US20040242787A1 - Process for preparing linear block copolymer - Google Patents
Process for preparing linear block copolymer Download PDFInfo
- Publication number
- US20040242787A1 US20040242787A1 US10/250,851 US25085103A US2004242787A1 US 20040242787 A1 US20040242787 A1 US 20040242787A1 US 25085103 A US25085103 A US 25085103A US 2004242787 A1 US2004242787 A1 US 2004242787A1
- Authority
- US
- United States
- Prior art keywords
- lithium
- block copolymer
- aromatic hydrocarbon
- vinyl aromatic
- conjugated diene
- 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.)
- Abandoned
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 66
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 64
- 150000001993 dienes Chemical class 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 150000002900 organolithium compounds Chemical class 0.000 claims description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 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
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 claims description 2
- RRRXUCMQOPNVAT-UHFFFAOYSA-N 1-ethenyl-4-(4-methylphenyl)benzene Chemical compound C1=CC(C)=CC=C1C1=CC=C(C=C)C=C1 RRRXUCMQOPNVAT-UHFFFAOYSA-N 0.000 claims description 2
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 claims description 2
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-UHFFFAOYSA-N 0.000 claims description 2
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 claims description 2
- ZATOFRITFRPYBT-UHFFFAOYSA-N C1=CC=C2C([Li])=CC=CC2=C1 Chemical compound C1=CC=C2C([Li])=CC=CC2=C1 ZATOFRITFRPYBT-UHFFFAOYSA-N 0.000 claims description 2
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 claims description 2
- SEVZJBPKDJZGFW-UHFFFAOYSA-N [Li]C1=CC=C(CCCC)C=C1 Chemical compound [Li]C1=CC=C(CCCC)C=C1 SEVZJBPKDJZGFW-UHFFFAOYSA-N 0.000 claims description 2
- XAGXFZXSTCZIQR-UHFFFAOYSA-N [Li]C1CC(CCCCCCC)CC(CCCCCCC)C1 Chemical compound [Li]C1CC(CCCCCCC)CC(CCCCCCC)C1 XAGXFZXSTCZIQR-UHFFFAOYSA-N 0.000 claims description 2
- SHJXVDAAVHAKFB-UHFFFAOYSA-N [Li]CCCCCCCCCC Chemical compound [Li]CCCCCCCCCC SHJXVDAAVHAKFB-UHFFFAOYSA-N 0.000 claims description 2
- WZBHJENIKYQMHC-UHFFFAOYSA-N [Li]CCCCCCCCCCCCCCCCCCCC Chemical compound [Li]CCCCCCCCCCCCCCCCCCCC WZBHJENIKYQMHC-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 claims description 2
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims 1
- LFASRCHQAYIROH-UHFFFAOYSA-N [Li]C1CCCC1 Chemical compound [Li]C1CCCC1 LFASRCHQAYIROH-UHFFFAOYSA-N 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
Definitions
- the present invention relates to a linear block copolymer and a process for preparing the same, and particularly to a linear block copolymer in which a conjugated diene/vinyl aromatic hydrocarbon copolymer block is located in a block copolymer and a process for preparing the same.
- Vinyl aromatic hydrocarbon/conjugated diene block copolymers prepared using organolithium and hydrocarbon solvent differ in their microstructures according to a ratio of vinyl aromatic hydrocarbon and conjugated diene, and processing conditions and physical properties of resultant products also differ.
- a rubber phase block copolymer having vinyl aromatic hydrocarbon contents of 50% or less is prepared by sequentially polymerizing a vinyl aromatic hydrocarbon and a conjugated diene and then introducing a coupling reactant.
- WO 95/12644 has disclosed using a halogenous silane compound as a coupling reactant, which can shorten polymerization time and obtain a copolymer having vinyl aromatic hydrocarbon polymer blocks of the same molecular weights, but a lithium compound produced in the coupling reaction as a by-product causes discoloration during processing.
- a vinyl aromatic hydrocarbon block and a conjugated diene block are sequentially prepared and then the vinyl aromatic hydrocarbon is polymerized again, thereby preparing a linear triblock copolymer.
