US20220144976A1 - Block copolymer and method for preparing the same - Google Patents
Block copolymer and method for preparing the same Download PDFInfo
- Publication number
- US20220144976A1 US20220144976A1 US17/649,160 US202217649160A US2022144976A1 US 20220144976 A1 US20220144976 A1 US 20220144976A1 US 202217649160 A US202217649160 A US 202217649160A US 2022144976 A1 US2022144976 A1 US 2022144976A1
- Authority
- US
- United States
- Prior art keywords
- alkyl
- independently
- present disclosure
- block copolymer
- formula
- 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
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims abstract description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 8
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000203 mixture Substances 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 0 [7*]C(CC(C)C)(C(=O)[8*]C)C(C)C Chemical compound [7*]C(CC(C)C)(C(=O)[8*]C)C(C)C 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- -1 —OTMS Chemical group 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JNOGVQJEBGEKMG-UHFFFAOYSA-N (1-methoxy-2-methylprop-1-enoxy)-trimethylsilane Chemical compound COC(=C(C)C)O[Si](C)(C)C JNOGVQJEBGEKMG-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- SPUNGLVNMRYBEO-UHFFFAOYSA-N [V]=O.OC(=O)C1=CC=CC=C1 Chemical compound [V]=O.OC(=O)C1=CC=CC=C1 SPUNGLVNMRYBEO-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000001052 yellow pigment Substances 0.000 description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium dioxide Chemical compound O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000006564 (C4-C8) cycloalkyl group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OVXNLJHNNUAEMR-UHFFFAOYSA-N CCC(C)c1ccc(S(=O)(=O)O)cc1 Chemical compound CCC(C)c1ccc(S(=O)(=O)O)cc1 OVXNLJHNNUAEMR-UHFFFAOYSA-N 0.000 description 1
- 229910004140 HfO Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910002785 ReO3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- ZMFKXOMVFFKPEC-UHFFFAOYSA-D [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZMFKXOMVFFKPEC-UHFFFAOYSA-D 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- FAQSSRBQWPBYQC-VGKOASNMSA-N dioxomolybdenum;(z)-4-hydroxypent-3-en-2-one Chemical compound O=[Mo]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FAQSSRBQWPBYQC-VGKOASNMSA-N 0.000 description 1
- ASLHVQCNFUOEEN-UHFFFAOYSA-N dioxomolybdenum;dihydrochloride Chemical compound Cl.Cl.O=[Mo]=O ASLHVQCNFUOEEN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten dioxide Inorganic materials O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08F297/06—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 coordination type
-
- C—CHEMISTRY; METALLURGY
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- 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
- C08F297/026—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 acrylic acid, methacrylic acid or derivatives thereof
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7095—Cobalt, nickel or compounds thereof
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7095—Cobalt, nickel or compounds thereof
- C08F4/7096—Cobalt or compounds thereof
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7095—Cobalt, nickel or compounds thereof
- C08F4/7098—Nickel or compounds thereof
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
Definitions
- the present invention relates to a block copolymer and a method for preparing the same and, more particularly, to a triblock copolymer and a method for synthesizing a block copolymer by using an oxometallic complex as a catalyst.
- Pigments are widely used in inks and paints because they have good stability to light, heat, water, etc., as compared to dyes.
- pigments are solid particles which are insoluble in water, so aggregation and uneven dispersion are likely to occur during preparation, use, or preservation, which accordingly affects the pigment quality. Therefore, the dispersibility of the pigments is one of the key factors affecting the quality.
- Dispersants are often used as necessary additives and have the advantages of promoting dispersion of pigment particles and improving stability.
- conventional small molecule dispersants have poor stability and poor dispersion effect, and have gradually been replaced by polymer dispersants, among which block type polymer dispersants have received particular attention.
- the synthesis of catalytic block copolymer mostly requires the use of 1 to 2 equivalents of the catalyst for reaction, which is low in reaction efficiency and high in cost.
- the present disclosure provides a block copolymer and a method for preparing the block copolymer, which utilizes an oxometallic complex as a catalyst to catalyze the synthesis of the block copolymer and only needs to use a catalytic amount of catalyst for reaction, thereby reducing the cost.
- the oxometallic complex is biochemically absorbable and metabolizable, and thus can reduce the environmental burden.
- the present disclosure provides a method for preparing a block copolymer.
