CN1360604A - Method for producing polymers with modified shock resistnace in the presence of solvants - Google Patents
Method for producing polymers with modified shock resistnace in the presence of solvants Download PDFInfo
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- CN1360604A CN1360604A CN00810027A CN00810027A CN1360604A CN 1360604 A CN1360604 A CN 1360604A CN 00810027 A CN00810027 A CN 00810027A CN 00810027 A CN00810027 A CN 00810027A CN 1360604 A CN1360604 A CN 1360604A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 230000035939 shock Effects 0.000 title abstract 2
- 229920001971 elastomer Polymers 0.000 claims abstract description 65
- 239000005060 rubber Substances 0.000 claims abstract description 65
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 50
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 230000009466 transformation Effects 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000009826 distribution Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 150000002825 nitriles Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
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- 238000002156 mixing Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003999 initiator Substances 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
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- 238000009835 boiling Methods 0.000 claims description 2
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- 230000008859 change Effects 0.000 claims description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 claims description 2
- 150000004978 peroxycarbonates Chemical class 0.000 claims description 2
- 229950010765 pivalate Drugs 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
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- IUGYQRQAERSCNH-UHFFFAOYSA-M pivalate Chemical compound CC(C)(C)C([O-])=O IUGYQRQAERSCNH-UHFFFAOYSA-M 0.000 claims 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 22
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 22
- 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 21
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 15
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 8
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 5
- 239000000206 moulding compound Substances 0.000 description 5
- 239000005662 Paraffin oil Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
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- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 238000004566 IR spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical group O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Polymerization Catalysts (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a multi-stage method for producing ABS polymers with a modified resistance to shock, by non-aqueous radical polymerization in the presence of solvents and soluble rubber. The solvent or solvents are only introduced to the process after at least 6 to approximately 30 wt. % 5 of the starting monomer mixture has reacted.
Description
The present invention relates to a kind of by polymerization in the presence of solvent and solubility rubber to prepare the method for impact modified polymkeric substance.
Impact modified polymkeric substance by aromatic monomer and olefinically unsaturated nitriles monomer carry out the radical polymerization preparation in the presence of rubber is known as " abs polymer " or " ABS moulding compound " (ABS is from English " acrylonitrile-butadiene-styrene (ABS) " speech).
Here, by aromatics mono-alkenyl compound, olefinically unsaturated nitriles and the optional radical polymerization of other copolymerizations in the presence of solubility, gel-free polybutadiene rubber, particularly continual (continuously) body or solution polymerization, the non-water preparation that realizes the ABS moulding compound is described in, especially, among patent application EP 700941 and the EP 824122, see HoubenWeyl, " organic chemistry method (Methoden der Organischen Chemie) ", volume E20, part I, p.182～217, Georg Thieme press, the Stuttgart; And following patent specification:
DE-OS?25?16?834，DE?43?21?196?A1，EP?0?277
687，EP?0?376?232?B1，EP?0?477?764?B1，EP?0?657?479，EP?0?659?770?A1，EP?0?727
449?A2，US?3?538?190，US?3?449?471，US?5?414?045，US?5?506?304，US?5?569?709
And US 4 315 083.
But the advantage that the characteristics of ABS mass polymerization or ABS solution polymerization are its ecological and economic aspect with and the product inherent colour is shallow and product process during exudate content lower, favourable processing characteristics, high rubber activity and Gao Re distortional point.Body or the solution polymerization in the presence of solubility rubber, carried out about mono-alkenyl compound and olefinically unsaturated nitriles, the problem that research and technos are devoted for years to solution is, the molecular weight distribution of resin phase and grafted rubber particles resin in mutually form and the adjusting problem of distribution of sizes.Particularly processing characteristics, surface luster and hardness/rubber (snappiness)/flexible relation all depends on these factors.
Solution polymerization combines with modern, economic polymkeric substance evaporation technique and enjoys advantage with respect to the known mass polymerization technology of high-impact polystyrene (HI-PS), that is, reaction good reliability and the polymerization technique that carries out in stirring tank are simpler.In addition, it also is provided at and exceeds the possibility that azeotropic monomer composition scope is carried out copolymerization.
According to prior art, ABS industry solution method be by continuously feeding, entirely mix tandem reactor series that tank reactor (CSTR) forms, beat in round-robin annular-pipe reactor or the plug flow reactor (so-called tower reactor) by pump and to carry out continuously.Solution polymerization generally proceeds to incomplete conversion constipation bundle.Solvent, monomer and survival amount conditioning agent are separated by evaporation technique, and partly are recycled in the process.
In hitherto known solution methods, when polymerization began, solvent had been incorporated in the process.In the method for carrying out incessantly, a certain proportion of recovery monomer, molecular weight regulator and solvent, just circulation is returned and is incorporated in first step of reaction before rubber phase changes.Rubber phase changes a speech and is interpreted as a kind of like this process, and wherein, rubber phase changes interior disperse phase into by outer external phase, and simultaneously correspondingly, remaining then changes outer external phase into by interior disperse phase mutually.At prior art, the purpose of this invention is to provide a kind of universal method for preparing impact modified polymkeric substance, can obtain the product that processing characteristics is better, surface dulling (degree) is lower or gloss is higher and rubber/toughness/hardness relation improves by this method.