- a linear or star block copolymer having vinyl aromatic hydrocarbon contents of 60 ⁇ 80% has superior transparency and impact strength and thus is used for packaging containers, etc.
- the block copolymer is also used for compensating impact strength of general-purpose polystyrene, and it is preferable to use a block copolymer having vinyl aromatic hydrocarbon contents of 70 ⁇ 80% for improving impact strength of polystyrene and for maintaining transparency.
- a linear or star copolymer having vinyl aromatic hydrocarbon contents of 20 ⁇ 50% has been blended with general-purpose polystyrene.
- the linear vinyl aromatic hydrocarbon/conjugated diene block copolymer prepared by sequentially introducing monomers does not generate side reactions such as discoloration during the polymerization process, it is suitable for molded products requiring high transparency, and it has superior dispersibility when blended with other resins and thus is suitable for improving impact resistance of polystyrene and for maintaining transparency.
- U.S. Pat. No. 6,140,433 has disclosed a block copolymer with polydispersity that can improve impact resistance of other resins by sequentially introducing monomers when preparing a vinyl aromatic hydrocarbon/conjugated diene block copolymer, by introducing an initiator twice and introducing a vinyl aromatic hydrocarbon/conjugated diene copolymer block.
- this method can easily control physical properties and processibility of a product, it is required that an exact amount of initiator is introduced and that polymerization should proceed at a high temperature. Additionally, the copolymer may lower transparency of the product due to side reactions generated by conducting polymerization at a high temperature.
- a 1 , A 2 , and A 3 are independently vinyl aromatic hydrocarbon blocks having average molecular weights of 100 ⁇ 100,000,
- B 1 is a conjugated diene block having an average molecular weight of 100 ⁇ 100,000, and
- (B/A) is a conjugated diene/vinyl aromatic hydrocarbon copolymer block having an average molecular weight of 100 ⁇ 100,000.)
- the present invention also provides a process for preparing a linear block copolymer comprising the steps of:
- step b) simultaneously introducing a vinyl aromatic hydrocarbon and a conjugated diene monomer in the reactor of step a) to polymerize until at least 99% of monomers are consumed;
- step b) introducing a vinyl aromatic hydrocarbon in the reactor of step b) to polymerize until at least 99% of monomers are consumed.
- the present inventors while studying a process for improving transparency of a block copolymer, sequentially introduced a vinyl aromatic hydrocarbon, a vinyl aromatic hydrocarbon and a conjugated diene monomer, and a vinyl aromatic hydrocarbon, to polymerize them in the presence of a hydrocarbon solvent and an organolithium compound, and they confirmed superior effects for improving transparency and transmissivity of the block copolymer and completed the present invention.
- the present invention relates to a block copolymer represented by the following Chemical Formula 1 in which a vinyl aromatic hydrocarbon/conjugated diene copolymer block is introduced into a block copolymer by sequentially introducing a vinyl aromatic hydrocarbon, a vinyl aromatic hydrocarbon and a conjugated diene monomer, and a vinyl aromatic hydrocarbon, to polymerize them in the presence of an organolithium compound and a polymerization initiator.
- a 1 , A 2 , and A 3 are independently vinyl aromatic hydrocarbon blocks having average molecular weights of 100 ⁇ 100,000,
- B 1 is a conjugated diene block having an average molecular weight of 100 ⁇ 100,000
- (B/A) is a conjugated diene/vinyl aromatic hydrocarbon copolymer block having an average molecular weight of 100 ⁇ 100,000.)
- the ratio of the A 1 block and (A 2 +A 3 ) block of the copolymer is preferably 0.1 ⁇ 10, and the ratio of vinyl aromatic hydrocarbon/conjugated diene monomer in the block copolymer is preferably 25:75 ⁇ 50:50.
- the block copolymer represented by the above Chemical Formula 1 of the present invention preferably has an average molecular weight of 400 ⁇ 400,000, and it may have a monodispersive or polydispersive molecular weight distribution.