- the method comprises the following steps: (A) mixing a compound of formula (I), a catalyst of formula (II), and a first solvent to obtain a first mixture; (B) adding a first monomer into the first mixture for reaction to obtain a second mixture; and (C) adding a second monomer into the second mixture for reaction to obtain a third mixture.
- D, E, and F are each independently a compound of formula (VI), and D, E, and F are different from each other; and x, y, and z are each independently an integer from 1 to 40; wherein the compound of formula (VI) is shown below:
- a 2 is O, or S; R 7 is H, or a C 1-6 alkyl; and R 8 is a C 1-12 alkyl, (CH 2 ) q N(R 11 ) 2 , CH 2 (CH 2 OCH 2 ) r CH 2 N(R 12 ) 2 , or CH 2 (CH 2 OCH 2 ) s CH 2 OR 13 , wherein R 11 , R 12 , and R 13 are each independently a C 1-6 alkyl; and q, r, and s are each independently an integer from 1 to 10.
- the compound of formula (I) is used as a starting material for synthesizing the block copolymer, wherein the compound of formula (I) is as follows:
- a 1 is a bond, O, or S; and R 1 , R 2 , and R 3 are each independently H, a C 1-6 alkyl, —COOR 4 , or —CH 2 P( ⁇ O)R 5 R 6 ; or R 1 and R 2 are bonded to each other to form a C 4-8 cycloalkyl group or a C 3-7 heterocycloalkyl group; or R 2 and R 3 are bonded to each other to form a C 5-8 cycloalkyl group; wherein R 4 , R 5 , and R 6 are each independently a C 1-6 alkyl, a C 1-6 alkoxyl, —OTMS, or an amino group substituted by a C 1-6 alkyl.
- a 1 is O and R 1 , R 2 , and R 3 are each independently H or a C 1-6 alkyl, but the present disclosure is not limited thereto.
- the catalyst used in the method for preparing a block copolymer is shown as the following formula (II):
- M is an element of group IB, IVB, VB, VIB, VIIB, and VIIIB elements
- X is Cl, Br, I, OH, OAc, OC(O)Ar, OC(O)(CF 2 ) c CF 3 , OC(O)C 12 H 25 , [(OSO 2 C 6 H 4 —CHCH 2 ) n ], OTf, OTs, SO 4 , SO 3 C 12 H 25 , acetylacetonate (acac), or a mixture thereof;
- a is an integer from 0 to 3;
- b is an integer from 1 to 4;
- m is an integer from 2 to 4;
- n is an integer from 1 to 2; and
- c is an integer from 1 to 6; wherein Ar is a C 6-20 aryl, and [(OSO 2 C 6 H 4 —CHCH 2 ) n ] has a structure of
- a may be 0, and M is Ti(IV), Zr(IV), Hf(IV), V(III), Fe(II/III), Cu(I/II), Mn(II/III), Co(II), or Ni(II).
- M(O) a may be BiO, VO, VO 3 , ZrO, HfO, WO 2 , MoO 2 , CrO 2 , or ReO 3 .
- Hf(O)Cl 2 , V(O)Cl 2 , V(O)[(OSC 6 H 4 CHCH 2 ) n ] 2 , V(O)Cl 3 , V(O)(OTf) 2 , V(O)(OCOR) 2 , MoO 2 Cl 2 , Mn(O)(OCOR), FeCl 3 , Zr(O)Cl 2 , Zr(OAc)(OH) x (x+y 4), Ti(O)(acac) 2 , V(O)SO 4 , V(O)(acac) 2 , MoO 2 (acac) 2 , Mn(II)SO 4 , and FeSO 4 are included, but the present disclosure is not limited thereto, and the catalysts may be used singly or in combination thereof, wherein R is a C 6-20 aryl.
- the content of the catalyst is not particularly limited as long as the synthesis of the block copolymer can be catalyzed.
- the catalyst is present in an amount of from 0.1% to 20% by weight based on a total weight of the first mixture, for example from 0.1% to 15% by weight, from 0.1% to 10% by weight, or from 0.1% to 5% by weight, but the present disclosure is not limited thereto.
- step (C) after the third mixture is obtained in step (C), the third monomer is further added into the third mixture to obtain a fourth mixture.
- the first monomer, the second monomer, and the third monomer are each independently an acrylate compound or a diacrylate compound.