Surprisingly, this purpose can realize by the following method for preparing impact modified polymkeric substance according to currently known methods: aromatic monomer and olefinically unsaturated nitriles monomer carry out polymerization in the presence of solvent and solubility rubber (particularly polybutadiene rubber), preferably press radical polymerization.Yet unlike the prior art, according to the present invention, this solvent (or multiple solvent) reaches up to transformation efficiency and just is incorporated in the process after being benchmark at least 6～about 30wt% in the initial monomers mixture.
Here, the adding of solvent is preferably implemented after rubber phase changes.
Have now found that, adopt the inventive method can change molecular weight distribution, grafting polybutadiene rubber particulate size-grade distribution and the graft(ing) degree (grafted-on content) of resin phase, make it to help processing characteristics, reduce surface dulling or improve gloss and improve rubber/toughness/hardness relation.
Monomer that reclaims and/or molecular weight regulator also can be introduced or circulate to turn back in the process and go together with solvent.This kind circulation suits from economy and ecological view, because at preparation method's terminal point, what described material obtained after separating from abs polymer is a kind of useless form.
In solution polymerization, reach the superiority that 6～30wt% just adds solvent later on up to transformation efficiency, especially at least three are connected in series reactor, preparing in the process of ABS by uninterrupted (continuously) method, show that the mono-alkenyl aromatic copolymer among this ABS comprises greater than 25wt% bonded olefinically unsaturated nitriles monomer.
The present invention can divide several stages to implement by the method that the non-aqueous solution polymerization prepares the ABS moulding compound of rubber impact modification, particularly is divided into following steps:
A) fs
A) 12～40 weight part olefinically unsaturated nitriles monomers or its mixture of equal value with
B) 88～60 weight part mono-alkenyl aromatic monomers or its mixture of equal value, wherein 0～30 weight part is replaceable be other and a) and b) copolymerization vinyl-, (methyl) acryloyl-, the Malaysia-, Fu Ma-(Furan-), clothing health-, indenes-or norbornylene-monomer, perhaps its mixture of equal value
Gel-frees 5～20 weight part solubilities, preferred, the ready-formed divinyl rubber in the presence of stir, this mixture utilizes free radical initiation carrying out solvent-free polymeric then, until monomer conversion reach with polymerization single polymerization monomer a) and b) sum is benchmark 6～30wt%, changes later state until rubber phase;
B) follow-up phase
Be metered into 10～200 parts by weight solvent or solvent mixture, randomly together with the monomer of other parts a) and b) and/or reclaim monomer a) and b), this polyreaction causes by free radical and under agitation proceeds then, reach until monomer conversion, with monomer a) and b) be benchmark 50～98wt%.
Spendable solvent be make resin maintain mutually in the solution, boiling point is between about 60～160 ℃ polymerization-inert organic compound, can use separately or in the presence of olefinically unsaturated nitriles is monomeric.This type of organic compound for example be benzene,toluene,xylene, ethylbenzene, chlorobenzene, the trimethyl carbinol, hexalin, pimelinketone, butanone, methyl propyl ketone, methyl just-or different-propyl group or-butyl ketone, a phenalgin, cyclopentanone, tetrahydrofuran (THF), dioxane, butylacetate, acetonitrile, propyl acetate or butyl ester, propionitrile and just-or isopropyl cyanide.Toluene, ethylbenzene, butanone and tetrahydrofuran (THF) are preferred.The isomer of solvent above-mentioned and/or mixture also can use.
This polymerization can be implemented by intermittent mode.This polymerization also can be pressed intermittent mode and be implemented on feed process.
Polymerization preferably incessantly (continuously) at least 3 placed in-line reactors in front and back, carry out, wherein first reactor of this multistage (multistage) process preferably Continuous Flow, mix tank reactor (CSTR) or beat the round-robin annular-pipe reactor entirely by pump, wherein operational stage can maintain the stable state monomer conversion of 6～30wt%.Be dissolved in rubber in the monomer and constitute external phase in the first solvent-free reaction stage charging.
Solvent or solvent mixture and any monomer segment of adding and/or recovery monomer and molecular weight regulator, be metered in this complete hybrid second step of reaction, preferably after rubber phase changes (beating in the round-robin annular-pipe reactor) at uninterrupted program: CSTR or by pump.Good thorough mixing, employing powerful mixing stirring component and/or utilization are installed in the on-line mixing device in the endless tube (loop), and utilize static mixer or utilize hybrid element movable and that rotate, and be for example known in the art, is vital.
In uninterrupted polymerization, what is called " finally " reactor that monomer conversion is until reaching desired final transformation efficiency---this numerical value can between 50～98%---, both can be to mix tank reactor entirely, beat the round-robin annular-pipe reactor by pump, also can be the plug flow character reactor, so-called " piston flow " or " tower reactor ".The prior art of relevant reactor is described in Gerrens, and " chemical engineering technology (Chem.Ing.Techn.) " is in 1980,52,477～488 (1980).