- the vinyl aromatic hydrocarbon used in the present invention includes styrene, ⁇ -methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinyinaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, or 1-vinyl-5-hexylnaphthalene, etc., and styrene or methylstyrene is preferable.
- 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, or 2-phenyl-1,3-butadiene, etc. can be used alone or in combination, and preferably 1,3-butadiene or isoprene is used.
- the organolithium compound plays a function as a polymerization initiator.
- an alkyl lithium compound can be used, and particularly an alkyl lithium compound having a C 3-10 alkyl group is preferable.
- Other organolithium compounds can be used in addition to the alkyl lithium compound.
- organolithium compounds methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-decyl lithium, tert-octyl lithium, phenyl lithium, 1-naphthyl lithium, n-eicosyl lithium, 4-butylphenyl lithium, 4-tollyl lithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, or 4-cylcopentyl lithium, etc. can be used, and n-butyl lithium or sec-butyl lithium is preferable.
- n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, or xylene, etc. can be used, and other aromatic hydrocarbons or naphthalene hydrocarbons can be used.
- n-hexane, cyclohexane or a mixed solution thereof is preferable.
- polar solvent plays a function for controlling vinyl contents and improving polymerization speed when polymerizing a conjugated diene monomer.
- polar solvent tetrahydrofuran, ethylether, or tetramethylethylenediamine, etc. can be used, and tetrahydrofuran is preferable.
- the present invention also provides a process for preparing the above-mentioned linear block copolymer.
- a vinyl aromatic hydrocarbon is introduced and polymerized until at least 99% of monomers are consumed.
- the structure of the produced active polymer is A 1 .
- the vinyl aromatic hydrocarbon and conjugated diene monomer are simultaneously introduced and polymerized until at least 99% of monomers are consumed.
- the conjugated diene is initially consumed to form the conjugated diene block first, and when most of the conjugated diene is consumed, the vinyl aromatic hydrocarbon begins to be consumed to sequentially form a conjugated diene/vinyl aromatic hydrocarbon copolymer block and a vinyl aromatic hydrocarbon block.
- the structure of the active polymer produced in the second step is A 1 -B 1 -(B/A)-A 2 .
- a vinyl aromatic hydrocarbon is introduced and polymerized until at least 99% of monomers are consumed.
- the structure of the produced active polymer is A 1 -B 1 -(B/A)-A 2 -A 3 .
- water or alcohol is added to the reactor to arrest activity of the active polymer.
- the polymerization is preferably conducted at a temperature range of ⁇ 50 ⁇ 150° C. and under a pressure range sufficient for maintaining a reactant liquid phase.
- the block copolymer prepared according to the present invention has superior transparency, and it also has superior transparency when used as an impact reinforcing agent for other resins or molded products.
- a block copolymer having styrene weight contents of 40% and comprising a butadiene/styrene copolymer block was prepared as follows.
- styrene as a vinyl aromatic hydrocarbon were introduced and polymerization was conducted until monomers were completely consumed, and 0.5 g of water was added to the reactor to terminate activity of the active copolymer.
- the molecular weight of the prepared block copolymer was 68,000 g/mol, and the block styrene contents were 36 wt %.
- a block copolymer having styrene weight contents of 40% was prepared as follows.
- styrene 300 g were introduced therein as a vinyl aromatic hydrocarbon to polymerize until the styrene was completely consumed, and 0.5 g of water was added to the reactor to terminate activity of the active copolymer.
- 7.5 g of Irganox1076 and 15.0 g of TNPP were added to the polymerization solution as an antioxidant to prepare a block copolymer.
- the molecular weight of the prepared block copolymer was 69,000 g/mol, and the block styrene contents were 39 wt %.
- Example 1 The block copolymers prepared in Example 1 and Comparative Example 1 were made into samples of 2 mm thickness after removing the solvent, and transmissivity and Haze value were measured and are shown in Table 1. TABLE 1 Transparency Example 1 Comparative Example 1 Transmissivity 89.6 89.6 Haze value 5.6 10.3
- the block copolymer of Example 1 of the present invention in which vinyl aromatic hydrocarbon/conjugated diene copolymer block was introduced into a block copolymer has a low Haze value and thus superior transparency compared to that of Comparative Example 1.
