CN111171421A - Hydrogenated polymer blend material and preparation method thereof - Google Patents
Hydrogenated polymer blend material and preparation method thereof Download PDFInfo
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- CN111171421A CN111171421A CN202010105912.0A CN202010105912A CN111171421A CN 111171421 A CN111171421 A CN 111171421A CN 202010105912 A CN202010105912 A CN 202010105912A CN 111171421 A CN111171421 A CN 111171421A
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- 229920002959 polymer blend Polymers 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 41
- 239000003292 glue Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 150000001993 dienes Chemical class 0.000 claims abstract description 30
- 230000001376 precipitating effect Effects 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000002861 polymer material Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 22
- 229920003049 isoprene rubber Polymers 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 229920005604 random copolymer Polymers 0.000 claims description 12
- 229920001400 block copolymer Polymers 0.000 claims description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical group Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 claims description 9
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012968 metallocene catalyst Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical group [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000000899 Gutta-Percha Substances 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 240000000342 Palaquium gutta Species 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229920000588 gutta-percha Polymers 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 239000011115 styrene butadiene Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- FWSNWLUFIVFHDW-UHFFFAOYSA-K [Rh](Cl)(Cl)Cl.C(C)P(CC)CC Chemical compound [Rh](Cl)(Cl)Cl.C(C)P(CC)CC FWSNWLUFIVFHDW-UHFFFAOYSA-K 0.000 claims description 3
- PYYCSXINHTZCLT-UHFFFAOYSA-K [Rh](Cl)(Cl)Cl.CP(C)C Chemical compound [Rh](Cl)(Cl)Cl.CP(C)C PYYCSXINHTZCLT-UHFFFAOYSA-K 0.000 claims description 3
- GTEGCGVGTSWOGG-UHFFFAOYSA-K [Ru](Cl)(Cl)Cl.C(C)P(CC)CC Chemical compound [Ru](Cl)(Cl)Cl.C(C)P(CC)CC GTEGCGVGTSWOGG-UHFFFAOYSA-K 0.000 claims description 3
- ZVNLTHGRHNCHAQ-UHFFFAOYSA-K [Ru](Cl)(Cl)Cl.CP(C)C Chemical compound [Ru](Cl)(Cl)Cl.CP(C)C ZVNLTHGRHNCHAQ-UHFFFAOYSA-K 0.000 claims description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- CMTKJYPJPSONIT-UHFFFAOYSA-K trichlororuthenium;triphenylphosphane Chemical compound Cl[Ru](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMTKJYPJPSONIT-UHFFFAOYSA-K 0.000 claims description 3
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 20
- 238000005979 thermal decomposition reaction Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical class CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 1
- CSEGCHWAMVIXSA-UHFFFAOYSA-L cyclopenta-1,3-diene;hafnium(4+);dichloride Chemical compound [Cl-].[Cl-].[Hf+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 CSEGCHWAMVIXSA-UHFFFAOYSA-L 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/02—Hydrogenation
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a hydrogenated blending polymer material and a preparation method thereof, belonging to the technical field of blending materials. Mixing more than two conjugated diene polymers, a catalyst and an organic solvent, and carrying out hydrogenation reaction to obtain hydrogenation reaction glue solution; mixing the hydrogenation reaction glue solution with a precipitation agent, and performing solid precipitation to obtain a hydrogenated blended polymer material; the precipitating agent is ethanol or hot water, and the temperature of the hot water is 90-100 ℃. The preparation method provided by the invention is simpler and easy to regulate, the hydrogenated polymer blend materials with different structures and saturation degrees can be obtained by simply regulating parameters according to needs, the problem of poor compatibility does not exist, and the obtained materials have good aging resistance.
Description
Technical Field
The invention relates to the technical field of blending materials, in particular to a hydrogenated blending polymer material and a preparation method thereof.
Background
The polyolefin blend can be realized by two ways, one is an in-kettle blending method, namely, the blending of different olefins is realized by adding a plurality of catalysts in the polymerization process, such as isotactic polypropylene (iPP)/ethylene-propylene random copolymer (EPR), and after the propylene is all agglomerated, ethylene monomer is added for copolymerization to obtain the polyolefin blend. Yet another method is post-reaction blending, i.e., mixing of the pre-obtained polyolefin with other polymers by means of an extruder, roller or intensive mixer, at a temperature above the viscous flow temperature of the amorphous polymer component contained in the mixture and above the melting point of the crystalline polymer component contained therein. The physical and mechanical properties and the processing property of the polymer material can be improved by blending, the cost can be reduced, the application range can be enlarged, and the method is one of important ways for realizing the modification of the polymer and producing a new material with multiple properties.
Hydrogenated polymer blend material refers to a material in which the polymer blend contains at least one hydrogenated polymer, and the hydrogenated polymer blend can improve the mechanical and aging resistance of the material to expand the application range of the material. For example, the hydrogenated block copolymer can be blended with homopolymer to prevent stress cracking of olefin polymer and improve cold flow, and the hydrogenated styrene block copolymer can be used as adhesive, thickener, viscosity regulator, etc. Patent CN103102584A discloses a hydrogenated block copolymer elastomer-polypropylene blend, which is prepared by mechanically blending a hydrogenated block copolymer and polypropylene, and the formed blend has good transparency, easy coloring and high gloss, does not generate silver streaks particularly when deformed by stress, has good physical and mechanical properties and low production cost; patent CN102264460A discloses a blend of hydrogenated styrenic block copolymers with polypropylene, which is a mechanical blend of at least about 70 wt% polypropylene or polypropylene random copolymer, up to about 30 wt% hydrogenated block copolymer, up to about 0.70 wt% clarifying agent, useful as molded articles.
However, most of hydrogenated polymer blends in the prior art are prepared by mechanically blending a hydrogenated polymer and other polymers, the product has a single structure, the hydrogenated polymer is prepared by hydrogenation reaction firstly and then mechanically blended to obtain the product, the polymer is degraded in the mechanical blending process, and different polymer systems have the problem of poor compatibility, so that the blend is not uniformly mixed.
Disclosure of Invention
The invention aims to provide a hydrogenated polymer blend material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a hydrogenated polymer blend material, which comprises the following steps:
mixing more than two conjugated diene polymers, a catalyst and an organic solvent, and carrying out hydrogenation reaction to obtain hydrogenation reaction glue solution;
mixing the hydrogenation reaction glue solution with a precipitation agent, and performing solid precipitation to obtain a hydrogenated blended polymer material; the precipitating agent is ethanol or hot water, and the temperature of the hot water is 90-100 ℃.
Preferably, the two or more conjugated diene polymers are at least two of natural rubber, isoprene rubber, natural gutta percha, trans-isoprene rubber, a styrene-isoprene random copolymer, a styrene-isoprene block copolymer, a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a styrene-isoprene-butadiene random copolymer, and a styrene-isoprene-butadiene block copolymer.
Preferably, the catalyst is a noble metal catalyst, a metallocene catalyst or a transition metal catalyst; the noble metal catalyst is triphenylphosphine rhodium chloride, trimethylphosphine rhodium chloride, triethylphosphine rhodium chloride, triphenylphosphine palladium chloride, trimethylphosphine palladium chloride, triethylphosphine palladium chloride, triphenylphosphine ruthenium chloride, trimethylphosphine ruthenium chloride or triethylphosphine ruthenium chloride; the metallocene catalyst is a titanium metallocene compound, a zirconium metallocene compound or a hafnium metallocene compound; the transition metal catalyst is nickel naphthenate, cobalt naphthenate, iron naphthenate or chromium naphthenate.
Preferably, the organic solvent is at least one of gasoline, cyclohexane, n-hexane, heptane, toluene, benzene, xylene, carbon tetrachloride, chloroform and dichloromethane.
Preferably, the process of mixing the two or more conjugated diene polymers, the catalyst and the organic solvent is to dissolve the two or more conjugated diene polymers in the organic solvent to obtain a polymer solution, and then to add the catalyst.
Preferably, the total concentration of the conjugated diene polymer in the polymer solution is 1 to 50 wt%.
Preferably, the mass ratio of the catalyst to the total amount of the conjugated diene polymer is (0.1 to 200). times.10-3:1。
Preferably, the hydrogen pressure of the hydrogenation reaction is 0.05-20 MPa, the temperature of the hydrogenation reaction is 50-150 ℃, and the time is 1-10 h.
Preferably, when the precipitating agent is ethanol, the volume ratio of the precipitating agent to the organic solvent is 0.5-5: 1; when the precipitating agent is hot water, the volume ratio of the precipitating agent to the organic solvent is 1-10: 1.
The invention also provides a hydrogenated polymer blend material obtained by the preparation method in the technical scheme.
According to the invention, more than two conjugated diene polymers are directly hydrogenated in the solution to obtain hydrogenated reaction glue solution, the hydrogenated reaction glue solution contains more than two hydrogenated polymers, then a precipitating agent is added, and the hydrogenated polymers are precipitated to directly obtain hydrogenated blended polymer material.
Detailed Description
The invention provides a preparation method of a hydrogenated polymer blend material, which comprises the following steps:
mixing more than two conjugated diene polymers, a catalyst and an organic solvent, and carrying out hydrogenation reaction to obtain hydrogenation reaction glue solution;
mixing the hydrogenation reaction glue solution with a precipitation agent, and performing solid precipitation to obtain a hydrogenated blended polymer material; the precipitating agent is ethanol or hot water, and the temperature of the hot water is 90-100 ℃.
The invention mixes more than two conjugated diene polymers, a catalyst and an organic solvent to carry out hydrogenation reaction to obtain hydrogenation reaction glue solution.
In the present invention, the two or more conjugated diene polymers are preferably at least two of natural rubber, isoprene rubber, natural gutta percha, trans-isoprene rubber, a styrene-isoprene random copolymer, a styrene-isoprene block copolymer, a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a styrene-isoprene-butadiene random copolymer, and a styrene-isoprene-butadiene block copolymer. The ratio of the two or more conjugated diene polymers is not particularly limited in the present invention, and can be adjusted as needed by those skilled in the art. In the embodiment of the present invention, when two conjugated diene polymers are selected, the mass ratio of the two conjugated diene polymers is preferably 1: 1; the two conjugated diene polymers are preferably isoprene rubber and a styrene-isoprene block copolymer, or isoprene rubber and trans-isoprene rubber, or a styrene-isoprene block copolymer and a styrene-butadiene block copolymer.
In the present invention, the catalyst is preferably a noble metal catalyst, a metallocene catalyst or a transition metal catalyst; the noble metal catalyst is preferably a group VIII noble metal catalyst, more preferably triphenylphosphine rhodium chloride, trimethylphosphine rhodium chloride, triethylphosphine rhodium chloride, triphenylphosphine palladium chloride, trimethylphosphine palladium chloride, triethylphosphine palladium chloride, triphenylphosphine ruthenium chloride, trimethylphosphine ruthenium chloride or triethylphosphine ruthenium chloride, and most preferably triphenylphosphine rhodium chloride; the metallocene catalyst is preferably a metallocene compound of titanium, a metallocene compound of zirconium or a metallocene compound of hafnium, more preferably a metallocene compound of titanium, the metallocene compound of titanium is preferably titanocene dichloride, titanocene dimethyl or titanocene di-p-tolyl, more preferably titanocene dichloride, the metallocene compound of zirconium is preferably zirconocene dichloride, hafnocene dichloride or zirconocene di-p-tolyl, and the metallocene compound of hafnium is preferably zirconocene dimethyl, hafnocene dimethyl or hafnocene di-p-tolyl; the transition metal catalyst is preferably nickel naphthenate, cobalt naphthenate, iron naphthenate, or chromium naphthenate, more preferably nickel naphthenate.
In the present invention, the mass ratio of the catalyst to the total amount of the conjugated diene polymer is preferably (0.1 to 200). times.10-31, more preferably 0.0002 to 0.17: 1.
The type of the organic solvent is not particularly limited in the present invention, and the conjugated diene polymer can be dissolved, and in the embodiment of the present invention, the organic solvent is preferably at least one of gasoline, cyclohexane, n-hexane, heptane, toluene, benzene, xylene, carbon tetrachloride, chloroform, and dichloromethane; when the organic solvent is more than two, the proportion of the organic solvent is not specially limited, and the conjugated diene polymer can be dissolved; the organic solvent is more preferably toluene or cyclohexane.
In the present invention, the process of mixing the two or more conjugated diene polymers, the catalyst and the organic solvent is preferably a process of dissolving the two or more conjugated diene polymers in the organic solvent to obtain a polymer solution, and then adding the catalyst to obtain a raw material mixed solution. In the invention, the total concentration of the conjugated diene polymer in the polymer solution is preferably 1 to 50 wt%, and more preferably 2 to 20 wt%.
In the invention, the hydrogen pressure of the hydrogenation reaction is preferably 0.05-20 MPa, more preferably 0.5-7 MPa, the temperature of the hydrogenation reaction is preferably 50-150 ℃, more preferably 60-90 ℃, and the time is preferably 1-10 h, more preferably 2-7 h.
In the present invention, the kind and amount of the above-mentioned catalyst, the kind of the conjugated diene polymer, and the parameters of the hydrogenation reaction can be adjusted by those skilled in the art according to the needs to obtain hydrogenated polymer blend materials with different structures and saturation degrees.
In the present invention, the hydrogen atmosphere of the hydrogenation reaction is preferably obtained by: and (3) placing the raw material mixed solution into a high-pressure reaction kettle, replacing air in the high-pressure reaction kettle with nitrogen for 3 times, and then introducing hydrogen for 10min to maintain the pressure required by hydrogenation reaction.
After the hydrogenation reaction is finished, the temperature is preferably reduced to room temperature, and then the pressure is released to obtain hydrogenation reaction glue liquid.
After obtaining a hydrogenation reaction glue solution, mixing the hydrogenation reaction glue solution with a precipitating agent, and carrying out solid precipitation to obtain a hydrogenated blending polymer material; the precipitating agent is ethanol or hot water, and the temperature of the hot water is 90-100 ℃, preferably 100 ℃.
In the invention, when the precipitating agent is ethanol, the volume ratio of the precipitating agent to the organic solvent is preferably 0.5-5: 1, and more preferably 1: 1; when the precipitating agent is hot water, the volume ratio of the precipitating agent to the organic solvent is preferably 1-10: 1, and more preferably 6: 1; the ethanol is preferably anhydrous ethanol.
In the invention, when the precipitating agent is ethanol, the hydrogenation reaction glue solution is mixed with the precipitating agent, preferably, the precipitating agent is added into the hydrogenation reaction glue solution; when the precipitating agent is hot water, the hydrogenation reaction glue solution and the precipitating agent are preferably mixed, and the hydrogenation reaction glue solution is preferably added into the hot water. In the invention, the precipitating agent can precipitate the product obtained by hydrogenation reaction, and then the organic solvent can be removed through solid-liquid separation; when the precipitating agent is ethanol, the product obtained by the hydrogenation reaction is precipitated in the form of precipitate and is precipitated at the bottom of the system, and when the precipitating agent is hot water, the product obtained by the hydrogenation reaction is dispersed in the system in the form of solid particles and can be separated by solid-liquid separation.
The time for precipitating the solid is not particularly limited, and no new precipitate is precipitated; in the embodiment of the invention, after the precipitating agent is mixed with the hydrogenation reaction glue solution, the hydrogenated polymer blend can be precipitated after being stirred for a few times.
After the solid is separated out, the invention preferably carries out solid-liquid separation on the obtained reaction liquid, and the obtained solid is dried to obtain the hydrogenated polymer blend material; the solid-liquid separation mode is not particularly limited, and a conventional solid-liquid separation mode is adopted, and in the embodiment of the invention, a solid product is precipitated in a gel block form and can be directly taken out. The invention also provides a hydrogenated polymer blend material obtained by the preparation method in the technical scheme; the hydrogenated polymer blend material comprises at least two of hydrogenated natural rubber, hydrogenated isoprene rubber, hydrogenated natural gutta percha, hydrogenated trans-isoprene rubber, hydrogenated styrene-isoprene random copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene-butadiene random copolymer, and hydrogenated styrene-isoprene-butadiene block copolymer; the saturation degree of the hydrogenated polymer blend material is preferably 0.001-100%, and more preferably 70-98%.
The present invention provides a hydrogenated polymer blend material and a method for preparing the same, which are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Dissolving isoprene rubber and a styrene-isoprene block copolymer in toluene according to the mass ratio of 1:1 to obtain 435g of polymer solution with the total polymer concentration of 2 wt%, adding 0.35g of triphenylphosphine rhodium chloride, closing the reactor, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reactor at 7MPa, raising the temperature of the reactor to 80 ℃, reacting for 7h, stopping the reaction, cooling the reactor to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the toluene is 1:1 to generate precipitates, then filtering, and drying the obtained solid under vacuum condition to obtain the hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 70% saturated as determined by iodometry.
A Q50 thermogravimetric analyzer is adopted to test the thermal decomposition temperature of the hydrogenated blended polymer material under the conditions that 10mg of the hydrogenated blended polymer material is placed in a crucible under the nitrogen atmosphere, the heating rate is 10 ℃/min, the temperature range is 50-600 ℃, and the nitrogen flow rate is 50 mL/min. The results show that the thermal decomposition temperatures of the resulting hydrogenated polymer blend materials are 410.67 ℃ and 450.12 ℃.
Example 2
Dissolving isoprene rubber and a styrene-isoprene block copolymer in toluene according to the mass ratio of 1:1 to obtain 435g of polymer solution with the total polymer concentration of 2 wt%, adding 0.75g of triphenylphosphine rhodium chloride, closing the reactor, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reactor at 7MPa, raising the temperature of the reactor to 80 ℃, reacting for 7h, stopping the reaction, cooling the reactor to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the toluene is 1:1 to generate precipitates, then filtering, and drying the obtained solid under vacuum condition to obtain the hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 92% saturated as measured by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 421.69 ℃ and 470.12 ℃ according to the method of example 1.
Example 3
Dissolving isoprene rubber and a styrene-isoprene block copolymer in toluene according to a mass ratio of 1:1 to obtain 435g of a polymer solution with a total polymer concentration of 2 wt%, adding 1.5g of triphenylphosphine rhodium chloride, closing the reactor, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reactor at 7MPa, raising the temperature of the reactor to 80 ℃, reacting for 7h, stopping the reaction, cooling the reactor to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the toluene is 1:1 to generate precipitates, then filtering, and drying the obtained solid under a vacuum condition to obtain a hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 95% saturated as determined by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 420.83 ℃ and 471.24 ℃ according to the method of example 1.
Example 4
Dissolving isoprene rubber and trans-isoprene rubber in toluene according to the mass ratio of 1:1 in a high-pressure reaction kettle to obtain 435g of polymer solution with the total polymer concentration of 2 wt%, adding 0.8g of triphenylphosphine rhodium chloride, closing the kettle, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reaction kettle at 7MPa, heating the reaction kettle to 80 ℃, reacting for 7h, stopping the reaction, cooling the reaction kettle to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, allowing the volume ratio of the absolute ethyl alcohol to the toluene to be 1:1, generating precipitates, filtering, and drying the obtained solid under vacuum conditions to obtain the hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 94% saturated as measured by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 423.76 ℃ and 397.23 ℃ according to the method of example 1.
Example 5
Dissolving isoprene rubber and a styrene-isoprene block copolymer in cyclohexane according to the mass ratio of 1:1 to obtain 500g of a polymer solution with the total polymer concentration of 5 wt%, adding 2.4g of titanocene dichloride, closing the kettle, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the kettle at 0.5MPa, raising the temperature of the kettle to 90 ℃, reacting for 2h, stopping the reaction, cooling the kettle to room temperature, releasing pressure, taking out a hydrogenated reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the cyclohexane is 1:1 to generate a precipitate, then filtering, and drying the obtained solid under a vacuum condition to obtain a hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 97% saturated as determined by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 422.63 ℃ and 470.25 ℃ according to the method of example 1.
Example 6
Dissolving a styrene-isoprene block copolymer and a styrene-butadiene block copolymer in cyclohexane according to the mass ratio of 1:1 to obtain 500g of a polymer solution with the total polymer concentration of 5 wt%, adding 2.4g of titanocene dichloride, closing the kettle, then starting electromagnetic stirring, sequentially filling and exhausting nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the kettle at 0.5MPa, raising the temperature of the kettle to 90 ℃, reacting for 2h, stopping the reaction, cooling the kettle to room temperature, releasing pressure, taking out a hydrogenation reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the cyclohexane is 1:1 to generate a precipitate, filtering, and drying the obtained solid under a vacuum condition to obtain the hydrogenation blending polymer material.
The resulting hydrogenated polymer blend was 98% saturated as measured by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 467.84 ℃ and 485.98 ℃ according to the method of example 1.
Example 7
Dissolving a styrene-butadiene-isoprene block copolymer and a styrene-butadiene block copolymer in cyclohexane according to the mass ratio of 1:1 to obtain 300g of a polymer solution with the total polymer concentration of 20 wt%, adding 5.6g of titanocene dichloride, closing the kettle, then starting electromagnetic stirring, sequentially filling and exhausting nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the kettle at 2MPa, raising the temperature of the kettle to 75 ℃, reacting for 3h, stopping the reaction, cooling the kettle to room temperature, releasing pressure, taking out a hydrogenation reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the cyclohexane is 1:1 to generate a precipitate, filtering, and drying the obtained solid under a vacuum condition to obtain the hydrogenation blending polymer material.
The resulting hydrogenated polymer blend was 86% saturated as determined by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 457.23 ℃ and 471.09 ℃ according to the method of example 1.
Example 8
Dissolving isoprene rubber and a styrene-isoprene block copolymer in cyclohexane according to the mass ratio of 1:1 to obtain 500g of a polymer solution with the total polymer concentration of 10 wt%, adding 0.01g of nickel naphthenate, closing the reactor, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reactor at 4MPa, raising the temperature of the reactor to 60 ℃, reacting for 3h, stopping the reaction, cooling the reactor to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, adding absolute ethyl alcohol into the reaction glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the cyclohexane is 1:1, generating precipitates, then filtering, and drying the obtained solid under vacuum condition to obtain the hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 98% saturated as measured by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 426.04 ℃ and 465.25 ℃ according to the method of example 1.
Example 9
Dissolving isoprene rubber and trans-isoprene rubber in toluene according to the mass ratio of 1:1 in a high-pressure reaction kettle to obtain 435g of polymer solution with the total polymer concentration of 2 wt%, adding 0.8g of triphenylphosphine rhodium chloride, closing the kettle, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reaction kettle at 7MPa, heating the reaction kettle to 80 ℃, reacting for 7h, stopping the reaction, cooling the reaction kettle to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, adding the reaction glue solution into hot water at 100 ℃ for stirring, wherein the volume ratio of the hot water to the toluene is 6:1, separating out solid, filtering, and drying the obtained solid under vacuum conditions to obtain the hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was 95% saturated as determined by iodometry.
The hydrogenated polymer blend material obtained in this example was tested for thermal decomposition temperatures of 420.55 ℃ and 398.42 ℃ according to the method of example 1.
From examples 1 to 9, it can be seen that hydrogenated polymer blend materials with different saturation degrees and thermal decomposition temperatures can be obtained by changing the amount of the catalyst, the type of the conjugated diene polymer, the conditions of the hydrogenation reaction, and the like, so as to meet the requirements of different fields, and the thermal decomposition temperature of the obtained material is higher, which indicates that the aging resistance is good.
Comparative example 1
Respectively putting 217.5g of 2 wt% isoprene rubber toluene solution and 217.5g of 2 wt% styrene-isoprene block copolymer toluene solution into a reaction kettle, respectively adding 0.188g and 0.162g of triphenylphosphine rhodium chloride, closing the reaction kettle, then starting electromagnetic stirring, sequentially filling nitrogen for 3 times, purging with hydrogen for 10min, then maintaining the pressure of the reaction kettle at 7MPa, raising the temperature of the reaction kettle to 80 ℃, reacting for 7h, stopping the reaction, cooling the reaction kettle to room temperature, releasing pressure, taking out hydrogenated reaction glue solution, mixing the reaction glue solution, adding absolute ethyl alcohol into the mixed glue solution, stirring, wherein the volume ratio of the absolute ethyl alcohol to the toluene is 1:1, generating precipitates, filtering, and drying the obtained solid under vacuum condition to obtain the hydrogenated blended polymer material.
The resulting hydrogenated polymer blend was found to have a degree of saturation of 68% by iodometric measurement, which is slightly lower than that of example 1, indicating that the hydrogenated blend obtained by hydrogenating two conjugated diene polymers in the same solution had a much greater degree of saturation.
A Q50 thermogravimetric analyzer is adopted to test the thermal decomposition temperature of the hydrogenated blended polymer material under the conditions that 10mg of the hydrogenated blended polymer material is placed in a crucible under the nitrogen atmosphere, the heating rate is 10 ℃/min, the temperature range is 50-600 ℃, and the nitrogen flow rate is 50 mL/min. The resulting hydrogenated polymer blend material had thermal decomposition temperatures of 406.54 ℃ and 443.42 ℃ which were slightly lower than those of example 1, indicating that it had slightly poorer aging resistance than example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method of preparing a hydrogenated polymer blend material, comprising the steps of:
mixing more than two conjugated diene polymers, a catalyst and an organic solvent, and carrying out hydrogenation reaction to obtain hydrogenation reaction glue solution;
mixing the hydrogenation reaction glue solution with a precipitation agent, and performing solid precipitation to obtain a hydrogenated blended polymer material; the precipitating agent is ethanol or hot water, and the temperature of the hot water is 90-100 ℃.
2. The method according to claim 1, wherein the two or more conjugated diene polymers are at least two of natural rubber, isoprene rubber, natural gutta percha, trans-isoprene rubber, a random copolymer of styrene-isoprene, a block copolymer of styrene-isoprene, a random copolymer of styrene-butadiene, a block copolymer of styrene-butadiene, a random copolymer of styrene-isoprene-butadiene, and a block copolymer of styrene-isoprene-butadiene.
3. The production method according to claim 1, wherein the catalyst is a noble metal catalyst, a metallocene catalyst or a transition metal catalyst; the noble metal catalyst is triphenylphosphine rhodium chloride, trimethylphosphine rhodium chloride, triethylphosphine rhodium chloride, triphenylphosphine palladium chloride, trimethylphosphine palladium chloride, triethylphosphine palladium chloride, triphenylphosphine ruthenium chloride, trimethylphosphine ruthenium chloride or triethylphosphine ruthenium chloride; the metallocene catalyst is a titanium metallocene compound, a zirconium metallocene compound or a hafnium metallocene compound; the transition metal catalyst is nickel naphthenate, cobalt naphthenate, iron naphthenate or chromium naphthenate.
4. The method according to claim 1, wherein the organic solvent is at least one of gasoline, cyclohexane, n-hexane, heptane, toluene, benzene, xylene, carbon tetrachloride, chloroform and methylene chloride.
5. The method according to any one of claims 1 to 4, wherein the mixing of the two or more conjugated diene polymers, the catalyst and the organic solvent comprises dissolving the two or more conjugated diene polymers in the organic solvent to obtain a polymer solution, and then adding the catalyst.
6. The method according to claim 5, wherein the total concentration of the conjugated diene polymer in the polymer solution is 1 to 50 wt%.
7. The production method according to claim 1 or 6, wherein the mass ratio of the catalyst to the total amount of the conjugated diene polymer is (0.1 to 200). times.10-3:1。
8. The method according to claim 1, wherein the hydrogen pressure of the hydrogenation reaction is 0.05 to 20MPa, the temperature of the hydrogenation reaction is 50 to 150 ℃, and the time is 1 to 10 hours.
9. The preparation method according to claim 1, wherein when the precipitating agent is ethanol, the volume ratio of the precipitating agent to the organic solvent is 0.5-5: 1; when the precipitating agent is hot water, the volume ratio of the precipitating agent to the organic solvent is 1-10: 1.
10. A hydrogenated polymer blend material obtained by the production process according to any one of claims 1 to 9.
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