When monomer conversion reaches after 50～maximum 98%, can utilize conventional art to shift out solvent, residual monomer and other volatile constituents (oligopolymer and molecular weight regulator), for example at heat exchange vaporizer, flash evaporator, extrude in vaporizer, film or thin layer evaporator or the screw rod vaporizer, and randomly, reach after 6～30% at transformation efficiency, preferably after former continuous rubber phase has changed disperse phase into, be recycled to second and/or one of subsequent reactions stage in.
In preparation process, add with monomer a) and b) be traditional molecular weight regulator, for example mercaptan, allylic cpd, two poly alpha methylstyrenes and terpinolene of benchmark 0.01～about 1.5wt%.
Polyreaction is caused by free radical.Preferred low temperature dissociative grafting living radical initiator, particularly superoxide, for example peroxy carbonates, peroxide two carbonic ethers, peroxide diacyl, peroxy ketal, peroxy esters and peroxide dialkyl group and/or azo-compound or its mixture of using.The pivalate excessively of example, the particularly tertiary butyl, mistake octanoate, perbenzoate and mistake neodecanoic acid ester.The consumption of these initiators, with monomer a) and b) be that benchmark is between 0.01～1wt%.
This polymerization also can completely or partially be undertaken by thermal initiation free radical chain type polyreaction." thermal initiation ", for example as of the prior art, can be referring to K.Kirchner and K.Riedel, Angew.Makromol.Chem., 111,1～16 (1983).
When temperature is higher than about 130 ℃, will generate Diels-Alder adduct in the monomer mixture, it can produce free radical in contrary diene dissociation reaction, therefore the carrying out that can keep Raolical polymerizable.This technology that is known as " thermal initiation " especially can be used for the 3rd and any further step of reaction in.
Polyreaction is carried out in about 60～160 ℃ temperature.Proved that advantageously the first solvent-free reaction stage (transformation efficiency is between 6～30%) had been lower than 120 ℃, preferred 70～90 ℃ temperature is carried out.
Until the polymerization time that meets the requirements of final transformation efficiency is 2～12h, preferred 3～6h.
Conventional additive is dyestuff, oxidation inhibitor, lubricant such as hydrocarbon ils, stablizer and so on for example, can add between polymerization period or before the post-treatment.
Butadiene polymer solubility, gel-free is random and/or the polyhutadiene of block form and even star form and styrene/butadiene copolymers, its contents of ethylene, by two keys, between 2～40%, preferred 8～25%, molecular weight is between 10,000～500,000, the gel particles content that is insoluble to toluene is lower than 1,000ppm.
Ring-alkylated styrenes that aromatics mono-alkenyl compound preferably replaces on vinylbenzene, alpha-methyl styrene, the nuclear and nuclear are gone up the chloro-styrene that replaces.
Olefinically unsaturated nitriles is vinyl cyanide and methacrylonitrile preferably.
Comonomer for example is an acrylate, for example (methyl) methyl acrylate, (methyl) ethyl propenoate and (methyl) tert-butyl acrylate, rich horse and itaconic ester, maleic acid derivatives, the maleimide that replaces of maleic anhydride, maleic acid ester, N-for example, for example advantageously, the N-cyclohexyl-or N-phenyl-maleimide, the N-alkyl phenyl maleimide that replaces on the nuclear, vinylformic acid, methacrylic acid, (methyl) acrylamide, fumaric acid, methylene-succinic acid and acid amides thereof are arranged again.
But the present invention also provides the thermoplastic processing moulding compound by the inventive method preparation, and wherein rubber content is between 6～25wt%, and the preferred content of olefinically unsaturated nitriles monomer in the mono-alkenyl aromatic copolymer is greater than 25wt%.
The notable feature of product of the present invention is its high grafting rubbers degree, grafting content in the high rubber particles that deducts the quotient representation that rubber content obtains divided by rubber content again with gel content:
(gel content-rubber content)/(rubber content),
Wherein gel content is meant and is insoluble to rubber content proportion tetrahydrofuran (THF), crosslinked and that have grafted branches.
This quotient of product of the present invention is between 0.4～2.0.
Rubber particle size and distribute is determined by the turbidity of the dispersion of working sample in Texacar PC, adopt " particle size distribution analysis instrument CAPA 700 ", it by HORIBA (Europe) company (61449, Steinbach) make.
The rubber particles of the ABS resin of the inventive method preparation, and from solvent in solution polymerization at the beginning, before just rubber phase changed, just the particle of those methods that add was compared, and has narrow especially distribution.In product of the present invention, distribution range is used ratio u=D
w/ D
n(weight average (distribution) diameter is divided by number average (distribution) diameter) characterizes, less than 2.5, preferably less than 2.0.The advantage of multistage method of the present invention is, generates the rubber particles that is lower than 100nm and is higher than 1 μ m hardly.One skilled in the art will appreciate that this kind distribution has favourable influence to the surface luster of moulding compound.
The phase structure of this ABS system can utilize Dynamic Analyzer (kinetic analyzer) RDAII (production of Rheometrics company) measure complex shear modulus in-150 ℃～200 ℃ scopes along with variation of temperature is determined.
The soft phase content that one skilled in the art will appreciate that mechanical activation among the ABS can be determined according to the area below the rubber/glass transition peak of loss factor tan δ under the room temperature or according to the modulus size.If rubber content is known, then be wrapped in styrol copolymer content (interior grafting) in the rubber particles just can determine thus.