- the acrylate compound may be a compound of formula (III) below:
- a 2 is O or S; R 7 is H or a C 1-6 alkyl; and R 8 is a C 1-12 alkyl, (CH 2 ) q N(R 11 ) 2 , CH 2 (CH 2 OCH 2 ) r CH 2 N(R 12 ) 2 , or CH 2 (CH 2 OCH 2 ) s CH 2 OR 13 ; wherein R 11 , R 12 , and R 13 are each independently a C 1-6 alkyl; and q, r, and s are each independently an integer from 1 to 10.
- a 2 is O; R 7 is H or a C 1-6 alkyl; and R 8 is a C 1-10 alkyl, (CH 2 ) q N(R 11 ) 2 , CH 2 (CH 2 OCH 2 ) r CH 2 N(R 12 ) 2 , or CH 2 (CH 2 OCH 2 )SCH 2 OR 13 ; wherein R 11 , R 12 , and R 13 are each independently a C 1-6 alkyl; and q, r, and s are each independently an integer from 1 to 6.
- the diacrylate compound may be a compound of formula (IV) below:
- Y is O, NH, or S
- R 9 is H, or a C 1-6 alkyl
- R 10 is a C 1-6 alkyl, or a C 6-20 aryl
- p is an integer from 1 to 12.
- Y is O or NH
- R 9 is H or a C 1-6 alkyl
- R 10 is a C 1-6 alkyl or a C 6-20 aryl
- p is an integer from 1 to 8.
- a step (D) of adding the third mixture into a second solvent may be further included.
- the second solvent is not particularly limited as long as it can induce the product to precipitate.
- the second solvent may be water, an alcohol, a C 5-10 alkane, or a mixture thereof.
- the alcohol comprises methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, 2-methyl butanol, sec-amyl alcohol, or a mixture thereof, but the present disclosure is not limited thereto.
- the C 5-10 alkane comprises pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or a mixture thereof, but the present disclosure is not limited thereto.
- a step (E) of adding the fourth mixture into a second solvent may be further included.
- the second solvent is not particularly limited as long as it can induce the product to precipitate.
- the second solvent is water, an alcohol, a C 5-10 alkane, or a mixture thereof.
- the alcohol comprises methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, 2-methyl butanol, sec-amyl alcohol, or a mixture thereof, but the present disclosure is not limited thereto.
- the C 5-10 alkane comprises pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or a mixture thereof, but the present disclosure is not limited thereto.
- the first solvent is not particularly limited as long as it can serve as a solvent for the reaction.
- the first solvent is an ether solvent, such as tetrahydrofuran or ethyl ether, but the present disclosure is not limited thereto.
- x, y, and z are each independently an integer from 1 to 20.
- x, y, and z are each independently an integer from 1 to 15, but the present disclosure is not limited thereto.
- a 2 is O; R 7 is H or a C 1-3 alkyl; and R is a C 1-8 alkyl, (CH 2 ) q N(R 11 ) 2 , CH 2 (CH 2 OCH 2 ) r CH 2 N(R 2 ) 2 , or CH 2 (CH 2 OCH 2 ) s CH 2 OR 13 , wherein R 11 , R 12 , and R 13 are each independently a C 1-3 alkyl; and q, r, and s are each independently an integer from 1 to 6.
- the block copolymer comprises an end group represented by formula (VII) below:
- R 1 is a C 1-6 alkyl
- R 2 and R 3 are each independently H or a C 1-6 alkyl.
- At least one of D, E, and F is a compound of formula (VIII) below:
- R 7 is H or a C 1-6 alkyl
- R 8 is (CH 2 ) q N(R 11 ) 2 or CH 2 (CH 2 OCH 2 ) r CH 2 N(R 12 ) 2 , wherein R 11 and R 12 are each independently a C 1-6 alkyl; and q and r are each independently an integer from 1 to 10.
- R 7 is H or a C 1-3 alkyl
- R 8 is (CH 2 ) q N(R 11 ) 2 or CH 2 (CH 2 OCH 2 ) r CH 2 N(R 12 ) 2 , wherein R 11 and R 12 are each independently a C 1-3 alkyl; and q and r are each independently an integer from 1 to 6.
- the catalyst can be synthesized according to the following reaction formulae.
- Vanadium sulphate (VOSO 4 -5H 2 O, 2.5 mmol) was placed in a dry double-necked round bottom flask (50 mL), followed by anhydrous methanol (2.5 mL).