- the block copolymer of the present invention can remarkably improve transparency by introducing a vinyl aromatic hydrocarbon/conjugated diene copolymer block into a block copolymer, it can be polymerized at a comparatively low temperature by introducing an initiator once, and it has superior transparency when used for an impact reinforcing agent for other resins or molded products.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/234,521 US7160952B2 (en) | 2001-11-14 | 2005-09-23 | Process for preparing linear block copolymer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2001-0070840A KR100425243B1 (ko) | 2001-11-14 | 2001-11-14 | 선형의 블록 공중합체의 제조방법 |
| KR2001-70840 | 2001-11-14 | ||
| PCT/KR2002/002129 WO2003042266A1 (en) | 2001-11-14 | 2002-11-14 | Process for preparing linear block copolymer |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/234,521 Continuation-In-Part US7160952B2 (en) | 2001-11-14 | 2005-09-23 | Process for preparing linear block copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20040242787A1 true US20040242787A1 (en) | 2004-12-02 |
Family
ID=19715975
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/250,851 Abandoned US20040242787A1 (en) | 2001-11-14 | 2002-11-14 | Process for preparing linear block copolymer |
| US11/234,521 Expired - Lifetime US7160952B2 (en) | 2001-11-14 | 2005-09-23 | Process for preparing linear block copolymer |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US11/234,521 Expired - Lifetime US7160952B2 (en) | 2001-11-14 | 2005-09-23 | Process for preparing linear block copolymer |
Country Status (9)
| Country | Link |
|---|---|
| US (2) | US20040242787A1 (no) |
| EP (1) | EP1444280B1 (no) |
| JP (1) | JP2005509066A (no) |
| KR (1) | KR100425243B1 (no) |
| CN (1) | CN100344661C (no) |
| DE (1) | DE60230439D1 (no) |
| NO (1) | NO330460B1 (no) |
| TW (1) | TWI304815B (no) |
| WO (1) | WO2003042266A1 (no) |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160311958A1 (en) * | 2013-12-06 | 2016-10-27 | Lg Chem, Ltd. | Block copolymer |
| US10081698B2 (en) | 2013-12-06 | 2018-09-25 | Lg Chem, Ltd. | Block copolymer |
| US10087276B2 (en) | 2013-12-06 | 2018-10-02 | Lg Chem, Ltd. | Block copolymer |
| US10150832B2 (en) | 2013-12-06 | 2018-12-11 | Lg Chem, Ltd. | Block copolymer |
| US10160822B2 (en) | 2013-12-06 | 2018-12-25 | Lg Chem, Ltd. | Monomer and block copolymer |
| US10184021B2 (en) | 2013-12-06 | 2019-01-22 | Lg Chem, Ltd. | Block copolymer |
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| US10370529B2 (en) | 2014-09-30 | 2019-08-06 | Lg Chem, Ltd. | Method of manufacturing patterned substrate |
| US10377894B2 (en) | 2014-09-30 | 2019-08-13 | Lg Chem, Ltd. | Block copolymer |
| US10633533B2 (en) | 2014-09-30 | 2020-04-28 | Lg Chem, Ltd. | Block copolymer |
| US10703897B2 (en) | 2014-09-30 | 2020-07-07 | Lg Chem, Ltd. | Block copolymer |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040032488A (ko) * | 2002-10-10 | 2004-04-17 | 금호석유화학 주식회사 | 3원 블록 공중합체 및 제조방법 |
| KR100961383B1 (ko) | 2007-05-31 | 2010-06-07 | 주식회사 엘지화학 | 폴리실록산 말단변성 비닐 방향족 탄화수소-공액디엔 블록공중합체 및 이의 제조방법 |
| JP7105240B2 (ja) * | 2017-08-29 | 2022-07-22 | Ｅｎｅｏｓクレイトンエラストマー株式会社 | 耐摩耗性に優れた感光性印刷版材用ブロック共重合体及びその製造方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10227436B2 (en) | 2013-12-06 | 2019-03-12 | Lg Chem, Ltd. | Block copolymer |
| US10253130B2 (en) | 2013-12-06 | 2019-04-09 | Lg Chem, Ltd. | Block copolymer |
| US10087276B2 (en) | 2013-12-06 | 2018-10-02 | Lg Chem, Ltd. | Block copolymer |
| US10150832B2 (en) | 2013-12-06 | 2018-12-11 | Lg Chem, Ltd. | Block copolymer |
| US10160822B2 (en) | 2013-12-06 | 2018-12-25 | Lg Chem, Ltd. | Monomer and block copolymer |
| US10184021B2 (en) | 2013-12-06 | 2019-01-22 | Lg Chem, Ltd. | Block copolymer |
| US10196475B2 (en) | 2013-12-06 | 2019-02-05 | Lg Chem, Ltd. | Block copolymer |
| US10196474B2 (en) | 2013-12-06 | 2019-02-05 | Lg Chem, Ltd. | Block copolymer |
| US10202480B2 (en) | 2013-12-06 | 2019-02-12 | Lg Chem, Ltd. | Block copolymer |
| US10202481B2 (en) | 2013-12-06 | 2019-02-12 | Lg Chem, Ltd. | Block copolymer |
| US10227437B2 (en) * | 2013-12-06 | 2019-03-12 | Lg Chem, Ltd. | Block copolymer |
| US10227438B2 (en) | 2013-12-06 | 2019-03-12 | Lg Chem, Ltd. | Block copolymer |
| US10081698B2 (en) | 2013-12-06 | 2018-09-25 | Lg Chem, Ltd. | Block copolymer |
| US10239980B2 (en) | 2013-12-06 | 2019-03-26 | Lg Chem, Ltd. | Block copolymer |
| US20160311958A1 (en) * | 2013-12-06 | 2016-10-27 | Lg Chem, Ltd. | Block copolymer |
| US10370529B2 (en) | 2014-09-30 | 2019-08-06 | Lg Chem, Ltd. | Method of manufacturing patterned substrate |
| US10281820B2 (en) | 2014-09-30 | 2019-05-07 | Lg Chem, Ltd. | Block copolymer |
| US10287429B2 (en) | 2014-09-30 | 2019-05-14 | Lg Chem, Ltd. | Block copolymer |
| US10287430B2 (en) | 2014-09-30 | 2019-05-14 | Lg Chem, Ltd. | Method of manufacturing patterned substrate |
| US10295908B2 (en) | 2014-09-30 | 2019-05-21 | Lg Chem, Ltd. | Block copolymer |
| US10310378B2 (en) | 2014-09-30 | 2019-06-04 | Lg Chem, Ltd. | Block copolymer |
| US10240035B2 (en) | 2014-09-30 | 2019-03-26 | Lg Chem, Ltd. | Block copolymer |
| US10377894B2 (en) | 2014-09-30 | 2019-08-13 | Lg Chem, Ltd. | Block copolymer |
| US10633533B2 (en) | 2014-09-30 | 2020-04-28 | Lg Chem, Ltd. | Block copolymer |
| US10703897B2 (en) | 2014-09-30 | 2020-07-07 | Lg Chem, Ltd. | Block copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20033086L (no) | 2003-07-07 |
| CN1479758A (zh) | 2004-03-03 |
| WO2003042266A1 (en) | 2003-05-22 |
| KR20030039789A (ko) | 2003-05-22 |
| NO330460B1 (no) | 2011-04-18 |
| NO20033086D0 (no) | 2003-07-07 |
| JP2005509066A (ja) | 2005-04-07 |
| EP1444280A1 (en) | 2004-08-11 |
| KR100425243B1 (ko) | 2004-03-30 |
| US20060217509A1 (en) | 2006-09-28 |
| TWI304815B (en) | 2009-01-01 |
| TW200407340A (en) | 2004-05-16 |
| EP1444280B1 (en) | 2008-12-17 |
| CN100344661C (zh) | 2007-10-24 |
| DE60230439D1 (de) | 2009-01-29 |
| US7160952B2 (en) | 2007-01-09 |
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