WO2022123185A1 - Polymerisation en suspension des alcoxyamines avec des monomeres styreniques et (meth) acryliques - Google Patents
Polymerisation en suspension des alcoxyamines avec des monomeres styreniques et (meth) acryliques Download PDFInfo
- Publication number
- WO2022123185A1 WO2022123185A1 PCT/FR2021/052267 FR2021052267W WO2022123185A1 WO 2022123185 A1 WO2022123185 A1 WO 2022123185A1 FR 2021052267 W FR2021052267 W FR 2021052267W WO 2022123185 A1 WO2022123185 A1 WO 2022123185A1
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- WO
- WIPO (PCT)
- Prior art keywords
- monomers
- nitroxide
- mass
- polymerization
- alkoxyamine
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims abstract description 57
- 125000005262 alkoxyamine group Chemical group 0.000 title claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 230000008569 process Effects 0.000 claims abstract description 56
- 239000011324 bead Substances 0.000 claims abstract description 22
- -1 N-tert-Butyl-1-diethylphosphono-2,2-dimethylpropyl Nitroxide Chemical group 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 21
- 229920001400 block copolymer Polymers 0.000 claims description 21
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000008346 aqueous phase Substances 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 9
- 239000011049 pearl Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000000375 suspending agent Substances 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 6
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003277 amino group Chemical group 0.000 claims description 3
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- LHCFAZQDKKRUDE-UHFFFAOYSA-N 2-[tert-butyl-(1-diethoxyphosphoryl-2,2-dimethylpropyl)amino]oxy-2-methylpropanoic acid Chemical group CCOP(=O)(OCC)C(C(C)(C)C)N(C(C)(C)C)OC(C)(C)C(O)=O LHCFAZQDKKRUDE-UHFFFAOYSA-N 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 238000012705 nitroxide-mediated radical polymerization Methods 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
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- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QEDGLQDJPVXWJX-UHFFFAOYSA-N 1-ethyl-3-hydroxyimidazolidin-2-one;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCN1CCN(O)C1=O QEDGLQDJPVXWJX-UHFFFAOYSA-N 0.000 description 2
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
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- 150000003440 styrenes Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical class C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- YWOYCXNNAGNDKT-UHFFFAOYSA-N 1-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OC(C)OC(=O)C=C YWOYCXNNAGNDKT-UHFFFAOYSA-N 0.000 description 1
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- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
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- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PFPUZMSQZJFLBK-UHFFFAOYSA-N 2-(2-oxoimidazolidin-1-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCNC1=O PFPUZMSQZJFLBK-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical class CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical class OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
Definitions
- TITLE Suspension polymerization of alkoxyamines with styrenic and (meth)acrylic monomers.
- the present invention relates to a process for the suspension polymerization of alkoxyamines with styrenic and (meth)acrylic monomers, the beads and compositions thus obtained, as well as the use of these beads and compositions.
- Block copolymers are polymers that are difficult to manufacture, but they have advantages due to their very block structure, which allows the establishment and adjustment of morphologies at the nanometric scale. Their physical behavior such as mechanical, optical for example, and chemical such as their resistance to chemical agents are superior to homopolymers or random copolymers.
- NMP nitroxides
- alkoxyamines are used which, by balancing the radicals with a nitroxide released at a certain temperature, make it possible to control the polymerization of the blocks. This technology is described for example in the article by Nicolas J. et al, Progress in Polymer Science 38 (2013) 63-235. With the chemistry of alkoxyamines, the dispersity of block copolymers can vary from 1.2 to 2 depending on the conversion at which the polymerization is conducted.
- a monofunctional alkoxyamine is reacted in a reactor in the presence of a first monomer or group of monomers M1 in a solvent or not until a conversion of approximately 70%, then the monomers M1 generally remaining by evaporation.
- the macro-alkoxyamine obtained is then placed in the presence of a second monomer or group of monomers M2 to form the second block and follows the same process of conversion/elimination of M2.
- a PolyMI-PolyM2 diblock copolymer is then obtained.