- a solution of BaX 2 (1 equivalent, 2.5 mmol) for example, Ba(OAc) 2 , BaOTs 2 , BaOTf 2 , or Ba[(O 3 SC 6 H 4 CHCH 2 ) n ] 2
- methanol 2.5 mL
- the mixture was filtered through a plug of celite, and the obtained filtrate was evaporated to give a dark blue solid.
- the resulting solid was dried under vacuum at 120° C. for 4 hours.
- the product obtained can be stored in a dry box for several weeks and can be used directly.
- Example 3 The copolymer of Example 3 (1 g) and the commercially available dispersant (1 g) were dissolved in 1 mL of tetrahydrofuran, into which 135 uL of yellow pigment (from a solution of 500 mg yellow pigment in 3 mL of tetrahydrofuran) was added, followed by grinding and stirring for 30 seconds. The dispersion of the yellow pigment was observed and shown in Table 1.
Abstract
[D]x-[E]y-[F]z (V)
-
- wherein D, E, and F are each independently a compound of formula (VI) below, and D, E, and F are different from each other; and x, y, and z are each independently an integer from 1 to 40;
-
- wherein A2 is O or S; R7 is H or a C1-6 alkyl; and R8 is a C1-12 alkyl, (CH2)qN(R11)2, CH2(CH2OCH2)rCH2N(R12)2, or CH2(CH2OCH2)sCH2OR13, wherein R11, R12, and R13 are each independently a C1-6 alkyl; and q, r, and s are each independently an integer from 1 to 10.
Description
- This application claims the benefits of the Taiwan Patent Application Serial Number 107133172, filed on Sep. 20, 2018, the subject matter of which is incorporated herein by reference.
- This application is a division of U.S. Patent application for “Block copolymer and method for preparing the same”, U.S. application Ser. No. 16/574,885 filed on Sep. 18, 2019, and the subject matter of which is incorporated herein by reference.
- The present invention relates to a block copolymer and a method for preparing the same and, more particularly, to a triblock copolymer and a method for synthesizing a block copolymer by using an oxometallic complex as a catalyst.
- Pigments are widely used in inks and paints because they have good stability to light, heat, water, etc., as compared to dyes. However, pigments are solid particles which are insoluble in water, so aggregation and uneven dispersion are likely to occur during preparation, use, or preservation, which accordingly affects the pigment quality. Therefore, the dispersibility of the pigments is one of the key factors affecting the quality.
- Dispersants are often used as necessary additives and have the advantages of promoting dispersion of pigment particles and improving stability. However, conventional small molecule dispersants have poor stability and poor dispersion effect, and have gradually been replaced by polymer dispersants, among which block type polymer dispersants have received particular attention. In general, the synthesis of catalytic block copolymer mostly requires the use of 1 to 2 equivalents of the catalyst for reaction, which is low in reaction efficiency and high in cost.
- Therefore, it is still necessary to continuously study the block copolymer for providing industrial utilization, and develop a new preparation method to simplify the process or reduce the cost.
- In view of the above, the present disclosure provides a block copolymer and a method for preparing the block copolymer, which utilizes an oxometallic complex as a catalyst to catalyze the synthesis of the block copolymer and only needs to use a catalytic amount of catalyst for reaction, thereby reducing the cost. In addition, the oxometallic complex is biochemically absorbable and metabolizable, and thus can reduce the environmental burden.
- The present disclosure provides a method for preparing a block copolymer. The method comprises the following steps: (A) mixing a compound of formula (I), a catalyst of formula (II), and a first solvent to obtain a first mixture; (B) adding a first monomer into the first mixture for reaction to obtain a second mixture; and (C) adding a second monomer into the second mixture for reaction to obtain a third mixture.
- Further, the present disclosure also provides a block copolymer having a structure of formula (V) below:
-
[D]x-[E]y-[F]z (V) - wherein D, E, and F are each independently a compound of formula (VI), and D, E, and F are different from each other; and x, y, and z are each independently an integer from 1 to 40; wherein the compound of formula (VI) is shown below:
- wherein A2 is O, or S; R7 is H, or a C1-6 alkyl; and R8 is a C1-12 alkyl, (CH2)qN(R11)2, CH2(CH2OCH2)rCH2N(R12)2, or CH2(CH2OCH2)sCH2OR13, wherein R11, R12, and R13 are each independently a C1-6 alkyl; and q, r, and s are each independently an integer from 1 to 10.
- In the present disclosure, the compound of formula (I) is used as a starting material for synthesizing the block copolymer, wherein the compound of formula (I) is as follows:
- wherein A1 is a bond, O, or S; and R1, R2, and R3 are each independently H, a C1-6 alkyl, —COOR4, or —CH2P(═O)R5R6; or R1 and R2 are bonded to each other to form a C4-8 cycloalkyl group or a C3-7 heterocycloalkyl group; or R2 and R3 are bonded to each other to form a C5-8 cycloalkyl group; wherein R4, R5, and R6 are each independently a C1-6 alkyl, a C1-6 alkoxyl, —OTMS, or an amino group substituted by a C1-6 alkyl.
- In one embodiment of the present disclosure, it is optional for the compound of formula (I) that A1 is O and R1, R2, and R3 are each independently H or a C1-6 alkyl, but the present disclosure is not limited thereto.
- In the present disclosure, the catalyst used in the method for preparing a block copolymer is shown as the following formula (II):
-
[M(O)a]m+Xb n− (II) - wherein M is an element of group IB, IVB, VB, VIB, VIIB, and VIIIB elements; X is Cl, Br, I, OH, OAc, OC(O)Ar, OC(O)(CF2)cCF3, OC(O)C12H25, [(OSO2C6H4—CHCH2)n], OTf, OTs, SO4, SO3C12H25, acetylacetonate (acac), or a mixture thereof; a is an integer from 0 to 3; b is an integer from 1 to 4; m is an integer from 2 to 4; n is an integer from 1 to 2; and c is an integer from 1 to 6; wherein Ar is a C6-20 aryl, and [(OSO2C6H4—CHCH2)n] has a structure of
- For the catalyst of formula (II) in the present disclosure, a may be 0, and M is Ti(IV), Zr(IV), Hf(IV), V(III), Fe(II/III), Cu(I/II), Mn(II/III), Co(II), or Ni(II).
- For the catalyst of formula (II) in the present disclosure, M(O)a may be BiO, VO, VO3, ZrO, HfO, WO2, MoO2, CrO2, or ReO3.
- Among the catalyst of formula (II) in the present disclosure, Hf(O)Cl2, V(O)Cl2, V(O)[(OSC6H4CHCH2)n]2, V(O)Cl3, V(O)(OTf)2, V(O)(OCOR)2, MoO2Cl2, Mn(O)(OCOR), FeCl3, Zr(O)Cl2, Zr(OAc)(OH)x(x+y=4), Ti(O)(acac)2, V(O)SO4, V(O)(acac)2, MoO2(acac)2, Mn(II)SO4, and FeSO4 are included, but the present disclosure is not limited thereto, and the catalysts may be used singly or in combination thereof, wherein R is a C6-20 aryl.
- In one embodiment of the present disclosure, the content of the catalyst is not particularly limited as long as the synthesis of the block copolymer can be catalyzed. Preferably, the catalyst is present in an amount of from 0.1% to 20% by weight based on a total weight of the first mixture, for example from 0.1% to 15% by weight, from 0.1% to 10% by weight, or from 0.1% to 5% by weight, but the present disclosure is not limited thereto.
- In one embodiment of the present disclosure, after the third mixture is obtained in step (C), the third monomer is further added into the third mixture to obtain a fourth mixture.
- In the present disclosure, the first monomer, the second monomer, and the third monomer are each independently an acrylate compound or a diacrylate compound.
- In one embodiment of the present disclosure, the acrylate compound may be a compound of formula (III) below:
- wherein A2 is O or S; R7 is H or a C1-6 alkyl; and R8 is a C1-12 alkyl, (CH2)qN(R11)2, CH2(CH2OCH2)rCH2N(R12)2, or CH2(CH2OCH2)sCH2OR13; wherein R11, R12, and R13 are each independently a C1-6 alkyl; and q, r, and s are each independently an integer from 1 to 10.
- In one embodiment of the present disclosure, it is optional for the compound of formula (III) that A2 is O; R7 is H or a C1-6 alkyl; and R8 is a C1-10 alkyl, (CH2)qN(R11)2, CH2(CH2OCH2)rCH2N(R12)2, or CH2(CH2OCH2)SCH2OR13; wherein R11, R12, and R13 are each independently a C1-6 alkyl; and q, r, and s are each independently an integer from 1 to 6.
- In one embodiment of the present disclosure, the diacrylate compound may be a compound of formula (IV) below:
- wherein Y is O, NH, or S; R9 is H, or a C1-6 alkyl; R10 is a C1-6 alkyl, or a C6-20 aryl; and p is an integer from 1 to 12.
- In one embodiment of the present disclosure, it is optional for the compound of formula (IV) that Y is O or NH; R9 is H or a C1-6 alkyl; R10 is a C1-6 alkyl or a C6-20 aryl; and p is an integer from 1 to 8.
- In the method according to one embodiment of the present disclosure, after step (C), a step (D) of adding the third mixture into a second solvent may be further included. The second solvent is not particularly limited as long as it can induce the product to precipitate. For example, the second solvent may be water, an alcohol, a C5-10 alkane, or a mixture thereof. In particular, the alcohol comprises methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, 2-methyl butanol, sec-amyl alcohol, or a mixture thereof, but the present disclosure is not limited thereto. The C5-10 alkane comprises pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or a mixture thereof, but the present disclosure is not limited thereto.
- In the method according to another embodiment of the present disclosure, after step (C), a step (E) of adding the fourth mixture into a second solvent may be further included. The second solvent is not particularly limited as long as it can induce the product to precipitate. The second solvent is water, an alcohol, a C5-10 alkane, or a mixture thereof. In particular, the alcohol comprises methanol, ethanol, n-propanol, isopropanol, 2-butanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, 2-methyl butanol, sec-amyl alcohol, or a mixture thereof, but the present disclosure is not limited thereto. The C5-10 alkane comprises pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or a mixture thereof, but the present disclosure is not limited thereto.
- In one embodiment of the present disclosure, the first solvent is not particularly limited as long as it can serve as a solvent for the reaction. Preferably, the first solvent is an ether solvent, such as tetrahydrofuran or ethyl ether, but the present disclosure is not limited thereto.
- In one embodiment of the present disclosure, it is optional for the structure of formula (V) that x, y, and z are each independently an integer from 1 to 20. For example, x, y, and z are each independently an integer from 1 to 15, but the present disclosure is not limited thereto.
- In one embodiment of the present disclosure, it is optional for the compound of formula (VI) that A2 is O; R7 is H or a C1-3 alkyl; and R is a C1-8 alkyl, (CH2)qN(R11)2, CH2(CH2OCH2)rCH2N(R2)2, or CH2(CH2OCH2)sCH2OR13, wherein R11, R12, and R13 are each independently a C1-3 alkyl; and q, r, and s are each independently an integer from 1 to 6.
- In one embodiment of the present disclosure, the block copolymer comprises an end group represented by formula (VII) below:
- wherein R1 is a C1-6 alkyl; and R2 and R3 are each independently H or a C1-6 alkyl.
- In one embodiment of the block copolymer of the present disclosure, at least one of D, E, and F is a compound of formula (VIII) below:
- wherein R7 is H or a C1-6 alkyl; and R8 is (CH2)qN(R11)2 or CH2(CH2OCH2)rCH2N(R12)2, wherein R11 and R12 are each independently a C1-6 alkyl; and q and r are each independently an integer from 1 to 10.
- In one embodiment of the block copolymer of the present disclosure, it is optional for the compound of formula (VIII) that R7 is H or a C1-3 alkyl; and R8 is (CH2)qN(R11)2 or CH2(CH2OCH2)rCH2N(R12)2, wherein R11 and R12 are each independently a C1-3 alkyl; and q and r are each independently an integer from 1 to 6.
- The detailed description of the present disclosure is described below by way of specific embodiments, and those skilled in the art can readily appreciate the other advantages and efficacies of the present disclosure from the specification. The present disclosure may also be implemented or applied by other different embodiments. The details of the specification may also be applied to various aspects and applications, and various modifications and variations may be made without departing from the spirit of the present invention.
- In the present embodiment, the catalyst can be synthesized according to the following reaction formulae.
-
V(O)SO4(aq)+BaX2(aq)→V(O)X2(aq)+BaSO4(s) -
V(O)SO4(aq)+Ba(OC(O)R)2(aq)→V(O)(OC(O)R)2(aq)+BaSO4(s) -
V(O)SO4(aq)+Ba(OTf)2(aq)→V(O)(OTf)2(aq)+BaSO4(s) -
V(O)SO4(aq)+Ba(OTs)2(aq)→V(O)(OTs)2(aq)+BaSO4(s) -
V(O)SO4(aq)+Ba[(O3SC6H4CHCH2)n]2(aq)→V(O)[(O3SC6H4CHCH2)n]2(aq)+BaSO4(s) - Vanadium sulphate (VOSO4-5H2O, 2.5 mmol) was placed in a dry double-necked round bottom flask (50 mL), followed by anhydrous methanol (2.5 mL). To the resulting solution, a solution of BaX2 (1 equivalent, 2.5 mmol) (for example, Ba(OAc)2, BaOTs2, BaOTf2, or Ba[(O3SC6H4CHCH2)n]2) in methanol (2.5 mL) was slowly added at room temperature. After stirring for 30 minutes, the reaction mixture is cloudy and is accompanied by a large amount of barium sulfate precipitation. The mixture was filtered through a plug of celite, and the obtained filtrate was evaporated to give a dark blue solid. The resulting solid was dried under vacuum at 120° C. for 4 hours. The product obtained can be stored in a dry box for several weeks and can be used directly.
- To a round bottom flask (100 mL) containing the benzoic acid oxovanadium catalyst (2.5 mg), 1-methoxy-2-methyl-1-(trimethylsilyloxy)propene (MTS, 0.20 mL, 0.99 mmol) dissolved in tetrahydrofuran (20 mL) was added. The round bottom flask was previously sealed with a membrane and purged with argon gas. Then, butyl methacrylate (BuMA, 2.2 mL, 11.2 mmol) was injected, and the temperature was raised from 20° C. to 33° C. After 30 minutes, the exothermic reaction was weak, and two 0.1 mL aliquots of the reaction solution were extracted and analyzed by GPC and 1H NMR, respectively. Afterwards, 2-(dimethylamino)ethyl methacrylate (DMAEMA, 2.65 mL, 15.7 mmol) was added and the temperature was observed to rise from 22° C. to 34° C. The crude product was poured into hexane to induce precipitation, and the purified copolymer was filtered to remove small molecule impurities, obtaining a final product.
- 1H NMR (400 MHz, CDCl3) δ 0.88 (br, 55H), 0.94 (br, 56H), 1.04 (br, 39H), 1.40 (br, 40H), 1.61 (br, 35H), 1.81-1.90 (br, 82H), 2.28 (br, 107H), 2.56 (br, 36H), 3.94 (br, 33H), 4.06 (br, 35H).
- Mn=4104 (THF); Mw=4785; PDI=1.17.
- To a round bottom flask (100 mL) containing the benzoic acid oxovanadium catalyst (2.5 mg), 1-methoxy-2-methyl-1-(trimethylsilyloxy)propene (MTS, 0.20 mL, 0.99 mmol) dissolved in tetrahydrofuran (20 mL) was added. The round bottom flask was previously sealed with a membrane and purged with argon gas. Then, hexyl methacrylate (HexMA, 2.2 mL, 11.2 mmol) was injected, and the temperature was raised from 20° C. to 33° C. After 30 minutes, the exothermic reaction was weak, and two 0.1 mL aliquots of the reaction solution were extracted and analyzed by GPC and 1H NMR, respectively. Afterwards, PEGMA (0.095 mL (a 50 vol % solution), 2.1 mmol, MW=500) dissolved in tetrahydrofuran was added and the temperature was raised from 25° C. to 27° C. Next, two 0.1 mL aliquots were extracted and analyzed by GPC and 1H NMR, respectively. Afterwards, 2-(dimethylamino)ethyl methacrylate (DMAEMA, 2.65 mL, 15.7 mmol) was added and the temperature was observed to rise from 22° C. to 34° C. The crude product was poured into hexane to induce precipitation, and the purified copolymer was filtered to remove small molecule impurities, obtaining a final product.
- 1H NMR (400 MHz, CDCl3) δ 0.90 (br, 50H), 1.00 (br, 21H), 1.32 (br, 46H), 1.61-1.68 (br, 23H), 1.81-1.98 (br, 31H), 2.28 (br, 58H), 2.56 (br, 19H), 3.38 (br, 3H), 3.55 (br, 3H), 3.64 (br, 18H), 3.92 (br, 14H), 4.06 (br, 21H).
- Mn=6249 (THF); Mw=7811; PDI=1.25.
- To a round bottom flask (100 mL) containing the benzoic acid oxovanadium catalyst (2.5 mg), 1-methoxy-2-methyl-1-(trimethylsilyloxy)propene (MTS, 0.20 mL, 0.99 mmol) dissolved in tetrahydrofuran (20 mL) was added. The round bottom flask was previously sealed with a membrane and purged with argon gas. Then, a diacrylate compound (6.0 mL (a 33.3 vol % solution), 2.9 mmol) dissolved in tetrahydrofuran was added and the temperature was raised from 25° C. to 27° C. Next, two 0.1 mL aliquots were extracted and analyzed by GPC and 1H NMR, respectively. Afterwards, hexyl methacrylate (HexMA, 1.0 mL, 5.9 mmol) was injected, and the temperature was raised from 20° C. to 33° C. After 30 minutes, the exothermic reaction was weak, and two 0.1 mL aliquots of the reaction solution were extracted and analyzed by GPC and 1H NMR, respectively. The crude product was poured into hexane to induce precipitation, and the purified copolymer was filtered to remove small molecule impurities, obtaining a final product.
- 1H NMR (400 MHz, CDCl3) δ 0.99-1.18 (br, 10H), 1.32-1.35 (br, 7H), 1.62 (s, 8H), 1.95 (br, 3H), 3.64-3.71 (br, 17H), 3.83 (s, 2H), 3.95 (s, 2H), 6.79 (br, 2H), 7.11 (br, 2H).
- Mn=6249 (THF); Mw=7811; PDI=1.25.
- The copolymer of Example 3 (1 g) and the commercially available dispersant (1 g) were dissolved in 1 mL of tetrahydrofuran, into which 135 uL of yellow pigment (from a solution of 500 mg yellow pigment in 3 mL of tetrahydrofuran) was added, followed by grinding and stirring for 30 seconds. The dispersion of the yellow pigment was observed and shown in Table 1.
-
TABLE 1 Dispersion effect Particle suspension Copolymer of Example 2 Excellent No particle suspension or uneven dispersion Copolymer of Example 3 Excellent No particle suspension or uneven dispersion Commercially available Good Significant particle dispersant suspension - The above specific embodiments are to be construed as illustrative only and do not limit the remainder of this disclosure in any way.
- Although the present invention has been explained in relation to its preferred embodiment, it is to be understood that many other possible modifications and variations can be made without departing from the spirit and scope of the invention as hereinafter claimed.
Claims (5)
[D]x-[E]y-[F]z (V)
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US6413306B1 (en) * | 1999-10-07 | 2002-07-02 | E. I. Du Pont De Nemours And Company | Pigment dispersions containing ABC-block polymer dispersant |
WO2013113071A1 (en) * | 2012-02-03 | 2013-08-08 | Commonwealth Scientific And Industrial Research Organisation | Branched polymers |
WO2018140977A1 (en) * | 2017-01-30 | 2018-08-02 | Massachusetts Institute Of Technology | Reactions enabled by thermoresponsive and photoresponsive gels |
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US4681918A (en) * | 1981-06-30 | 1987-07-21 | E. I. Du Pont De Nemours And Company | "Living" polymers and process for their preparation |
US4866145A (en) * | 1988-04-01 | 1989-09-12 | E. I. Du Pont De Nemours And Company | Catalyst for group transfer polymerization |
JP3434526B2 (en) * | 1992-12-01 | 2003-08-11 | 三井化学株式会社 | Method for producing epoxy-containing compound, α-hydroxycarbonyl compound or alkylsilyl or arylsilyl derivative of α-hydroxycarbonyl compound |
JPH07228620A (en) * | 1994-02-15 | 1995-08-29 | Mitsubishi Rayon Co Ltd | Production of methacrylic ester polymer |
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WO2013113071A1 (en) * | 2012-02-03 | 2013-08-08 | Commonwealth Scientific And Industrial Research Organisation | Branched polymers |
WO2018140977A1 (en) * | 2017-01-30 | 2018-08-02 | Massachusetts Institute Of Technology | Reactions enabled by thermoresponsive and photoresponsive gels |
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Title |
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Baeten, Evelien et al "RAFT multiblock reactor telescoping: from monomers to tetrablock copolymers in a continuous multistage reactor cascade" 2017 Polymer Chemistry, 8, 3815-3824 (Year: 2017) * |
Webster, Owen "Group Transfer polymerization: Mechanism and Comparison with other methods for controlled polymerization of Acrylic Monomers" 2004 Adv polymer Sci 167:1-34 (Year: 2004) * |
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