This rubber particles is compared with the particle that comes autoreaction to add those methods of solvent at the very start, has the interior grafting content in the particle of being wrapped in of increase.In product of the present invention, gum content is increased to more than 1.5 times of original soft phase content because of the styrol copolymer content that is wrapped in the particle, and is preferred more than 1.7 times.
In addition, those skilled in the art also know, in the rubber particles owing to wrapped up the increase of soft phase content due to the styrene copolymerized object area, under the constant and suitable PSD of rubber content (size-grade distribution) condition, the absorption merit that will cause ABS under deformation tension force (for example, notched Izod impact strength) raising, that is, and the raising of rubber usefulness.
Explain the present invention below in conjunction with embodiment and relevant drawings.
The rubber particle size of the embodiment of the invention 1 distribution (PSD) before Fig. 1 represents to evaporate
Fig. 2 represents the PSD of embodiment 4 before evaporation
Fig. 3 represents the PSD of embodiment 5 final products
Fig. 4 represents the PSD of embodiment 6 final products
Fig. 5 represents the PSD of embodiment 7 final products
Fig. 6 represents the PSD of embodiment 8 final products
Embodiment 1: by the semi-continuous polymerzation of the inventive method
Use mixes the reactor series that tandem reactor is formed entirely by 2 continuously feedings, is a full mixing reactor of intermittent feeding subsequently.Material level in first stirring tank is annotated to 0.66kg; In second reactor, to 1.14kg; In the intermittent feeding reactor, to 1.52kg.
The rubber solutions preparation: 80 weight parts 1, the line style of 2-contents of ethylene 11% gather cis-divinyl (BUNA CB HX 502C
, Bayer elastomerics (France) company) be dissolved in 403 parts by weight of styrene and 149 parts by weight of acrylonitrile together with 0.16 weight part 2,6 di tert butyl 4 methyl phenol and 1.38 weight parts, two poly alpha methylstyrenes.
This solution is fed in first reactor with the speed of 0.63kg/h, and anchor shape agitator is kept stirring with 80rpm in the reactor.Temperature of reaction maintains 75 ℃ under atmospheric pressure.Meanwhile, be metered into 0.50g/h with 25% solution form in hydro carbons-butanone mixture and cross the PIVALIC ACID CRUDE (25) tert-butyl ester.Material level maintains 0.66kg.After 3 mean residence times, set up the solids content of 31wt%, be equivalent to, be the transformation efficiency of benchmark 23wt% with vinylbenzene and vinyl cyanide.This operational stage changes later mutually.
The reaction mixture of first reactor is fed in second reactor continuously, and the latter adopts basket agitator to stir with the speed of 200rpm and keep 75 ℃ under atmospheric pressure.Meanwhile, and then add the mixture of 99.4 parts by weight of acrylonitrile, 268.6 parts by weight of styrene, 80 weight part butanone and 0.92 weight part, two poly alpha methylstyrenes with the metering rate of 0.45kg/h to this reactor, be metered into 0.33g with 1% solution form in butanone individually in addition and cross the PIVALIC ACID CRUDE (25) tert-butyl ester.Material level remains on 1.14kg.Setting up the solids content of 27wt%, be equivalent to, is the transformation efficiency of benchmark 25wt% with vinylbenzene and vinyl cyanide.
This program continues to close the input and output material logistics after the 6h.Temperature in second reactor is elevated to 78 ℃, the mixture of feeding 270g butanone and 4.6g two poly alpha methylstyrenes in the time of 20min.In addition individually, in 2h, be metered into 2.2g and cross the solution that the PIVALIC ACID CRUDE (25) tert-butyl ester is dissolved in the 60g butanone.Then, polyreaction is carried out 4h at 78 ℃, and reaching with vinylbenzene and vinyl cyanide is the final transformation efficiency of benchmark 73.6wt%.
20g butanone, 0.08g 2,6 di tert butyl 4 methyl phenol, 1.0g IRGANOX1076
The mixture of (Ciba-Geigy company, Switzerland) and 7.24g paraffin oil under agitation joins in the material of reactor, to reach stabilization.
Reaction mixture evaporates on the co-rotating twin screw vaporizer of 32mm laboratory.
Acquisition contains the ABS of 10.8wt% rubber (pressing infrared spectrometry measures); Acrylonitrile content among its poly--SAN (styrene acrylonitrile copolymer) is 27wt% (pressing infrared spectrometry measures); Gel content: 26.8wt%; Graft(ing) degree 1.5; Limiting viscosity [η]=61ml/g; The notched Izod impact strength of injection moulding standard spillikin, 9.4KJ/m
2, and have narrow size-grade distribution, the ratio D of its weight-average diameter/number average diameter
w/ D
n=1.7.Rubber particle size before the evaporation distributes, and CAPA-700 measures with HORIBA particle size distribution analysis instrument, is shown in (transverse axis: diameter d, μ m among Fig. 1; The longitudinal axis: relative weight content).D
w： 659nmD
n： 389nm ＜100nm： 0wt.％D
w/D
n： 1.7 ＞1,000nm： 9.1wt.％
Embodiment 2: according to semi-continuous polymerzation of the present invention
Repeat the program of embodiment 1, equal 58% but polymerization proceeds to final transformation efficiency.
