GB2156368A - Block copolymers and manufacture thereof - Google Patents
Block copolymers and manufacture thereof Download PDFInfo
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- GB2156368A GB2156368A GB08507762A GB8507762A GB2156368A GB 2156368 A GB2156368 A GB 2156368A GB 08507762 A GB08507762 A GB 08507762A GB 8507762 A GB8507762 A GB 8507762A GB 2156368 A GB2156368 A GB 2156368A
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000002243 precursor Substances 0.000 claims abstract description 11
- -1 vanadium halide Chemical class 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 125000001979 organolithium group Chemical group 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-XVNBXDOJSA-N [(1e)-buta-1,3-dienyl]benzene Chemical compound C=C\C=C\C1=CC=CC=C1 XZKRXPZXQLARHH-XVNBXDOJSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229940093470 ethylene Drugs 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
Block copolymers of formula (A)a(D)b(M)c, in which A is a vinyl aromatic block, D is a conjugated diene block, and M is a C3-13alpha-olefin block optionally including ethylene, a is 20-5000 and b is 1-10, are prepared by polymerising M in the presence of (i) a precursor polymer of formula (A)a(D)bLi and (ii) a titanium or vanadium halide. Certain block copolymers in which M is propylene are claimed per se.
Description
SPECIFICATION
Block copolymers and manufacture thereof
The present invention relates to block copolymers and to a process for their manufacture.
According to a first aspect of the present invention there is provided block copolymers comprising units derived from at least one conjugated diene D, units derived from at least one vinyl-aromatic compound A, and units derived from at least one a-ole- fin M, the structure of the block copolymer being representable by the formula (A)a(D)b(M)C, characterised in that: - a is greater than or equal to 20 and less than or equal to 5000,
- b is greater than or equal to 1 and less than or equal to 10,
- M is proplyene,
- the degree c of copolymerisation of propyiene is such that the number-average molecular weight of the polypropylene block is from 10,000 to 200,000 and
- the polypropylene block consists of a mixture of isotatic, heterotactic and syndiotactic triads.
The vinyl-aromatic compounds to be used in accordance with the invention are preferably compounds capable of undergoing anionic polymerisation such as, for example, styrene, amethylstyrene, vinylnaphthalene, vinyltoluene, 2vinyltoluene, 2-vinylpyridine, 4- vinylpyridine, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate or mixtures of these substances. The conjugated dienes to be used are preferably 1,3-butadiene and substituted butadienes such as isoprene, piperylene, 2,3-dimethyl1,3-butadiene, 1-phenyl-1,3- butadiene or mixtures of these substances.
According to a preferred embodiment of the present invention, the polypropylene block of the block copolymer according to the invention consists of a mixture of isotactic, heterotactic and syndiotactic polymeric triads and this mixture may comprise from 30 to 60% of isotactic triads, from 20 to 35% of heterotactic triads and from 20 to 35% of syndiotactic triads.
According to a second aspect of the present invention there is provided a process for the manufacture of block copolymers by polymerising at least one monomer M chosen from among the aolefins having from 3 to 13 carbon atoms and mixtures of these a-olefins with ethylene, in at least one solvent and in the presence of a catalyst system comprising, firstly, a halide Mt of a transition metal chosen from among titanium and vanadium and, secondly, an organolithium polymer precursor of the formula (A)a(D)bLi, in which A is at least one vinyl-aromatic compound and D is at least one conjugated diene, the atomic ratio Li1Mt being from 1 to 3, characterised in that::
- the catalyst system essentially consists of the said organolithium polymer precursor and of a halide of the transition metal Mt, in which the metal is tetravalent,
- a is greater than or equal to 20 and less than or equal to 5000,
- b is greater than or equal to 1 and less than or equal to 10 and
- the concentration of the said precursor in the reaction mixture is from 2.10-3 to 5,10-2 mole per litre.
The process according to the invention can be carried out at a temperature of from 0 to +100"C under a pressure of, approximately, from 0.8 bar to 1000 bars and in the presence of at least one hydrocarbon solvent.
Preferably, the hydrocarbon solvents to be used in the present process are aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as hexane, heptane and the like, and cycloaliphatic hydrocarbons such as cyclopentane, cyclohexáne and methylcyclohexane. These solvents are inert and can be employed either alone or in the form of mixtures of two or more of them. The amount to be used of these hydrocarbon solvents may be generally from 1 to 20 parts by weight per part by weight of the total monomers. These solvents and the monomers should, before use, be completely freed from substances such as water, oxygen, carbon dioxide, certain sulphur compounds and acetylenes, which would destroy the initiators employed in the present process and the active ends of the growing polymer.According to another embodiment of the invention, it is also possible to obtain the block copolymer not only in solution but also in suspension in a solvent, by suitably choosing the sequence of addition of the solvents and of the monomers.
Among the transition metal halides present in the composition of the catalyst system according to the present invention, titanium tetrachloride, vanadium tetrachloride and mixtures of these are preferred.
The duration of the polymerisation reaction of the monomers M is advantageously fom 1 to 90 minutes depending on the chosen temperature and the chosen pressure.
Given the respective reactivities of ethylene and of the a-olefin in the presence of the catalyst system in question, it is preferable that the mixture subjected to polymerisation in the process according to the invention should comprise at least 20 mole% of a-olefin and at most 80 mole% of ethyl ene.
The examples which follow are given by way of illustration and are not intended to limit the present invention.
Example 1 An organolithium polymer precursor of the formula: (styrene),0O(butadiene)3Li is first of all prepared in accordance with the well- known methods described in particular by
J.E.L. ROOVERS and S. BYWATER in Macromolecules 8, 3 (1975). This precursor is reacted, in toluene, with titanium tetrachloride, using a molar ratio Li/Ti of 2. The organolithium precursor thus formed is then introduced into a glass reactor kept under an inert gas atmosphere at the same time as an additional amount of toluene, so chosen that the precursor concentration in the mixture is 6.5 x 10-3 mole per litre.
Propylene is introduced into the reactor until the pressure reaches 850 millibars and the polymerisation is carried out at a constant temperature of 20"C for 60 minutes. At the end of the reaction there is obtained, in a yield of 280 grams per hour per atmosphere pressure and per gram-atom of titanium per litre, two-block copolymer of the formula: (styrene)10(butadiene)3(prnpylene), This coploymer is analysed:
- first, by the gel permeation chromatography technique, in 1,2,4-trichlorobenzene at 140"C, using a WATERS GPC 200 apparatus, and
- secondly, by the carbon 13 nuclear magnetic resonance spectrometry technique, using
BRUCKER W.P. 60 D.S. and BRUCKER 250 apparatuses.
The number-average molecular weight of the polypropylene block, measured by the first-mentioned technique, is 30,500. Figure 1 shows the spectrum obtained by the second technique; this spectrum makes it possible to identify unambiguously the different blocks of the two-block copolymer and to establish that the polypropylene block contains 46% of isotactic triads, 27% of heterotactic triads and 27% of syndiotactic triads.
Example 2
Using the same catalyst system as in the preced
ing example, in an amount of 3 x 103 mole of pre
cursor per litre, a gas mixture consisting of 80
mole% of propylene and 20 mole% of ethylene is
introduced into the reactor until a pressure of 850
millibars is reached. The copolymerisation of these
monomers is carried out at a constant temperature
of 20"C for 60 minutes. At the end of the reaction,
a three-block copolymer is recovered in a yield of
655 grams per hour per atmosphere pressure and
per gram-atom of titanium per litre, and is ana
lysed in accordance with the same techniques as in
Example 1. The gel permeation chromatography
spectrum makes it possible to establish that the
poly-(ethylene, copropylene) block has a number
average molecular weight of 70,600 and that it comprises 50 mole% of units derived from ethylen
and 50 mole% of units derived from propylene.
Figure 2 shows the carbon 13 nuclear magnetic
resonance spectrum determined on the three-block
copolymer obtained.
Claims (13)
1. Block coploymers comprising units derived
from at least one conjugated diene D, units derived
from at least one vinyl-aromatic compound A, and
units derived from at least one a-olefin M, the
structure of the block copolymer being represented
by the formula (A),(D)b(M),, wherein:
a is greater than or equal to 20 and less than or
equal to 5000.
b is greater than or equal to 1 and less than or
equal to 10,
M is propylene.
the degree c of copolymerisation of propylene is such that the average molecular weight of the polypropylene block is from 10,000 to 200,000 and
the polypropylene block consists of a mixture of isotactic, heterotactic and syndiotactic triads.
2. Block copolymers according to Claim 1, wherein the mixture constituting the block (M) comprises from 30 to 60% of isotactic triads, from 20 to 35% of heterotactic triads and from 20 to 35% of syndiotactic triads.
3. Block copolymers according to Claim 1 or
Claim 2 wherein the vinyl-aromatic compound is chosen from among styrene; a-methylstyrene, vinylnaphthalene, vinyltoluene and mixtures thereof.
4. Block copolymers according to any one of
Claims 1 to 3 wherein the conjugated diene is chosen from among 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl- 1,3-butadiene, 1-phenyl-1,3butadiene and mixtures thereof.
5. Process for the manufacture of block copolymers by polymerising at least one monomer M chosen from among the a-olefins having from 3 to 13 carbon atoms and mixtures of such a-oiefins with ethylene, in at least one solvent and in the presence of a catalyst system comprising (i) a halide of a transition metal M, chosen from among titanium and vanadium, and (ii) an organolithium polymer precursor of the formula (a)a(D)bLi, in which A is at least one vinyl-aromatic compound and D is at least one conjugated diene, the atomic ratio Li/Mt being from 1 to 3, wherein::
the transition metal Mt is tetravalent,
a is greater than or equal to 20 and less than or equal to 5000,
b is greater than or equal to 1 and less than or equal to 10, and
the concentration of the said precursor in the reaction mixture is from 2 x 1O-3 to 5 x 10-2 mole per litre.
6. Process according to Claim 5, wherein the reaction pressure is from 0.8 bar to 1000 bars.
7. Process according to Claim 5 or Claim 6, wherein the reaction temperature is from 0 C to +100"C.
8. Process according to any one of Claims 5 to 7, wherein the solvent is chosen from among aliphatic, aromatic and cycloaliphatic hydrocarbons.
9. Process according to any one of Claims 5 to 8, wherein the solvent is used in an amount of from 1 to 20 parts by weight per part by weight of the total monomers
10. Process according to any one of Claims 5 to 9, wherein the monomer M is a mixture comprising at least 20 mole% of a-olefins and at most 80 mole % of ethylene.
11. Block copolymers substantially as hereinbefore described in Example 1 or Example 2.
12. Process for the manufacture of block copolymers substantially as hereinbefore described in
Example 1 or Example 2.
13. Block copolymers whenever produced by the process of any one of Claims 5 to 10 and 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8404824A FR2562079B1 (en) | 1984-03-28 | 1984-03-28 | BLOCK COPOLYMERS AND A PROCESS FOR THEIR MANUFACTURE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8507762D0 GB8507762D0 (en) | 1985-05-01 |
| GB2156368A true GB2156368A (en) | 1985-10-09 |
| GB2156368B GB2156368B (en) | 1987-10-28 |
Family
ID=9302550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08507762A Expired GB2156368B (en) | 1984-03-28 | 1985-03-26 | Block copolymers and manufacture thereof |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS6112712A (en) |
| BE (1) | BE902035A (en) |
| CA (1) | CA1281451C (en) |
| CH (1) | CH662574A5 (en) |
| DE (1) | DE3510624A1 (en) |
| ES (1) | ES541366A0 (en) |
| FR (1) | FR2562079B1 (en) |
| GB (1) | GB2156368B (en) |
| GR (1) | GR850760B (en) |
| IE (1) | IE58344B1 (en) |
| IT (1) | IT1182724B (en) |
| LU (1) | LU85818A1 (en) |
| NL (1) | NL8500919A (en) |
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|---|---|---|---|---|
| CN108137749A (en) * | 2015-10-16 | 2018-06-08 | 株式会社普利司通 | Multiple copolymer, resin combination, cross-linkable resin composition and product |
| CN108137765A (en) * | 2015-10-16 | 2018-06-08 | 株式会社普利司通 | Multiple copolymer, rubber composition, crosslinked rubber composition and rubber |
| CN108137759A (en) * | 2015-10-16 | 2018-06-08 | 株式会社普利司通 | Multiple copolymer, rubber composition, crosslinked rubber composition and rubber |
| EP3363838A4 (en) * | 2015-10-16 | 2018-09-05 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition, and rubber article |
| EP3363839A4 (en) * | 2015-10-16 | 2019-01-09 | Bridgestone Corporation | Multicomponent copolymer, rubber composition, cross-linked rubber composition, and rubber article |
| US10920003B2 (en) | 2015-10-16 | 2021-02-16 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2620442B2 (en) * | 1991-09-21 | 1997-06-11 | ジューキ 株式会社 | Needle thread supply device |
| JPH0687914B2 (en) * | 1991-09-21 | 1994-11-09 | ジューキ株式会社 | Upper thread feeder |
| JP7255070B2 (en) * | 2015-10-16 | 2023-04-11 | 株式会社ブリヂストン | Multidimensional copolymer, rubber composition, crosslinked rubber composition, rubber product, and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3418394A (en) * | 1966-01-07 | 1968-12-24 | Phillips Petroleum Co | Process for making block copolymers of conjugated dienes and vinyl-substituted aromatics |
| US3931126A (en) * | 1967-10-04 | 1976-01-06 | Phillips Petroleum Company | Modification of conjugated diene polymers by treatment with organolithium and n,n,n',n'-tetramethylalkylenediamine compounds |
| CH499644A (en) * | 1969-11-21 | 1970-11-30 | Fischer Ag Brugg Georg | Weft yarn cutting device on a weaving machine |
| US4122134A (en) * | 1974-02-13 | 1978-10-24 | Sumitomo Chemical Company, Limited | Method for producing transparent block copolymer resin |
| US4208356A (en) * | 1974-09-17 | 1980-06-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing mixture of block copolymers |
| US3992483A (en) * | 1975-09-25 | 1976-11-16 | Phillips Petroleum Company | Promoters in the polymerization of monovinyl-aromatic compounds with primary lithium initiators |
| US4107238A (en) * | 1976-01-22 | 1978-08-15 | Exxon Research & Engineering Co. | Graft copolymerization process |
| DE2938658A1 (en) * | 1979-09-25 | 1981-04-09 | Basf Ag, 6700 Ludwigshafen | SOLUTIONS OF BIFUNCTIONAL ORGANOLITHIUM COMPOUNDS IN NON-POLAR ORGANIC HYDROCARBONS AS SOLVENTS, METHOD FOR THE PRODUCTION OF SUCH SOLUTIONS AND THE USE THEREOF |
| DE3309748A1 (en) * | 1982-07-23 | 1984-03-01 | Veb Chemische Werke Buna, Ddr 4212 Schkopau | METHOD FOR PRODUCING MULTIFUNCTIONAL POLYMERIZATION INITIATORS |
-
1984
- 1984-03-28 FR FR8404824A patent/FR2562079B1/en not_active Expired
-
1985
- 1985-03-12 CH CH1109/85A patent/CH662574A5/en not_active IP Right Cessation
- 1985-03-18 ES ES541366A patent/ES541366A0/en active Granted
- 1985-03-20 LU LU85818A patent/LU85818A1/en unknown
- 1985-03-23 JP JP60059352A patent/JPS6112712A/en active Pending
- 1985-03-23 DE DE19853510624 patent/DE3510624A1/en not_active Ceased
- 1985-03-25 IT IT47857/85A patent/IT1182724B/en active
- 1985-03-26 GB GB08507762A patent/GB2156368B/en not_active Expired
- 1985-03-26 CA CA000477515A patent/CA1281451C/en not_active Expired - Fee Related
- 1985-03-27 GR GR850760A patent/GR850760B/el unknown
- 1985-03-27 BE BE0/214721A patent/BE902035A/en not_active IP Right Cessation
- 1985-03-27 IE IE77785A patent/IE58344B1/en not_active IP Right Cessation
- 1985-03-28 NL NL8500919A patent/NL8500919A/en not_active Application Discontinuation
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137749A (en) * | 2015-10-16 | 2018-06-08 | 株式会社普利司通 | Multiple copolymer, resin combination, cross-linkable resin composition and product |
| CN108137765A (en) * | 2015-10-16 | 2018-06-08 | 株式会社普利司通 | Multiple copolymer, rubber composition, crosslinked rubber composition and rubber |
| CN108137759A (en) * | 2015-10-16 | 2018-06-08 | 株式会社普利司通 | Multiple copolymer, rubber composition, crosslinked rubber composition and rubber |
| EP3363838A4 (en) * | 2015-10-16 | 2018-09-05 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition, and rubber article |
| US20180282459A1 (en) * | 2015-10-16 | 2018-10-04 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
| EP3363829A4 (en) * | 2015-10-16 | 2018-10-10 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition, and rubber article |
| US20180298130A1 (en) * | 2015-10-16 | 2018-10-18 | Bridgestone Corporation | Multi-component copolymer, resin composition, cross-linked resin composition, and product |
| EP3363839A4 (en) * | 2015-10-16 | 2019-01-09 | Bridgestone Corporation | Multicomponent copolymer, rubber composition, cross-linked rubber composition, and rubber article |
| EP3363837A4 (en) * | 2015-10-16 | 2019-01-23 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition, and rubber article |
| US10538649B2 (en) | 2015-10-16 | 2020-01-21 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
| US10550216B2 (en) * | 2015-10-16 | 2020-02-04 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
| US10669364B2 (en) | 2015-10-16 | 2020-06-02 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
| CN108137765B (en) * | 2015-10-16 | 2020-09-18 | 株式会社普利司通 | Multipolymers, rubber compositions, cross-linked rubber compositions and rubber products |
| US10920003B2 (en) | 2015-10-16 | 2021-02-16 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
| CN108137759B (en) * | 2015-10-16 | 2021-03-09 | 株式会社普利司通 | Multipolymer, rubber composition, crosslinked rubber composition and rubber product |
| US11059928B2 (en) | 2015-10-16 | 2021-07-13 | Bridgestone Corporation | Multi-component copolymer, rubber composition, crosslinked rubber composition and rubber article |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8547857A0 (en) | 1985-03-25 |
| IT1182724B (en) | 1987-10-05 |
| ES8603522A1 (en) | 1985-12-16 |
| GB2156368B (en) | 1987-10-28 |
| GB8507762D0 (en) | 1985-05-01 |
| CH662574A5 (en) | 1987-10-15 |
| IT8547857A1 (en) | 1986-09-25 |
| IE850777L (en) | 1985-09-28 |
| LU85818A1 (en) | 1985-12-12 |
| GR850760B (en) | 1985-11-25 |
| NL8500919A (en) | 1985-10-16 |
| IE58344B1 (en) | 1993-09-08 |
| CA1281451C (en) | 1991-03-12 |
| BE902035A (en) | 1985-09-27 |
| JPS6112712A (en) | 1986-01-21 |
| FR2562079B1 (en) | 1986-08-29 |
| ES541366A0 (en) | 1985-12-16 |
| FR2562079A1 (en) | 1985-10-04 |
| DE3510624A1 (en) | 1985-11-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940326 |