- This method makes it possible to obtain products with targeted properties but the conditions of the process penalize some of them such as optical, or thermal, without a link being able to be made between impurities or the exact nature of the block copolymers as well manufactured.
- a second process called emulsion has been attempted, but the transfer to an industrial scale is complicated (synthesis, recovery of the product).
- a third so-called suspension process seems to have advantages when it comes to obtaining compositions of copolymers making it possible to maximize certain properties such as mechanical, thermal or optical.
- the compositions obtained by this suspension process differ because part of the monomers is found in the form of homopolymer or random copolymer and not block copolymers.
- Suspension polymerization consists in polymerizing the reaction mixture within droplets dispersed in water. For this, good agitation is used in the reactor and a so-called “suspension” agent, allowing the preparation of beads, or balls whose diameters can vary or even be adjusted from a few microns to a few hundred microns.
- the conversion is maximized even if it means undergoing a drift in the dispersity of the block obtained.
- This suspension process uses as alkoxyamine the structure 3-(((2-cyanopropan-2-yl)oxy)(cyclohexyl)amino)-2,2-dimethyl-3-phenylpropanenitrile.
- a first block is prepared using acrylate and/or styrenic monomers, the other blocks being made up of blocks made up of methacrylate and/or styrenic entities.
- the second step carried out mainly with methacrylates is done in an uncontrolled way because it is a characteristic of this family of alkoxyamines used in the context of the invention.
- the presence of a mercaptan from the beginning of this second step does not interfere with the polymerization process from the Poly M1 block, the synthesis of the block copolymer does take place and random entities are jointly synthesized
- the conversion is accelerated when compared to products obtained without the presence of mercaptan ( Figure 1).
- the products obtained in the presence of mercaptan during the second step are much more thermally stable as can be verified by thermogravimetric analysis.
- the applicant shows that it is possible to convert up to 90 and even 95% of the monomers within the process resulting from the synthesis of the various blocks.
- the small proportions of unconverted monomers are polymerized using a water-soluble initiator at the end of the second stage.
- a surfactant can be added from the first step.
- copolymers obtained have a high viscosity, which complicates the transformation steps, in an extruder or an injection molding machine for example.
- the compositions of the invention have better fluidity than the products obtained with a bulk process.
- compositions of block copolymer and of polymer resulting from the radical process linked to the presence of the mercaptan is therefore obtained.
- This composition has characteristics of the sequence of the monomers or of the copolymers different from those obtained using the other processes because the reactivity ratios of the monomers in a suspension process are different (see in particular PJ Dowding, B. Vincent: Colloids and Surfaces A: Physicochem. Eng. Aspects 161 (2000) 263-264.
- These compositions less well defined in structure than the block copolymers resulting from the mass process are therefore new.They nevertheless prove to be efficient by presenting superior optical properties and better thermal stabilities.
- compositions of copolymers obtained using the process of the invention allow uses in applications requiring optical qualities, heat resistance, easy transformation conditions or optimal mechanical performance. They can be used in three-dimensional printing by sintering beads.
- the invention relates to a process for the suspension polymerization of (meth)acrylic and/or styrenic monomers to obtain beads of a composition comprising at least one block copolymer comprising the following two successive synthesis steps:
- Step 1
- an organic phase is introduced consisting of at least an alkoxyamine and at least one acrylic and/or styrenic monomer with a nitroxide/molar molar ratio of between 1/50 and 1/1000 and an aqueous phase/organic phase mass ratio of between 3 and 10, said alkoxyamine being a carrier at least one nitroxide corresponding to the following formula: [Chem 1 ]
- Ra and Rb denoting identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked together so as to form a cycle and optionally substituted by hydroxy, alkoxy or amino groups,
- RL denoting a monovalent group with a molar mass greater than 15.42 g/mol
- Ra and Rb denoting identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked together so as to form a cycle and optionally substituted by hydroxy groups , alkoxy or amino,
- RL designating a monovalent group with a molar mass greater than 15.42 g/mol.
- the invention relates to the suspension polymerization of monomers and alkoxyamines carrying a nitroxide whose general formula (1) is as follows:
- Ra and Rb denoting identical or different alkyl groups having from 1 to 40 carbon atoms, optionally linked together so as to form a cycle and optionally substituted by hydroxy, alkoxy or amino groups
- RL denoting a monovalent group of higher molar mass at 15.42 g/mol, preferably greater than 30 g/mol.
- the RL group can for example have a molar mass of between 40 and 450 g/mol. It is preferably a phosphorus group of the following general formula:
- X and Y which can be identical or different, can be chosen from alkyl, cycloalkyl, alkoxyl, aryloxyl, aryl, aralkyloxy, perfluoroalkyl, aralkyl radicals and can comprise from 1 to 20 carbon atoms;
- X and/or Y can also be a halogen atom such as a chlorine, bromine or fluorine atom.
- RL is a phosphonate group of formula: [Chem 4] in which Rc and Rd are two identical or different alkyl groups, optionally connected so as to form a cycle, comprising from 1 to 40 carbon atoms, optionally substituted or not.
- the RL group can also comprise at least one aromatic ring such as the phenyl radical or the naphthyl radical, substituted for example by one or more alkyl radical(s) comprising from 1 to 10 carbon atoms.
- nitroxides of formula 1 are preferred because they make it possible to obtain good control of the radical polymerization of (meth)acrylic monomers, as is taught in WO 03/062293.
- the alkoxyamines (2) of following formula having a nitroxide of formula (1) are therefore preferred:
- Z denotes a multivalent group
- the preferred alkoxyamines bearing these nitroxides are derived from the following monomalkoxyamine (4):
- This alkoxyamine (4) is monofunctional in alkoxyamine and therefore in nitroxide, it leads to compositions of diblock copolymers within the scope of the invention constituting one of the preferences of the invention.
- This alkoxyamine (4) can be added to di, tri or multifunctional monomers to lead to multifunctional alkoxyamines in alkoxyamine and therefore in nitroxide.
- Such multifunctional alkoxyamines are described in EP1526138.
- These multifunctional alkoxyamines (5) constitute a second preference of the invention with a preference for the dialkoxyamines (6).
- C2-C10 alkyl diol diacrylates typical di-alkoxyamines of the invention are obtained; they make it possible to prepare compositions of triblock copolymers.
- C2 to C6 alkyls, and more preferably C2-C4 alkyls ethane diol diacrylate, propane diol diacrylate, butane diol diacrylate
- the addition product of the alkoxyamine (4) on the butane diol diacrylate is in particular preferred and leads to the dialkoxyamine (7).
- di or multifunctional compounds can be used to prepare the di, tri or multi aloxyamines which can be used in the context of the invention, whether they are of the acrylic or styrenic type.
- the monomers used for the preparation of the block copolymer compositions of the invention are chosen from the following list:
- Monomers of (meth)acrylic type and vinylaromatic monomers such as styrene or substituted styrenes, in particular alpha-methylstyrene, silylated styrenes, acrylic monomers such as acrylic acid or its salts, alkyl acrylates, cycloalkyl or aryl such as methyl, ethyl, butyl, ethylhexyl or phenyl acrylate, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, etheralkyl acrylates such as 2-methoxyethyl acrylate, alkoxy- or aryloxy-polyalkylene glycol acrylates such as acrylates of methoxypolyethylene glycol, ethoxypolyethylene glycol acrylates, methoxypolypropylene glycol acrylates, methoxy-polyethylene glycol-polypropylene glycol acrylates or mixtures thereof, aminoalkyl
- these are alkyl acrylates and methacrylates, butyl acrylate in particular, 2-ethyl hexyl acrylate, isobornyl acrylate and methacrylate, 4 ter butyl acrylate cyclohexyl, methyl methacrylate, acrylic and methacrylic acids and even more preferably butyl acrylate, styrene, methacrylic acid, and methyl methacrylate.
- alkyl acrylates and methacrylates butyl acrylate in particular, 2-ethyl hexyl acrylate, isobornyl acrylate and methacrylate, 4 ter butyl acrylate cyclohexyl, methyl methacrylate, acrylic and methacrylic acids and even more preferably butyl acrylate, styrene, methacrylic acid, and methyl methacrylate.
- the acrylic and styrenic monomers are used for the synthesis of stage 1 within the framework of the process of the invention
- the methacrylic and styrenic monomers are used for the synthesis of stage 2 within the framework of the process of the invention.
- the monomers of stage 1 are preferably chosen from butyl acrylate, 2-ethyl hexyl acrylate and styrene, alone or in combination, and the monomers of stage 2 are chosen from methyl methacrylate , methacrylic acid and styrene, alone or in combination.
- the nitroxide/molar molar ratio is between 1/50 and 1/1000.
- mercaptans used in step 2 of the process of the invention are mercaptans of any type denoted R-SH with R alkyl radical linear or non-functionalized or not, having from 3 to 12 carbon and from preferably 4 to 8 carbon. Mention may be made in particular of mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl, octyl, n-dodecyl mercaptans alone or in combination. Preferably, it is butyl or octyl mercaptan alone or in mixtures.
- the suspending agent used in the context of the invention is a typical suspending agent known to those skilled in the art. It can be polyvinyl alcohol, polyvinyl pyrrolidone, acid copolymers (meth) acrylic acid, or even copolymers of 2-acrylamido-2-methylpropanesulfonic acid, preferably polyvinyl alcohol or copolymers of 2-acrylamido-2-methylpropanesulfonic acid, and more preferably copolymers of 2- acrylamido-2- methylpropanesulfonic.
- This suspending agent is described in EP0683182 in Example 1.
- the suspending agent is present in a quantity of between 0.5 and 4% by mass relative to the aqueous phase.
- inorganic particles can be added to improve the stability of the suspension.
- a surfactant can be added to the aqueous phase in an amount of between 0 and 10,000 ppm relative to the aqueous phase, preferably between 0 and 5,000 ppm, more preferably between 0 and 400 ppm. It can be any type of ionic or non-ionic surfactant.
- a water-soluble initiator is added at the end of polymerization, when the suspension to be polymerized has reached a conversion greater than 95%, chosen for example from persulfates and in particular potassium persulfate in an amount which may vary from 0.1 to 2% and preferably between 0.1 and 1% by mass relative to the total organic phase.
- the water-soluble initiator makes it possible, at the end of the synthesis, to convert the last low percentages of monomers into a shell which attaches to the beads obtained in the process of the invention.
- an additional quantity of monomers from stage 2 of between 1 and 10% by mass in relation to the quantity of monomers from stages 1 and 2 and preferably between 3 and 7% by mass can be added. together with the water-soluble initiator.
- the mass ratio of the aqueous phase/organic phase in step 1 of the process of the invention is between 3 and 10 and preferably between 4 and 8.
- the molar ratio of monomers (acrylic and/or styrenic)/methacrylic monomers is between 25/45 and 70/30 and preferably between 25/75 and 55/45.
- a mercaptan is introduced with a mercaptan/nitroxide molar ratio of between 0.2 and 0.8 and preferably between 0.4 and 0.6.
- Agitation depends on the reactor used. For example, for a 20-litre reactor with an impeller-type agitator, it is several hundred revolutions per minute. For a 5000 liter reactor, it is between 100 and 250 revolutions per minute, always with an impeller-type stirring wheel. Other type of agitation can be used in the context of the present invention.
- the polymerization temperature is between 15 and 150°C and preferably between 100 and 135°C, more preferably between 125 and 135°C.
- the molecular mass by weight of the compositions obtained by the process of the invention is between 5000 and 300000 g/mole and preferably between 10000 and 200000 g/mole with a dispersity index between 2 and 4 and preferably between 2.5 and 3.3.
- the compositions are preferably compositions of diblock copolymers and random copolymers derived from a monoalkoxyamine.
- compositions are preferably compositions of triblock copolymers and random copolymers derived from a dialkoxyamine.
- the invention relates to the beads obtained using the method of the invention. They are in the form of spheres whose average diameter by weight is between 5 and 600 ⁇ m and preferably between 50 and 400 ⁇ m, more preferably between 50 and 250 ⁇ m, measured by laser diffraction in the dry process. using a device from Malvern.
- the beads consist of a nanostructured material consisting of a matrix of one of the blocks and a dispersed phase of the other block, and of a continuous shell of a hard phase of Tg > 20°C, said shell having a thickness varying from 30 to 150 nm.
- Beads having a continuous shell are a preferred aspect of beads obtained using the process of the invention.
- the invention also relates to the compositions obtained using the process of the invention because they are different both in their analytical aspect and in their properties from those obtained with the other processes (solvent, mass, emulsion).
- the invention also relates to the uses of the compositions of the invention or of the beads of the invention for manufacturing objects by molding, injection compression, extrusion.
- the invention also relates to the use of the beads obtained with the process of the invention in the field of three-dimensional printing known as laser sintering to form objects.
- Powder sintering technology under a laser beam is used to manufacture three-dimensional objects such as prototypes, models, but also functional parts, particularly in the automotive, nautical, aeronautical, aerospace, medical (prostheses, hearing systems , cellular fabrics, etc.), textiles, clothing, fashion, decoration, boxes for electronics, telephony, home automation, IT, lighting.
- a thin layer of powder is deposited on a horizontal plate held in an enclosure heated to a certain temperature.
- the laser provides the energy necessary to sinter the powder particles at different points of the powder layer according to a geometry corresponding to the object, for example using a computer having in memory the shape of the object and restoring the latter in the form of slices.
- the horizontal plate is lowered by a value corresponding to the thickness of a layer of powder (for example between 0.05 and 2 mm and generally of the order of 0.1 mm) then a new layer of powder is deposited and the laser provides the energy needed to sinter the powder particles according to a geometry corresponding to this new slice of the object and so on.
- the procedure is repeated until the entire object has been made.
- An object is obtained inside the enclosure surrounded by unsintered powder. The parts which were not sintered therefore remained in the powder state. After complete cooling, the object is separated from the powder which can be reused for another operation.
- Figure 1 is the conversion of methyl methacrylate during step 2 of the process of the invention.
- the curve with open circles represents the conversion in the presence of mercaptan such as in example 1 of the invention, that in filled circles represents the conversion during this same step without mercaptan such as in comparative example 2.
- Figure 2 is the degradation profile as a function of temperature (TGA) of the product obtained in the presence of mercaptan.
- TGA temperature at the peak of degradation.
- FIG. 3 is the degradation profile as a function of temperature (TGA) of the product obtained in the absence of mercaptan, indicating a much more accentuated degradation profile than in the presence of mercaptan. It can be noted that the degradations are more numerous and take place at lower temperatures (282, 290, 300°C). [Fig 4]:
- Figure 4 is an atomic force microscopy (AFM) photo of a section of a bead obtained according to the process of the invention with a water-soluble initiator (potassium persulfate).
- a water-soluble initiator potassium persulfate
- PMMA clear crown
- the interior of the pearl is made up of a clear dispersed phase (PMMA) and a dark continuous phase (polybutyl acrylate.
- PMMA clear dispersed phase
- PMMA dark continuous phase
- Such pearls lead to an easily handled, non-sticky powder.
- FIG. 5 is an atomic force microscopy (AFM) photo of a section of a bead obtained according to the method of the invention without a water-soluble initiator. There is an ill-defined diffuse zone on the outside of the pearl.
- the interior of the bead consists of a clear dispersed phase (PMMA) and a dark continuous phase (polybutyl acrylate).
- PMMA clear dispersed phase
- polybutyl acrylate polybutyl acrylate
- Figure 6 corresponds to the normalized profile of the LAC chromatogram of a PAbu block.
- This butyl polyacrylate corresponds to the block prepared at the end of the first stage of the process of the invention. It can therefore be reactivated for the second step of the process of the invention. It is obtained in example 1 in step 2.
- Figure 7 corresponds to the normalized profile of the LAC chromatogram of a composition of the invention.
- the PAbu alone almost disappeared (16 minutes elution), while a peak appears at 35 minutes attributable to a triblock copolymer.
- a peak appears which is attributable to a statistical composition rich in PMMA, coming from the interior of the pearl and the shell.
- Figure 8 corresponds to the normalized profile of the LAC chromatogram of a composition obtained by a mass process, as prepared in Example 3.
- composition is rich in triblock (peak at 34 minutes. Traces of composition rich in PMMA are visible with a peak at 38 minutes.
- Figure 9 corresponds to the normalized profile of the LAC chromatogram of a PMMA composition.
- the peaks visible at the start of the elution (before 10 minutes) come from impurities attributed to traces of solvents and other additives present in the commercial grade used for the analysis and should not be taken into account.
- LAC Liquid adsorption chromatography
- Liquid adsorption chromatography is a technique for separating complex mixtures of polymers from which each of its constituents can be eluted according to its chemical composition, therefore independently of its molar mass.
- the samples are injected into the WATERS ALLIANCE 2695 HPLC device.
- the eluent is a Gradient (Hexane/THF) acidified with 5% acetic acid and stabilized with BHT.
- the polar column used is a SunFire Prep Silica 5
- the flow rate is 1 ml/min and the volume of sample injected is 30 pl.
- the detector used is an Agilent ELSD (Evaporative Light Scattering Detector) 380 and a Waters 2487 Dual UV 254 nm.
- the polymer samples were prepared at 2 g/l in THF.
- the PMMA and PABu samples will serve as standards so that they can be identified at the end of the analysis of the PMMA-PABu/PMMA triblock.
- a volume of 30 pL is injected.
- Yellowing index This is measured according to the YIE313 standard (NF ISO 7724-3 1988).
- the yellow index (Yl) is measured on a Colorquest HunterLab (conditions: Illuminant: D65, Observation angle: 10°, Observation mode: Transmission).
- Example 1 (invention): synthesis of a composition according to the process of the invention:
- the starting alkoxyamine used is N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-0-(2-carboxyprop-2-yl)hydroxylamine, the structural formula of which is as follows:
- Diamins are prepared in ethanol from Blocbuilder MA® (Arkema) and butanedioldiacrylate (BDMA).
- a 1 L reactor is inerted with nitrogen. 114g of ethanol are introduced into a reactor, 60g of Blocbuilder MA® and 15.7g of BDMA.
- the reactor is stirred at 100 rpm and heated to 80° C. (1 bar) for 4 hours. The solid content is 35%. The temperature is lowered to 25°C. After evaporation of the ethanol, the diamins are recovered and can be used as is.
- a 5L reactor is used.
- the aqueous phase is prepared directly in the reactor and stirred at 500 rpm for 30 minutes.
- Aqueous phase Aqueous phase :
- Suspending agent 2-acrylamido-2-methylpropanesulfonic acid copolymer: 15.3 g (305.8 g for a 5% solution)
- surfactant a polyethoxylated C12-C14 alcohol (50 ethoxylated units) available for example from Cognis, Disponil® LS500): 0.5 g
- the organic phase is prepared in another container: diamins: 16.1 g
- the organic phase is added after alternating cycles of vacuum and nitrogen in the reactor.
- the suspension is then heated with the following cycle:
- step 2 of the process of the invention is a polymethyl methacrylate-poly(butyl acrylate)-polymethyl methacrylate copolymer composition
- the organic phase is prepared from methyl methacrylate and mercaptan.
- the organic phase is introduced into the reactor by vacuum.
- the mixture is heated according to the cycle:
- the bark is formed according to the following recipe:
- Demineralized water 92g
- Potassium persulfate 0.73g The polymerization takes place at 85° C. for 1 hour 30 minutes.
- the suspension is then recovered.
- the beads are filtered and washed twice with water and dried in an oven at 50°C.
- the product has the following properties:
- the mass composition determined by NMR is 45% PABu, and 55% PMMA.
- Example 1 is repeated but without addition of mercaptan in step 3.
- the process of the invention makes it possible to improve the kinetics (figure 1) and leads to better stability of the composition obtained (figures 2 and 3).
- the presence of a mercaptan during step 3 is decisive for the stability of the composition obtained.
- Example 3 bulk synthesis process.
- a comparative composition of a triblock copolymer prepared with the mass process is carried out.
- the copolymer obtained has a peak molecular weight (Mp) of 100,000 g/mole.
- Example 4 Evaluation of the yellow index on 50/50 mixtures by mass of PMMA with compositions of the invention of example 1 and compositions obtained according to example 3. These mixtures are obtained by extrusion then injection of samples at 240°C.
- the yellow index (Yl) is measured on a Colorquest HunterLab (conditions: Illuminant: D65, Observation angle: 10°, Observation mode: Transmission).
- Example 5 The applicant compared the rheology of the compositions obtained according to example 1 of the invention and according to example 3 by measuring the melt index (MFI, melt index flow).
- Block copolymers are used to improve the impact properties of commodity polymers.
- Block copolymers have a block with a low glass transition temperature ( ⁇ 0°C, for example butyl acrylate) and a block with a high glass transition temperature (>90°C, like PMMA). They improve the impact resistance of several materials, such as polyoxymethylene. A few percent of copolymers are added to the polymer to obtain a material with improved impact properties.
- block copolymers synthesized using a solvent can degrade polyoxymethylene and lead to the formation of formaldehyde during the implementation of the materials (mixtures formed at temperature). Synthesis by aqueous route according to the process of the invention allows the composition obtained to limit the degradation of the POM during the mixing stages and to obtain a material with improved properties.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
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Abstract
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2023535477A JP2023552611A (ja) | 2020-12-10 | 2021-12-09 | スチレン系及び(メタ)アクリル系モノマーを用いたアルコキシアミンの懸濁重合 |
US18/266,517 US20240043599A1 (en) | 2020-12-10 | 2021-12-09 | Suspension polymerization of alkoxyamines with styrenic and (meth)acrylic monomers |
CN202180083400.1A CN116601178A (zh) | 2020-12-10 | 2021-12-09 | 烷氧基胺与苯乙烯类和(甲基)丙烯酸类单体的悬浮聚合 |
EP21851819.9A EP4259675A1 (fr) | 2020-12-10 | 2021-12-09 | Polymerisation en suspension des alcoxyamines avec des monomeres styreniques et (meth) acryliques |
KR1020237022764A KR20230117206A (ko) | 2020-12-10 | 2021-12-09 | 알콕시아민과 스티렌 및 (메트)아크릴 단량체의 현탁중합 |
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FR2012988A FR3117487B1 (fr) | 2020-12-10 | 2020-12-10 | Polymérisation en suspension des alcoxyamines avec des monomères styréniques et (meth) acryliques. |
FRFR2012988 | 2020-12-10 |
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WO2022123185A1 true WO2022123185A1 (fr) | 2022-06-16 |
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PCT/FR2021/052267 WO2022123185A1 (fr) | 2020-12-10 | 2021-12-09 | Polymerisation en suspension des alcoxyamines avec des monomeres styreniques et (meth) acryliques |
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US (1) | US20240043599A1 (fr) |
EP (1) | EP4259675A1 (fr) |
JP (1) | JP2023552611A (fr) |
KR (1) | KR20230117206A (fr) |
CN (1) | CN116601178A (fr) |
FR (1) | FR3117487B1 (fr) |
WO (1) | WO2022123185A1 (fr) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0683182A2 (fr) | 1994-05-19 | 1995-11-22 | ELF ATOCHEM ITALIA S.r.l. | Procédé de préparation de polymères acryliques |
WO2003062293A1 (fr) | 2002-01-22 | 2003-07-31 | Atofina | Procede de fabrication et utilisation de materiaux renforces au choc contenant des copolymeres blocs obtenus par polymerisation radicalaire controlee en presence de nitroxydes |
EP1526138A1 (fr) | 2003-10-24 | 2005-04-27 | Arkema | Procédé de préparation de polyalcoaxyamines utilisables comme amorceurs pour la polymérisation radicalaire de (co)polymères vivants polyfonctionnels |
FR2924714A1 (fr) * | 2007-12-07 | 2009-06-12 | Arkema France | Procede de preparation d'une dispersion aqueuse de particules de polymeres par un procede de polymerisation radicalaire en dispersion, dispersions obtenues et revetements prepares avec celles-ci. |
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2020
- 2020-12-10 FR FR2012988A patent/FR3117487B1/fr active Active
-
2021
- 2021-12-09 US US18/266,517 patent/US20240043599A1/en active Pending
- 2021-12-09 JP JP2023535477A patent/JP2023552611A/ja active Pending
- 2021-12-09 KR KR1020237022764A patent/KR20230117206A/ko unknown
- 2021-12-09 WO PCT/FR2021/052267 patent/WO2022123185A1/fr active Application Filing
- 2021-12-09 CN CN202180083400.1A patent/CN116601178A/zh active Pending
- 2021-12-09 EP EP21851819.9A patent/EP4259675A1/fr active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0683182A2 (fr) | 1994-05-19 | 1995-11-22 | ELF ATOCHEM ITALIA S.r.l. | Procédé de préparation de polymères acryliques |
WO2003062293A1 (fr) | 2002-01-22 | 2003-07-31 | Atofina | Procede de fabrication et utilisation de materiaux renforces au choc contenant des copolymeres blocs obtenus par polymerisation radicalaire controlee en presence de nitroxydes |
EP1526138A1 (fr) | 2003-10-24 | 2005-04-27 | Arkema | Procédé de préparation de polyalcoaxyamines utilisables comme amorceurs pour la polymérisation radicalaire de (co)polymères vivants polyfonctionnels |
FR2924714A1 (fr) * | 2007-12-07 | 2009-06-12 | Arkema France | Procede de preparation d'une dispersion aqueuse de particules de polymeres par un procede de polymerisation radicalaire en dispersion, dispersions obtenues et revetements prepares avec celles-ci. |
Non-Patent Citations (6)
Title |
---|
BALLARD NICHOLAS ET AL: "Nitroxide mediated suspension polymerization of methacrylic monomers", CHEMICAL ENGENEERING JOURNAL, ELSEVIER, AMSTERDAM, NL, vol. 316, 5 February 2017 (2017-02-05), pages 655 - 662, XP029940598, ISSN: 1385-8947, DOI: 10.1016/J.CEJ.2017.02.006 * |
CHEMICAL ENGINEERING JOURNAL, vol. 316, 2017, pages 655 - 662 |
NICOLAS J. ET AL., PROGRESS IN POLYMER SCIENCE, vol. 38, 2013, pages 63 - 235 |
P.J. DOWDINGB. VINCENT, COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS, vol. 161, 2000, pages 263 - 264 |
SIMULA A. ET AL., EUROPEAN POLYMER JOURNAL, vol. 110, 2019, pages 319 - 329 |
TAUBE CARSTEN ET AL: "TEMPO-controlled radical suspension polymerization of poly(styrene)-block-poly(styrene-co-acrylonitrile) and poly(styrene)-block-poly(styrene-co-butyl methacrylate)", MACROMOLECULAR MATERIALS AND ENGINEERING., vol. 279, no. 1, 1 June 2000 (2000-06-01), DE, pages 26 - 33, XP055825920, ISSN: 1438-7492, DOI: 10.1002/1439-2054(20000601)279:1<26::AID-MAME26>3.0.CO;2-5 * |
Also Published As
Publication number | Publication date |
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FR3117487A1 (fr) | 2022-06-17 |
US20240043599A1 (en) | 2024-02-08 |
FR3117487B1 (fr) | 2022-12-23 |
EP4259675A1 (fr) | 2023-10-18 |
KR20230117206A (ko) | 2023-08-07 |
JP2023552611A (ja) | 2023-12-18 |
CN116601178A (zh) | 2023-08-15 |
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