Acquisition contains the ABS of 13.1wt% rubber; Acrylonitrile content among its poly--SAN is 26wt%; Gel content: 28.9wt%; Graft(ing) degree 1.2; Limiting viscosity [η]=66.5ml/g; The notched Izod impact strength of injection moulding standard spillikin, 22.6KJ/m
2
Embodiment 3: according to successive polymerization of the present invention
Repeat the program of embodiment 1, still
-0.16g/h crosses the PIVALIC ACID CRUDE (25) tert-butyl ester and is fed in first reactor with 25% solution form in hydrocarbon mixture/butanone.After 3 mean residence times, set up the solids content of 17.5wt%, being equivalent to vinylbenzene and vinyl cyanide is the transformation efficiency of benchmark 6.6wt%;
-0.66g/h crosses the PIVALIC ACID CRUDE (25) tert-butyl ester and is fed in second reactor with 25% solution form in hydrocarbon mixture/butanone.Set up the solids content of 21wt%, being equivalent to vinylbenzene and vinyl cyanide is the transformation efficiency of benchmark 18wt%;
-2.42g/h crosses the solution of the PIVALIC ACID CRUDE (25) tert-butyl ester in the 60g butanone and is metered in the post polymerization at intermittence (stage) in second reactor, and carries out polymerization at 78 ℃, reach until final transformation efficiency, and be benchmark with vinylbenzene and vinyl cyanide, 61wt%.
Acquisition contains the ABS of 13.5wt% rubber; Acrylonitrile content among its poly--SAN is 26wt%; Gel content: 27.5wt%; Graft(ing) degree 1.04; Limiting viscosity [η]=66ml/g; The notched Izod impact strength of injection moulding standard spillikin, 19.0KJ/m
2
Embodiment 4: the Comparative Examples of embodiment 1～3 is not according to method of the present invention
Use and embodiment 1 described identical tandem reactor series.The material level degree of filling is 1.03kg in first stirring tank; Second reactor, 1.44kg; The intermittent feeding reactor, 1.5kg.
The rubber solutions preparation: 80 weight parts 1, the line style of 2-contents of ethylene 11% gather cis-divinyl (BUNA CB HX 502C
, Bayer elastomerics (France) company) be dissolved in 525.9 parts by weight of styrene, 200 weight part butanone and 194.5 parts by weight of acrylonitrile together with 0.16 weight part 2,6 di tert butyl 4 methyl phenol.
This solution is fed in first reactor with the speed of 1.0kg/h, and anchor shape agitator is kept stirring with 80rpm in the reactor.Temperature of reaction maintains 75 ℃ under atmospheric pressure.Meanwhile, be metered into 0.98g/h with 3% solution form in butanone and cross the PIVALIC ACID CRUDE (25) tert-butyl ester.Material level maintains 1.03kg.After 3 mean residence times, set up the solids content of 21wt%, be equivalent to, be the transformation efficiency of benchmark 19wt% with vinylbenzene and vinyl cyanide.This operational stage changes later mutually.
The reaction mixture of first reactor is fed in second reactor continuously, and this second reactor adopts basket agitator stirring with the speed of 200rpm and keep 75 ℃ under atmospheric pressure.Meanwhile, and then the mixture that adds 53.9 parts by weight of acrylonitrile, 145.7 parts by weight of styrene, 170 weight part butanone and 6.9 weight parts, two poly alpha methylstyrenes with the metering rate of 0.38kg/h to this reactor, in addition individually, be metered into 0.48g with 2% solution form in butanone and cross the PIVALIC ACID CRUDE (25) tert-butyl ester.Material level remains on 1.44kg.Setting up the solids content of 19wt%, be equivalent to, is the transformation efficiency of benchmark 21wt% with vinylbenzene and vinyl cyanide.
This program continues to close the input and output material logistics after the 6h.Temperature in second reactor is elevated to 78 ℃, is metered into 3.32g and crosses the solution that the PIVALIC ACID CRUDE (25) tert-butyl ester is dissolved in the 60g butanone in 2h.Then, polyreaction is carried out 4h at 78 ℃, and reaching with vinylbenzene and vinyl cyanide is the final transformation efficiency of benchmark 61.5wt%.
10g butanone, 1.0g IRGANOX 1076
The mixture of (Ciba-Geigy company, Switzerland) and 7.24g paraffin oil under agitation joins in the material of reactor, to reach stabilization.
Reaction mixture evaporates on the co-rotating twin screw vaporizer of 32mm laboratory.
Acquisition contains the ABS of 12.4wt% rubber; Acrylonitrile content among its poly--SAN is 26wt%; Gel content: 30.1wt%; Graft(ing) degree 1.4; Limiting viscosity [η]=53ml/g; The notched Izod impact strength of injection moulding standard spillikin, 17.8KJ/m
2, and have wide, bomodal size distribution, D
w/ D
n=3.6.D
w： 356nmD
n： 100nm ＜100nm 16wt.％D
w/D
n： 3.56 ＞1,000nm： 7wt.％
Significantly different with the ABS of embodiment 1 (not adding solvent) in first step of reaction, when solvent joins the fs simultaneously, obtain a kind of unfavorable wide rubber particle size and distribute, have the rubber particles that is higher than 2 mu m ranges.
Embodiment 5: by successive polymerization of the present invention
Experiment is under carbonic acid gas, earlier by 2 continuously feedings, mix in the continuous lab setup that tandem reactor forms entirely, carries out in the reactor of the stirring of 4L piston flow residence time feature subsequently.
Raw mix comprises: 53.1 weight parts 1, the line style of 2-contents of ethylene 11% gather cis-divinyl (BUNA CB HX 502C
, Bayer elastomerics (France) company), line style polyhutadiene-polystyrene block copolymer (BUNA BL 8497 of 22.8 weight part polystyrene block content 30wt%
, Bayer elastomerics (France) company), 646 parts by weight of styrene, 227 parts by weight of acrylonitrile, 0.15 weight part 2,6 di tert butyl 4 methyl phenol and 2.18 weight parts, two poly alpha methylstyrenes.
In this lab setup, add the above-mentioned raw materials mixture of 1kg/h incessantly through heat exchanger heats to 60 ℃.Material level maintains 1kg, and the 0.16g that is added in 25% solution form in hydro carbons and the butanone mixture then continuously crosses the PIVALIC ACID CRUDE (25) tert-butyl ester.First reactor is kept 75 ℃ under atmospheric pressure.After 3 mean residence times, setting up with vinylbenzene and vinyl cyanide is the transformation efficiency of benchmark 16wt%.
Second reactor is kept 75 ℃ under atmospheric pressure.Product stream is fed into second reactor incessantly from first reactor, meanwhile, add 0.33g/h with 25% solution form in hydro carbons and butanone mixture and cross the PIVALIC ACID CRUDE (25) tert-butyl ester, under agitation add 0.87g/h two poly alpha methylstyrenes and 140g/h butanone then in addition individually.After 3 mean residence times, setting up with vinylbenzene and vinyl cyanide is the transformation efficiency of benchmark 25wt%.
1.17g/h crossing the PIVALIC ACID CRUDE (25) tert-butyl ester and 110g/h butanone is metered into incessantly from the material that second reactor is discharged, then mixture in plug flow reactor, 80 ℃ reach down through mean residence time 4h, be the transformation efficiency of benchmark 56.2wt% with vinylbenzene and vinyl cyanide.
0.08g/h 2,6 di tert butyl 4 methyl phenol, 0.95g/h IRGANOX1076
(Ciba-Geigy company) and 6.9g/h paraffin oil are dissolved in solution in the 10g/h butanone and are fed into continuously from plug flow reactor is flowed through the discharge logistics of on-line mixing device.Solution evaporates on 32mm co-rotating twin screw vaporizer.
Acquisition contains the ABS of 13.4wt% rubber; Acrylonitrile content among its poly--SAN is 25wt%; Gel content: 29.3wt%; Graft(ing) degree 1.2; Limiting viscosity [η]=85.5ml/g; The notched Izod impact strength of injection moulding standard spillikin, 31KJ/m
2, have D
w/ D
n=1.84 narrow size-grade distribution.D
w： 219nmD
n： 119nm ＜100nm： 9wt.％D
w/D
n： 1.84 ＞1,000nm： 0wt.％
Embodiment 6: by the successive polymerization of the inventive method
Repeat the foregoing description 5, adopt same amount and product stream strand, but in raw mix with 76 weight parts 1,2-vinyl double bond content equals line style polyhutadiene (the Buna HX 502 of 11wt%
, Bayer (France) company) and as unique solubility rubber.The second laboratory reaction device stirs with the anchor shape agitator of 100rpm, and also stirs with the 20mm diameter high speed dispersion head of 800rpm in addition.
The transformation efficiency of setting up is first reactor, 15wt% respectively; The second reactor 27wt% is a benchmark with vinylbenzene and vinyl cyanide.
Final transformation efficiency after the 3rd step of reaction is that benchmark is 62wt% with vinylbenzene and vinyl cyanide.
Acquisition contains the ABS of 12.1wt% rubber; Acrylonitrile content among its poly--SAN is 26wt%; Gel content: 28.3wt%; Graft(ing) degree 1.34; Limiting viscosity [η]=95.8ml/g; The notched Izod impact strength of injection moulding standard spillikin, 25KJ/m
2, have D
w/ D
n=2.1 narrow size-grade distribution.D
w： 200nmD
n： 94nm ＜100nm： 20.5wt.％D
w/D
n： 2.1 ＞1,000nm： 0.3wt.％
Embodiment 7: according to the batchwise polymerization of the inventive method
In strap clamp cover glass laboratory reactor and under carbonic acid gas, 96g1, line style polyhutadiene (the BUNA HX 502 of 2-vinyl double bond content 11%
, Bayer (France) company) be dissolved in the 805.9g vinylbenzene, add 2.76g two poly alpha methylstyrenes and 0.19g2 simultaneously, the 6-di-tert-butyl-4-methy phenol stirs adding 298.1g vinyl cyanide then.Mixture heating up to 75 ℃, the basket agitator of wire is kept stirring with 300rpm around here, polyreaction along with 0.5g cross the PIVALIC ACID CRUDE (25) tert-butyl ester with 25% in hydro carbons and butanone mixture the solution form adding and cause.Reaching with vinylbenzene and vinyl cyanide is after the transformation efficiency of benchmark 18wt%, add 450g butanone, 5.52g two poly alpha methylstyrenes, and, therewith dividually, 4.14g cross the PIVALIC ACID CRUDE (25) tert-butyl ester, temperature is elevated to 78 ℃, and mixture continues to stir 6h subsequently, is the final transformation efficiency of benchmark 59wt% until reaching with vinylbenzene and vinyl cyanide.0.1g2,6-di-tert-butyl-4-methy phenol, 1.2g IRGANOX 1076
(Ciba-Geigy company, Sweden), with the 8.7g paraffin oil with high speed agitator (Pentraulik laboratory mixing machine, 2,800rpm) mix, to reach stable, this solution evaporates rotating in the same way on the screw rod vaporizer of 32mm laboratory then.
Acquisition contains the ABS of 12.8wt% rubber; Acrylonitrile content among its poly--SAN is 26wt%; Gel content: 30.6wt%; Graft(ing) degree 1.4; Limiting viscosity [η]=57.5ml/g; The notched Izod impact strength of injection moulding standard spillikin, 24.3KJ/m
2, have D
w/ D
n=1.98 narrow size-grade distribution.D
w： 196nmD
n： 99nm ＜100nm： 19wt.％D
w/D
n： 1.98 ＞1,000nm： 0wt.％
Embodiment 8: according to the batchwise polymerization of the inventive method
Repeat above embodiment 7, but the consumption of the first polymerization stage molecular weight regulator reduces to 0.7g, solubilizing agent not, and after adding solvent, reduce to (adding) 1.3g two poly alpha methylstyrenes, to proceed to vinylbenzene and vinyl cyanide be the final transformation efficiency of benchmark 79.5wt% to polyreaction then.
Acquisition contains the ABS of 9.9wt% rubber; Acrylonitrile content among its poly--SAN is 28wt%; Gel content: 31.2wt%; Graft(ing) degree 2.1; Limiting viscosity [η]=99ml/g; The notched Izod impact strength of injection moulding standard spillikin, 24.4KJ/m
2, have D
w/ D
n=1.74 narrow size-grade distribution.D
w： 161nmD
n： 92nm ＜100nm： 26wt.％D
w/D
n： 1.74 ＞1,000nm： 0.2wt.％
Claims (18)
1. multistage method for preparing impact modified abs polymer by the non-water radical polymerization in the presence of solvent and solubility rubber, it is characterized in that one or more solvents just are incorporated in the process at least after transformation efficiency reaches 6 of starting monomer mixture～about 30wt%.
2. the method for claim 1 is characterized in that, these one or more solvents just are incorporated in the process when rubber exists with the disperse phase form.
3. the method for any one in the claim 1 or 2 is characterized in that, recovery monomer and/or molecular weight regulator are introduced into and circulate together with solvent and turn back in the process.
4. the method for any one in the claim 1～3 is characterized in that, it carries out in 3 or more a plurality of tandem reactor.
5. the method for any one in the claim 1～4 is characterized in that, it is divided into following steps and implements:
A) fs
A) 12～40 weight part olefinically unsaturated nitriles monomers or its mixture of equal value with
B) 88～60 weight part mono-alkenyl aromatic monomers or its mixture of equal value, wherein 0～30 weight part is replaceable be other and a) and b) copolymerization vinyl-, (methyl) acryloyl-, the Malaysia-, Fu Ma-, the clothing health-, indenes-or norbornylene-monomer, perhaps its mixture of equal value
In the presence of 5～20 weight part solubility divinyl rubbers, stir, this mixture utilizes free radical initiation carrying out solvent-free polymeric then, until monomer conversion reach with polymerization single polymerization monomer a) and b) sum is benchmark 6～30wt%, change later state until rubber phase, this moment, divinyl rubber existed as disperse phase;
B) follow-up phase
Be metered into 10～200 parts by weight solvent or solvent mixture, randomly together with the monomer of other parts a) and b) and/or reclaim monomer a) and b), this polyreaction causes by free radical and under agitation proceeds then, until monomer conversion reach with monomer a) and b) be benchmark 50～98wt%.
6. the method for any one in the claim 1～5 is characterized in that, this impact modified polymkeric substance comprises greater than 25wt% and is combined in olefinically unsaturated nitriles monomer in the mono-alkenyl aromatic copolymer.
7. the method for any one in the claim 1～6 is characterized in that, it is beaten in round-robin annular-pipe reactor and/or the piston flow characteristic reactions device at full mixing tank reactor, by pump and carries out.
8. the method for any one in the claim 1～7, it is characterized in that, as solvent, make resin maintain mutually in the solution, boiling point is between about 60～160 ℃ polymerization-inert organic compound, can use separately or in the presence of olefinically unsaturated nitriles is monomeric.
9. the method for claim 8, it is characterized in that, as solvent, use benzene,toluene,xylene, ethylbenzene, butanone, chlorobenzene, the trimethyl carbinol, hexalin, pimelinketone, butanone, methyl propyl ketone, methyl just-or different-propyl group or-butyl ketone, mono chloro benzene, cyclopentanone, tetrahydrofuran (THF), dioxane, butylacetate, acetonitrile, propyl acetate or butyl ester, propionitrile, just-or the isomer and/or the mixture of isopropyl cyanide and above-mentioned substance.
10. the method for any one in the claim 1～9; it is characterized in that; polyreaction adopts free radical to cause; initiator comprises low temperature dissociative grafting living radical initiator; particularly the crossing pivalate, cross octanoate of superoxide such as peroxy carbonates, peroxide two carbonic ethers, peroxide diacyl, peroxy ketal, peroxy esters, peroxide dialkyl group and/or the azo-compound or the tertiary butyl, perbenzoate and cross the neodecanoic acid ester, and composition thereof.
11. the method for any one is characterized in that in the claim 1～10, polyreaction is completely or partially undertaken by the polymerization of thermal initiation free radical chain type.
12. the method for any one is characterized in that in the claim 1～11, the solvent-free reaction of 6～30wt% of starting monomer mixture is to be lower than 120 ℃, and preferred 70～90 ℃ temperature is carried out.
13. the method for any one is characterized in that in the claim 1～12, as rubber, use the polyhutadiene and the styrene/butadiene copolymers of random and/or block form and/or star form, its contents of ethylene is by two keys, between 2～40%, preferred 8～25%, molecular weight is between 10,000～500, and 000, the gel particles content that is insoluble to toluene is lower than 1,000ppm.
14. but the polymkeric substance of an impact modified thermoplastic processing is characterized in that they are to prepare according to the method for any one in the claim 1～13.
15. the polymkeric substance of claim 14 is characterized in that, they have the rubber content of 6～25wt% and are preferably more than the olefinically unsaturated nitriles monomer content of 25wt% in the mono-alkenyl aromatic copolymer.
16. the polymkeric substance of any one is characterized in that in claim 14 or 15, it is 0.4～2.0 divided by the merchant of rubber content again that gel content deducts rubber content.
17. the polymkeric substance of any one is characterized in that in the claim 14～16, its rubber particles diameter Distribution scope is used ratio D
w/ D
nCharacterize, less than 2.5, especially preferably less than 2.0.
18. the polymkeric substance of any one is characterized in that in the claim 14～17, is less than 10%, preferably is less than 1% rubber particles and has less than 100nm or greater than the diameter of 1 μ m.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19931254A DE19931254A1 (en) | 1999-07-07 | 1999-07-07 | Process for the preparation of impact modified polymers in the presence of solvents |
| DE19931254.0 | 1999-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1360604A true CN1360604A (en) | 2002-07-24 |
Family
ID=7913883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00810027A Pending CN1360604A (en) | 1999-07-07 | 2000-06-26 | Method for producing polymers with modified shock resistnace in the presence of solvants |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1200497A1 (en) |
| JP (1) | JP2003504496A (en) |
| KR (1) | KR20020019948A (en) |
| CN (1) | CN1360604A (en) |
| AR (1) | AR025194A1 (en) |
| AU (1) | AU5978600A (en) |
| BR (1) | BR0012170A (en) |
| CA (1) | CA2378296A1 (en) |
| DE (1) | DE19931254A1 (en) |
| MX (1) | MXPA01013437A (en) |
| WO (1) | WO2001004169A1 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH069732A (en) * | 1992-06-24 | 1994-01-18 | Nippon Steel Chem Co Ltd | Production of rubber-modified styrene/acrylonitrile copolymer resin |
| MY111227A (en) * | 1993-06-29 | 1999-09-30 | Mitsui Chemicals Inc | Process for continuously preparing rubber modified styrene resins |
-
1999
- 1999-07-07 DE DE19931254A patent/DE19931254A1/en not_active Withdrawn
-
2000
- 2000-06-26 BR BR0012170-3A patent/BR0012170A/en not_active Withdrawn
- 2000-06-26 JP JP2001509778A patent/JP2003504496A/en active Pending
- 2000-06-26 EP EP00945821A patent/EP1200497A1/en not_active Withdrawn
- 2000-06-26 CN CN00810027A patent/CN1360604A/en active Pending
- 2000-06-26 AU AU59786/00A patent/AU5978600A/en not_active Abandoned
- 2000-06-26 WO PCT/EP2000/005894 patent/WO2001004169A1/en not_active Application Discontinuation
- 2000-06-26 KR KR1020027000143A patent/KR20020019948A/en not_active Application Discontinuation
- 2000-06-26 MX MXPA01013437A patent/MXPA01013437A/en not_active Application Discontinuation
- 2000-06-26 CA CA002378296A patent/CA2378296A1/en not_active Abandoned
- 2000-07-04 AR ARP000103409A patent/AR025194A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001004169A1 (en) | 2001-01-18 |
| BR0012170A (en) | 2002-03-19 |
| EP1200497A1 (en) | 2002-05-02 |
| KR20020019948A (en) | 2002-03-13 |
| JP2003504496A (en) | 2003-02-04 |
| MXPA01013437A (en) | 2002-07-30 |
| AR025194A1 (en) | 2002-11-13 |
| CA2378296A1 (en) | 2001-01-18 |
| AU5978600A (en) | 2001-01-30 |
| DE19931254A1 (en) | 2001-01-11 |
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| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |