirm ESCR through measuring elongation.The remaining flexible ESCR of relatively more definite use through exposure and unexposed tensile bars.The remaining flexible ESCR of use grade as using among this paper is: 0-9 is poor; 10-19 is good; 20-30 is very good; With＞30 excellences.
Specimen preparation: sample is according to ASTM program compression molding.Preferably in ten tensile bars of the situation molded of not using silicone release.Oil, railway grease or other chemical should not contact with batten to be tested.Should not touch the surface of waiting to be exposed to oleomargarine.Before test, should let batten shelve 1 hour.
Test: tensile bars is placed sample clamp.Then, smear mid point ± 1 of said batten with thin oleomargarine coating from them " and (that is, sprawl said sample about 2 " scope).Said sample is exposed in the baking oven of 65 ℃ (149 ° of F).Once sample is taken out from baking oven oleomargarine is wiped from sample.Before according to ASTM program determination percentage elongation, let sample shelve 1～2 hour.According to computes maximum strain (ASTM D-790): strain=(6Dd/L
2), wherein the maximum defluxion of D=center sill (deflection, deflection), the degree of depth or the thickness of L=support span (support span) and d=sample.
The measuring of RPVF
Final polymer composites experience dynamic mechanical analysis (DMA).By DMA result, utilize Stephane Jouenne etc. at Macromolecules 2008, the 41 volumes, the technology of discussing in the publication in the 9823-9830 page or leaf can be calculated rubber phase volume(tric)fraction RPVF.
Testing standard and note
1) socle girder impacts the test through ASTM D256
2) melt flow is through ASTM D1238 test
3) rubber particle size (unit, micron) uses methylethylketone to measure as solvent by Malvern 2000 analysers.
4) tensile property is through ASTM D638 test
5) flexural properties is through ASTM D790 test
6) swelling index, gel content and grafting be described among this paper and USP 4,777,210 in, this patent is introduced this paper as a reference fully.
7) the ESCR value is according to United States Patent(USP) No. 4,777, and 210 measure, and this patent is introduced this paper as a reference fully.
8) all tests are carried out through the ASTM standard, except as otherwise noted.
Depend on context, all introductions to this " invention " among this paper can only relate to some embodiments in some cases.In other cases, it can relate to cited theme in one or more (but being not necessarily all) of claim.Though more than relate to embodiment of the present invention, modification and embodiment (comprising it), the invention is not restricted to only these embodiments, modification and embodiment so that those of ordinary skills can carry out and utilize the present invention when the information in this patent is combined with technology with information available.Under the situation that does not break away from base region of the present invention, can expect of the present invention other with further embodiment, modification and embodiment, and the scope of the invention is indicated in the appended claims.
Claims (23)
1. make the method for high-impact polystyrene, comprising:
At least a vi-ny l aromatic monomers, elastomerics and radical initiator are fed to first linear flow reactor to form reaction mixture;
Make said reaction mixture in said first linear flow reactor be polymerized to point under the point that inversion of phases takes place to make first polyblend;
Said first polyblend is fed to second linear flow reactor from said first linear flow reactor;
Make phase inversion point that said first polyblend in said second linear flow reactor is polymerized to said at least mixture to make second polyblend; With
Said second polyblend is fed at least the trilinear flow reactor to carry out the back conversion polymerization of said second polyblend from said second linear flow reactor.
2. the process of claim 1 wherein that said method comprises the linear flow reactor of at least three arranged in series.
3. the process of claim 1 wherein that each linear flow reactor is a horizontal location.
4. the method for claim 3, wherein said second linear flow reactor is moved under the temperature that is higher than 230 ° of F.
5. the process of claim 1 wherein that product stream leaves the said at least the trilinear flow reactor and is delivered to the devolatilizer preheater that under the temperature that is no more than 470 ° of F, moves.
6. the process of claim 1 wherein said charging at first is delivered to the mixing tank before said first linear flow reactor.
7. the method for claim 1 comprises that further product stream leaves the said at least the trilinear flow reactor, and wherein said product stream has at least 20% remaining flexible ESCR value.
8. the method for claim 7, wherein said product stream have and are at least 25% remaining flexible ESCR value.
9. the method for claim 7, wherein said product stream has at least 20% remaining flexible ESCR value to be lower than 10 weight % rubber contents.
10. the method for claim 8, wherein said product stream has at least 25% remaining flexible ESCR value to be lower than 10 weight % rubber contents.
11. the process of claim 1 wherein that product stream leaves the said at least the trilinear flow reactor, has the RPS greater than 5 μ m.
12. make the method for high-impact polystyrene, comprising:
At least a vi-ny l aromatic monomers, elastomerics and radical initiator are fed to mixing tank to form reaction mixture;
Said reaction mixture is fed to first linear flow reactor from said mixing tank;
Make said reaction mixture in said first linear flow reactor be polymerized to point under the point that inversion of phases takes place to make first polyblend;
Said first polyblend is fed to second linear flow reactor from said first linear flow reactor;
Make phase inversion point that said first polyblend in said second linear flow reactor is polymerized to said at least mixture to make second polyblend; With
Said second polyblend is fed at least the trilinear flow reactor to carry out the back conversion polymerization of said second polyblend from said second linear flow reactor.
13. the method for claim 12, wherein said method comprises the linear flow reactor of at least three arranged in series.
14. the method for claim 12, wherein each linear flow reactor is a horizontal location.
15. the method for claim 12, wherein said second linear flow reactor is moved under the temperature that is higher than 230 ° of F.
16. the method for claim 12, wherein said mixing tank is without undergoing thermal source.
17. the method for claim 12 wherein is heated to the temperature that is lower than 230 ° of F with the said reaction mixture in the said mixing tank.
18. the method for claim 12, wherein product stream leaves the said at least the trilinear flow reactor and is delivered to the devolatilizer preheater that under the temperature that is lower than 470 ° of F, moves.
19. the method for claim 12 comprises that further product stream leaves the said at least the trilinear flow reactor, wherein said product stream has at least 10% remaining flexible ESCR value.
20. the method for claim 19, wherein said product stream has at least 15% remaining flexible ESCR value.
21. the method for claim 19, wherein said product stream has at least 10% remaining flexible ESCR value to be lower than 10% rubber content.
22. the method for claim 20, wherein said product stream has at least 15% remaining flexible ESCR value to be lower than 10% rubber content.
23. the method for claim 19, wherein said product stream has the RPS greater than 5 μ m.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40803510P | 2010-10-29 | 2010-10-29 | |
| US61/408,035 | 2010-10-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504119A true CN102504119A (en) | 2012-06-20 |
| CN102504119B CN102504119B (en) | 2016-01-20 |
Family
ID=46216258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110333600.6A Active CN102504119B (en) | 2010-10-29 | 2011-10-28 | The method of high rubber efficiency is realized in high-impact polystyrene reactor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102504119B (en) |
| TW (1) | TWI518099B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992739A (en) * | 2014-05-24 | 2014-08-20 | 南京武家嘴船舶制造有限公司 | Ship body processing process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177512B1 (en) * | 1999-08-02 | 2001-01-23 | Chevron Chemical Company Llc | High impact polystyrene containing polyphenylene oxide |
-
2011
- 2011-10-28 TW TW100139290A patent/TWI518099B/en active
- 2011-10-28 CN CN201110333600.6A patent/CN102504119B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992739A (en) * | 2014-05-24 | 2014-08-20 | 南京武家嘴船舶制造有限公司 | Ship body processing process |
| CN103992739B (en) * | 2014-05-24 | 2016-07-06 | 南京武家嘴船舶制造有限公司 | A kind of hull processes technique |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI518099B (en) | 2016-01-21 |
| CN102504119B (en) | 2016-01-20 |
| TW201217402A (en) | 2012-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1052015C (en) | Grafting, phase-inversion and cross-linking controlled multi-stage bulk process for making ABS graft copolymers | |
| CA1039437A (en) | Continuous mass polymerization process for polyblends | |
| KR940003476B1 (en) | Impact resistant polymer composition and preparation method thereof | |
| EP0015752B1 (en) | A continuous mass polymerization process for the production of polyblends having a dispersed rubber phase with bimodal rubber particle size | |
| US6569941B2 (en) | Process for manufacturing impact resistant monovinylaromatic polymers | |
| WO2007109167A2 (en) | Reactor system for the production of high impact polystyrene | |
| US6528591B2 (en) | Process for preparing extrusion grade ABS polymer | |
| KR101528088B1 (en) | Methods of making high impact polystyrene | |
| CN102348755B (en) | Refrigerator interior liner | |
| EP2300506B1 (en) | Improved low gloss abs compositions and methods | |
| CN102504119A (en) | Method for producing high impact polystyrene | |
| CN1142200C (en) | High impact polystyrene containing polyphenylene oxide | |
| EP2358773B1 (en) | Rubber-reinforced vinyl aromatic (co)polymer, having an optimum balance of physico-mechanical properties and a high gloss | |
| EP2315784A1 (en) | Process for the synthesis of functionalized poly(1,3-alkadienes) and use thereof in the preparation of high impact vinyl aromatic polymers | |
| CN104558429B (en) | Polyphenylacetylene combination production method and thus obtained polyphenylacetylene combination | |
| CN101405313A (en) | Reactor system for the production of high impact polystyrene | |
| KR100463348B1 (en) | Method for preparing rubber modified styrene resin having suprerior environmental stress cracking resistance | |
| HK1191661A (en) | Rubber-reinforced vinyl aromatic (co)polymer, having an optimum balance of physico-mechanical properties and a high gloss | |
| HK1152322A (en) | Process for the synthesis of functionalized poly(1,3-alkadienes) and use thereof in the preparation of high impact vinyl aromatic polymers | |
| HK1152322B (en) | Process for the synthesis of functionalized poly(1,3-alkadienes) and use thereof in the preparation of high impact vinyl aromatic polymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |