CN111819219A - Process for producing poly (vinylbenzyl) ether compound - Google Patents
Process for producing poly (vinylbenzyl) ether compound Download PDFInfo
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- CN111819219A CN111819219A CN201980016571.5A CN201980016571A CN111819219A CN 111819219 A CN111819219 A CN 111819219A CN 201980016571 A CN201980016571 A CN 201980016571A CN 111819219 A CN111819219 A CN 111819219A
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- Prior art keywords
- ether compound
- vinylbenzyl
- poly
- compound
- producing
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- -1 poly (vinylbenzyl) ether compound Chemical class 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 36
- 239000000460 chlorine Substances 0.000 claims abstract description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 35
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical class CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002798 polar solvent Substances 0.000 claims abstract description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 229920001955 polyphenylene ether Polymers 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004429 atom Chemical group 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001665 Poly-4-vinylphenol Polymers 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- 150000002366 halogen compounds Chemical class 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 43
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 14
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ALOXCDWHUMEDFU-UHFFFAOYSA-N [3-chloro-2-(chloromethyl)prop-1-enyl]benzene Chemical compound ClCC(CCl)=CC1=CC=CC=C1 ALOXCDWHUMEDFU-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 7
- 239000007810 chemical reaction solvent Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- TYTPPOBYRKMHAV-UHFFFAOYSA-N 2,6-dimethylphenol Chemical compound CC1=CC=CC(C)=C1O.CC1=CC=CC(C)=C1O TYTPPOBYRKMHAV-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- YUAYXCGERFHZJE-UHFFFAOYSA-N 1-(1-phenylprop-2-enoxy)prop-2-enylbenzene Chemical class C=1C=CC=CC=1C(C=C)OC(C=C)C1=CC=CC=C1 YUAYXCGERFHZJE-UHFFFAOYSA-N 0.000 description 1
- IZXSWEQCVDBMOL-UHFFFAOYSA-N 1-(bromomethyl)-2-ethenylbenzene Chemical compound BrCC1=CC=CC=C1C=C IZXSWEQCVDBMOL-UHFFFAOYSA-N 0.000 description 1
- WFCJSNUJPWSKNE-UHFFFAOYSA-N 1-(bromomethyl)-3-ethenylbenzene Chemical compound BrCC1=CC=CC(C=C)=C1 WFCJSNUJPWSKNE-UHFFFAOYSA-N 0.000 description 1
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 description 1
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- 125000004806 1-methylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- NYIZDTGSROGDOU-UHFFFAOYSA-N 2,3-dibromoprop-1-enylbenzene Chemical compound BrCC(Br)=CC1=CC=CC=C1 NYIZDTGSROGDOU-UHFFFAOYSA-N 0.000 description 1
- YZUGEPZYFSYZCP-UHFFFAOYSA-N 2,3-dichloroprop-1-enylbenzene Chemical compound ClCC(Cl)=CC1=CC=CC=C1 YZUGEPZYFSYZCP-UHFFFAOYSA-N 0.000 description 1
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-di-methyl phenol Natural products CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 1
- KMLUZJQTMWDZLI-UHFFFAOYSA-N 2,6-dimethylphenol;2,3,6-trimethylphenol Chemical compound CC1=CC=CC(C)=C1O.CC1=CC=C(C)C(O)=C1C KMLUZJQTMWDZLI-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- XTSFFGPWZRBWLG-UHFFFAOYSA-N 3,3-dibromoprop-1-enylbenzene Chemical compound BrC(C=CC1=CC=CC=C1)Br XTSFFGPWZRBWLG-UHFFFAOYSA-N 0.000 description 1
- PLNSKVFVQQBEMJ-UHFFFAOYSA-N 3,3-dichloroprop-1-enylbenzene Chemical compound ClC(Cl)C=CC1=CC=CC=C1 PLNSKVFVQQBEMJ-UHFFFAOYSA-N 0.000 description 1
- IIDBRZPFQJXKKO-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene prop-1-enylbenzene Chemical class ClCC=CC1=CC=CC=C1.CC=CC1=CC=CC=C1 IIDBRZPFQJXKKO-UHFFFAOYSA-N 0.000 description 1
- AVYSLHFYIRDRHX-UHFFFAOYSA-N CCC.CC1=CC=CC(C)=C1O Chemical compound CCC.CC1=CC=CC(C)=C1O AVYSLHFYIRDRHX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
Abstract
The present invention provides a process for producing a poly (vinylbenzyl) ether compound, which can reduce the amount of a halogen compound or a halide ion remaining and can reduce the production cost. A process for producing a poly (vinylbenzyl) ether compound by reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene, which comprises reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene represented by the following general formula (1) (X represents an atom selected from the group consisting of chlorine and bromine) in the presence of an aqueous alkali metal hydroxide solution in a solvent containing an aromatic hydrocarbon and an aprotic polar solventA reaction step of reacting the halogenated methylstyrene: c9H8X2(X represents any atom selected from chlorine and bromine) is 1.5% by mass or less, and the content of the aprotic polar solvent in the solvent is 5% by mass or more.
Description
Technical Field
The present invention relates to a method for producing a poly (vinylbenzyl) ether compound.
Background
Poly (vinylbenzyl) ether compounds are excellent in dielectric properties and resistance to moisture absorption, and have been used as materials for electronic devices that handle high-frequency signals.
In the use of electronic materials, it is generally necessary to reduce the residual amount of halogen compounds and halide ions that are hydrolyzed by moisture absorption to release chloride ions as much as possible from the viewpoint of durability and reliability of the products, and it is desirable to remove the halogen compounds and halide ions by a simple method from the viewpoint of the production process and the product cost.
As a method for producing a poly (vinylbenzyl) ether compound, for example, a method is disclosed in which a polyphenylene ether compound and a halogenated methylstyrene (vinylbenzyl halide) are reacted in a toluene solution in the presence of an alkali metal hydroxide, and the reaction solution is neutralized with an acid, washed, and then reprecipitated with a large amount of methanol (patent document 1).
However, although the production method of patent document 1 can remove the halogen compound and the halide ion, since the purification step by reprecipitation is included, the yield is lowered and the process time is prolonged, and thus improvement in production cost is desired.
In addition, as a method for removing a halogen-based compound (epichlorohydrin: having a boiling point of about 118 ℃) derived from an unreacted raw material, for example, as described in examples of patent document 2, the halogen-based compound is removed by distillation under reduced pressure, but it is difficult to remove the halogen-based compound by distillation under reduced pressure because the halogenated methylstyrene (chloromethylstyrene) used in the present invention has a boiling point of 229 to 240 ℃.
In addition, the method for producing a vinylbenzylated polyphenylene ether compound described in patent document 3 includes, as a purification step, a removal step of removing an unreacted vinylbenzyl halide by treating a reaction solution obtained in the reaction step with an aqueous alkali metal hydroxide solution in the presence of a phase transfer catalyst, and there is still room for further improvement in terms of yield and production cost.
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent publication No. 2009-96953
Patent document 2: japanese unexamined patent publication No. Hei 10-036484
Patent document 3: japanese unexamined patent publication No. 2014-189781
Disclosure of Invention
Technical problem to be solved by the invention
The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing a poly (vinylbenzyl) ether compound, which can reduce the residual amounts of a halogen compound and a halide ion and can reduce the production cost.
Means for solving the problems
The inventors of the present invention conducted extensive studies and found that: by using a halogenated methylstyrene having a small content of the specific by-product and conducting the reaction step in a solvent of a predetermined formulation, the residual amounts of the halogen compound and the halide ion can be reduced without a purification step such as reprecipitation.
That is, the process for producing a poly (vinylbenzyl) ether compound of the present invention is a process for producing a poly (vinylbenzyl) ether compound by reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene, which comprises reacting a compound having a phenolic hydroxyl group with a compound represented by the following general formulaA reaction step of reacting a halogenated methylstyrene represented by the formula (1) in the presence of an aqueous alkali metal hydroxide solution in a solvent containing an aromatic hydrocarbon and an aprotic polar solvent, wherein the halogenated methylstyrene is represented by the general formula: c9H8X2(X represents any atom selected from chlorine and bromine) is 1.5% by mass or less, and the content of the aprotic polar solvent in the solvent is 5% by mass or more.
[ solution 1]
In the formula (1), X represents any atom selected from chlorine and bromine.
The compound having a phenolic hydroxyl group may be at least one selected from the group consisting of a polyphenylene ether compound having a repeating unit represented by formula (2) or formula (3) and having a phenolic hydroxyl group at an end thereof, a terpene phenol resin, a dicyclopentadiene phenol resin, and a polyvinyl phenol resin.
[ solution 2]
In the formula (2), R1～R16Independently selected hydrogen atom or C1-5 alkyl, A represents a C20 or less linear, branched or cyclic divalent alkyl group, and m, n represent an integer of 0-100, at least one of which is not 0.
[ solution 3]
In the formula (3), R17～R20Each independently selected hydrogen atom or C1-5 alkyl, o is the average value of the number of repeating units and is an integer of 1-100.
The concentration of the alkali metal hydroxide aqueous solution may be 1.0 to 50.0 mass%.
The aromatic hydrocarbon may be one or two selected from the group consisting of toluene and xylene.
The solvent may further contain one or a mixture of two or more selected from the group consisting of aliphatic alcohols having 3 to 6 carbon atoms.
The aprotic polar solvent may be one or a mixture of two or more selected from the group consisting of dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, and propylene carbonate.
Effects of the invention
According to the present invention, since a purification step such as reprecipitation is not required, the production cost can be reduced, and a poly (vinylbenzyl) ether compound having high purity and low halogen compound and halide ion concentration can be obtained.
Drawings
FIG. 1 is a graph showing the results of gas chromatography (gaschrom chromatography) measurement of chloromethylstyrene used in example 1 of the present invention.
FIG. 2 is a graph showing the results of gas chromatography measurement of chloromethyl styrene used in example 5 of the present invention.
FIG. 3 is a graph showing the results of gas chromatography measurement of chloromethyl styrene used in examples 4 and 7 to 13 of the present invention.
Detailed Description
The following describes embodiments of the present invention.
The method for producing a poly (vinylbenzyl) ether compound of the present invention is a method for producing a poly (vinylbenzyl) ether compound by reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene, which generally includes a compound having a phenolic hydroxyl group and a halogenated methylstyrene represented by the following general formula (1) as a reaction by-product in a solvent containing an aromatic hydrocarbon and an aprotic polar solvent in the presence of an aqueous alkali metal hydroxide solution, wherein the halogenated methylstyrene comprises the following general formula: c9H8X2(X represents a group selected fromAny one atom of chlorine and bromine) is 1.5% by mass or less, and the content of the aprotic polar solvent in the reaction solvent is 5% by mass or more. In the present specification, when a dihalide compound is referred to as a dihalo compound alone, the dihalide compound is represented by the general formula: c9H8X2(X represents any atom selected from chlorine and bromine) and, when X is chlorine, it is also referred to as a dichloro compound.
[ solution 4]
In the formula (1), X represents any atom selected from chlorine and bromine.
When halogenated methylstyrene is produced by a known method, a mixture of (mono) halogenated methylstyrene represented by the general formula (1) and by-products is obtained, and details of the by-products are not limited, but it is considered to include isopropenylhalogenated benzene, a dihalide compound described later, bis (halogenated methyl) styrene, and the like. In the present specification, the term "halogenated methylstyrene" is used to mean a concept including these by-products.
Specific examples of the halogenated methylstyrene represented by the general formula (1) include: o-chloromethyl styrene, m-chloromethyl styrene, p-chloromethyl styrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, etc., and a mixture of two or more kinds selected from these may be used as it is.
In the present invention, the side product contained in the halogenated methylstyrene is represented by the general formula: c9H8X2The content of the dihalide compound represented by (X represents any atom selected from chlorine and bromine) is 1.5% by mass or less, preferably 1.2% by mass or less, more preferably 1.0% by mass or less, based on the total amount of halogenated methylstyrene. Specific examples of the dihalide compound include dichloromethylstyrene, chloro (chloromethyl) styrene, dibromomethylstyrene, bromo (bromomethyl) styrene, and the like. By makingThe content of the dihalide compound is 1.5% by mass or less, and a halogen compound and a poly (vinylbenzyl) ether compound having a low halide ion concentration can be easily obtained.
The compounding ratio of the halogenated methylstyrene used in the present invention is preferably 1.01 to 1.50 mol, and more preferably 1.05 to 1.30 mol, based on 1 mol of the hydroxyl group of the compound having a phenolic hydroxyl group. When the amount is less than 1.01 mol, the reaction rate decreases and the number of residual hydroxyl groups increases, so that when the amount is used as a material for electronic materials, the performance tends to be deteriorated, and when the amount is more than 1.5 mol, the process time for removing unreacted halogenated methylstyrene tends to be long.
The compound having a phenolic hydroxyl group used in the present invention is not particularly limited, and examples thereof include: a polyphenylene ether compound having a repeating unit represented by the following general formula (2) or (3) and having a phenolic hydroxyl group at an end thereof, a terpene phenol resin, a dicyclopentadiene phenol resin, a polyvinyl phenol resin.
[ solution 5]
In the general formula (2), R1～R16Independently selected hydrogen atom or C1-5 alkyl, A represents a C20 or less linear, branched or cyclic divalent alkyl group, and m, n represent an integer of 0-100, at least one of which is not 0.
Examples of A in the general formula (2) include: divalent organic groups such as methylene, ethylene (ethylidene), 1-methylethylene, 1-propylene (1,1-propylidene), 1, 4-phenylenebis (1-methylethylidene), 1, 3-phenylenebis (1-methylethylidene), cyclohexylene (cyclohexylidene), phenylmethylene, naphthylmethylene, and 1-phenylethylene, but are not limited thereto.
Specific examples of the polyphenylene ether compound represented by the general formula (2) include: 2, 2-bis (4-hydroxy-3, 5-methylphenyl) propane-2, 6-dimethylphenol polycondensate, 2-bis (4-hydroxy-3, 5-methylphenyl) propane-2, 3, 6-trimethylphenol polycondensate, 4 '-methylenebis (2, 6-dimethylphenol) -2, 6-dimethylphenol polycondensate, 4' -methylenebis (2, 6-dimethylphenol) -2, 3, 6-trimethylphenol polycondensate, and the like, but is not limited thereto. These polyphenylene ether compounds can be produced by a known method, and the production method is not particularly limited, and commercially available products can be used.
[ solution 6]
In addition, in the polyphenylene ether compound represented by the general formula (3) used in the present invention, provided that R is in the general formula (3)17～R20The polyphenylene ether compound is not particularly limited, and represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, each independently selected, and o is an average value of the number of repeating units and represents an integer of 1 to 100.
Specific examples of the polyphenylene ether compound represented by the general formula (3) include, but are not limited to, 2, 6-dimethylphenol polycondensate, 2,3, 6-trimethylphenol polycondensate, and the like. These polyphenylene ether compounds can be produced by a known method, and the production method is not particularly limited, and commercially available products can be used.
The aqueous alkali metal hydroxide solution used in the present invention is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, and mixtures thereof.
The mixing ratio of the alkali metal hydroxide aqueous solution is not particularly limited, and is preferably 1.2 mol to 4.0 mol with respect to 1 mol of the hydroxyl group of the compound having a phenolic hydroxyl group. When the amount is 1.2 mol or more, the reaction time tends to be shortened, and when the amount is 4.0 mol or less, unreacted alkali compound is less likely to remain. Further, the concentration of the alkali metal hydroxide aqueous solution is not particularly limited, and is preferably 1.0 to 50.0 mass% from the viewpoint of more rapid reaction.
Examples of the aromatic hydrocarbon used as a solvent in the present invention include: benzene, toluene, ethylbenzene, xylene, ethyltoluene, and the like. Among these, toluene or xylene is preferable from the viewpoint of being easily available and easily removable by reduced pressure.
The content of the aromatic hydrocarbon is not particularly limited, and is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, based on the total amount of the solvent.
The aprotic polar solvent used in the present invention is not particularly limited, and examples thereof include: dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone, propylene carbonate, and the like, and among these, dimethyl sulfoxide, dimethylformamide, acetonitrile can be preferably used in terms of ease of handling, ease of removal, and the like.
The content of the aprotic polar solvent is 5% by mass or more, preferably 10% by mass or more, in the total amount of the solvent. By containing 5 mass% or more of an aprotic polar solvent, a halogen compound and a poly (vinylbenzyl) ether compound having a low halide ion concentration can be easily obtained.
From the viewpoint of promoting the reaction, the solvent may contain an aliphatic alcohol together with the aromatic hydrocarbon and the aprotic polar solvent, and the aliphatic alcohol may be one or a mixture of two or more selected from the group consisting of aliphatic alcohols having 3 to 6 carbon atoms.
The aliphatic alcohol is preferably an aliphatic alcohol having 3 to 6 carbon atoms, and examples thereof include: n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, 2-ethylbutanol, n-hexanol, and the like. Among these, aliphatic alcohols having 3 or 4 carbon atoms are particularly preferable from the viewpoint of being easily removed by reducing the pressure.
When the aliphatic alcohol is used in combination, the content thereof is not particularly limited, and is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less in the total amount of the solvent. By setting the content of the aliphatic alcohol within the above range, the solubility of the compound having a phenolic hydroxyl group as a raw material can be maintained.
The total amount of the solvent used in the reaction is preferably 100 to 300 parts by mass with respect to 100 parts by mass of the compound having a phenolic hydroxyl group. If the amount is less than the above range, the viscosity of the reaction system increases, and unreacted raw materials are likely to remain, while if the amount is more than the above range, the yield per unit volume of the reaction vessel for the poly (vinylbenzyl) ether compound tends to decrease.
The other reaction conditions are not particularly limited as long as the reaction is carried out according to a method which has been conventionally used. That is, for example, a compound having a phenolic hydroxyl group and halogenated methylstyrene may be mixed with a solvent and stirred, and the reaction may be carried out while dropping an alkali metal hydroxide thereto. The reaction temperature is usually about 60 ℃ to 100 ℃ and the reaction time is about 2 hours to 16 hours.
The reaction solution obtained in the reaction step may be subjected to neutralization reaction by a method conventionally used. That is, for example, an organic solvent such as toluene or isopropyl alcohol and water are added to the reaction solution, and then neutralization is performed with an acid such as hydrochloric acid. The amount of the organic solvent and water used is not particularly limited, but the mass ratio of water/organic solvent is preferably 40/60 to 5/95, and more preferably 30/70 to 10/90.
The neutralized solution obtained in the neutralization step may be washed with a mixed solution containing water and an aliphatic alcohol as necessary to further reduce the halide ion concentration. The aliphatic alcohol used for the washing may be any of the above-mentioned reaction solvents. By using an aliphatic alcohol, the organic layer and the aqueous layer can be easily separated during washing. The amount of the aliphatic alcohol is preferably 99/1 to 20/80, more preferably 90/10 to 30/70, in terms of the mass ratio of water to aliphatic alcohol.
If the ratio of the aliphatic alcohol is less than the above range, the time required for separation of the organic layer from the aqueous layer may be long, or an intermediate layer may be formed between the organic layer and the aqueous layer. If the amount is more than the above range, the product tends to be easily dissolved in the washing solvent, and the yield tends to be lowered.
The amount of the mixed liquid containing water and an aliphatic alcohol used per one washing is preferably 20 to 150 parts by mass per 100 parts by mass of the polyphenylene ether compound. If the amount is less than the above range, washing tends to be insufficient, and if the amount is more than the above range, the amount of the poly (vinylbenzyl) ether compound dissolved as a product may increase, and the yield may decrease.
As the washing method, liquid-liquid separation may be performed according to a conventional method, and the target product can be obtained by washing, followed by dehydration and filtration.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. In the examples, "parts" and "%" are based on mass. The measurements in the examples and comparative examples were carried out according to the following methods and conditions.
[ reaction Rate ]
The reaction solution (1 g) was collected, reprecipitated with 40g of methanol, and the obtained resin was dried in a vacuum oven (120 ℃ C., 20mmHg) for 30 minutes. This was measured by the KBr method using a Fourier transform infrared spectrometer (FT-IR) (manufactured by Biorad) and FTS-135. The absorption wavelength of the hydroxyl group, 3610cm-1The reaction rate was calculated by the following equation.
Reaction rate (%) [1- (X/B) ] × 100
X: 3610cm of the measured sample-1Peak area of
B: 3610cm at the beginning of the reaction-1Peak area of
[ amount of residual chloromethyl styrene ]
The ratio (%) in the poly (vinylbenzyl) ether compound as a product was determined by measurement by gas chromatography under the following conditions.
< measurement Condition >
Column: "DB-1" manufactured by Agilent Technologies, having an inner diameter of 0.32mm, a length of 30m, and a film thickness of 0.25 μm
Measurement temperature: after keeping at 100 deg.C for 1 minute, heating at-10 deg.C/minute, keeping at-280 deg.C for 3 minutes
Injection port temperature: 300 deg.C
Detection port temperature: 300 deg.C
[ number average molecular weight, weight average molecular weight ]
The measurement was performed by Gel Permeation Chromatography (GPC) (polystyrene conversion).
[ method for measuring hydrolyzable chlorine amount ]
A sample (1.5 g) was weighed, and 15g of ultrapure water (water having a specific resistance of 18 M.OMEGA.. multidot.cm or more) was added thereto and hydrolyzed at 125 ℃ for 20 hours. The extract water in the upper layer was purified by ion chromatography (ICS-1500 manufactured by Dyan (Dionex) Co., Ltd.; column: IonPac AS 12A; eluent: 2.7mmol/L Na2CO3NaHCO 0.3mmol/L3Flow 1.5mL/min) was used. A calibration curve of the chlorine amount was prepared using an anion mixed standard solution IV (manufactured by kanto chemical corporation).
[ example 1]
158g (0.1 mol) of a polyphenylene ether compound represented by the general formula (2) (R of the general formula (2)) was charged in a 2L four-necked flask equipped with a temperature controller, a stirrer, a condenser and a dropping funnel1、R3、R5、R7、R10、R12、R14、R16Is methyl, R2、R4、R6、R8、R9、R11、R13、R15A is an isopropylidene group, m + n is an average of 12, and the number average molecular weight is 1580), toluene 221g, and dimethyl sulfoxide (hereinafter referred to as DMSO)94.8g were mixed to prepare a uniform solution, and then 0.96g of tetra-n-butylammonium bromide, chloromethyl styrene (dichloro compound content: GC area 0.0%, bis (chloromethyl) styrene content: GC area 0.9%) 32.7g (0.214 mole) and temperature was raised to 65 ℃. 53.3g (0.64 mol) of a 48% aqueous solution of sodium hydroxide was added dropwise thereto over 30 minutes, and the reaction was carried out at 65 ℃ for 8 hours, whereby the reaction rate was 98% or more.
Thereafter, the mixture was cooled to 50 ℃, and 295g of toluene, 126.4g of isopropyl alcohol (IPA), and 79g of water were added thereto, followed by neutralization with 46.7g of 35 mass% aqueous hydrochloric acid. Standing until the reaction solution is separated into two layers, and removing the lower aqueous solution layer. Further, 5 washes were performed with a mixture of 15.8g of isopropyl alcohol and 63.2g of water. The organic layer was dehydrated to 0.05% or less at 70 ℃ under 50mmHg, and the solution was filtered to obtain 345g of a 50% toluene solution of a vinylbenzylated polyphenylene ether compound (yield 95% based on the polyphenylene ether compound, hereinafter referred to as product). The vinylbenzylated polyphenylene ether compound had a residual chloromethylstyrene content (in terms of solid content) of less than 0.1%, a hydrolyzable chlorine content of 76ppm, a number average molecular weight of 2,180 and a weight average molecular weight of 3,680.
[ example 2]
The same operations as in example 1 were carried out except that the chloromethylstyrene used in the reaction was changed to 0.1% in the content of the dichloro compound and 0.0% in the content of bis (chloromethyl) styrene, to obtain 345g (95% in yield based on the polyphenylene ether compound) of a product. The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 103ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 3]
The same operations as in example 1 were carried out except that the chloromethylstyrene used in the reaction was changed to 0.3% in the content of the dichloro compound and 0.0% in the content of bis (chloromethyl) styrene, to obtain 345g (95% yield based on the polyphenylene ether compound) of a product. The obtained product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 169ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 4]
The same operations as in example 1 were carried out except that the chloromethylstyrene used in the reaction was changed to 0.8% in the content of the dichloro compound and 0.0% in the content of bis (chloromethyl) styrene, to obtain 345g (95% yield based on the polyphenylene ether compound) of a product. The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 227ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 5]
The same operations as in example 1 were carried out except that the chloromethylstyrene used in the reaction was changed to 1.1% in the content of the dichloro compound and 0.0% in the content of bis (chloromethyl) styrene, to obtain 345g (95% yield based on the polyphenylene ether compound) of a product. The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 409ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 6]
The same operations as in example 1 were carried out except that the chloromethylstyrene used in the reaction was changed to 1.5% in the content of the dichloro compound and 0.0% in the content of bis (chloromethyl) styrene, to obtain 345g (95% yield based on the polyphenylene ether compound) of a product. The obtained product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 595ppm, a number-average molecular weight of 2,180, and a weight-average molecular weight of 3,650.
[ example 7]
The same procedures used in example 4 were repeated except that 189.5g of toluene and 126.3g of DMSO were used as solvents to obtain 345g of a product (95% yield based on the polyphenylene ether compound). The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 210ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 8]
The same procedures as in example 4 were carried out except that the kinds and amounts of the solvents used in the reaction were 221g of toluene, 31.6g of isopropyl alcohol and 63.2g of DMSO, to obtain 345g of a product (yield 95% based on the polyphenylene ether compound). The resulting product had a residual chloromethylstyrene content of 0.2%, a hydrolyzable chlorine content of 310ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 9]
The same procedures as in example 4 were carried out except that the kinds and amounts of the solvents used in the reaction were 221g of toluene, 63.2g of isopropyl alcohol and 31.6g of DMSO, to obtain 345g of a product (yield 95% based on the polyphenylene ether compound). The resulting product had a residual chloromethylstyrene content of 0.3%, a hydrolyzable chlorine content of 350ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 10]
The same procedures as in example 4 were carried out except that the solvent used in the reaction was changed from 221g of toluene to 221g of xylene, to obtain 345g of a product (yield 95% based on the polyphenylene ether compound). The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 220ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 11]
The same procedures used in example 10 were repeated except for changing the kind of solvent used in the reaction from 94.8g of DMSO to 94.8g of N, N-Dimethylformamide (DMF), thereby obtaining 345g of a product (yield 95% based on the polyphenylene ether compound). The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 235ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
[ example 12]
The same operation as in example 5 was carried out except that the polyphenylene ether compound used in the reaction was changed to 140g (0.1 mol) of phenol resin A (terpene-phenol resin, amount of phenol was 1,400 g/mol), to obtain 273g of a product (yield 90% based on the terpene-phenol resin). The residual chloromethylstyrene content in the obtained product was less than 0.1%, and the hydrolyzable chlorine content was 212 ppm.
[ example 13]
The same procedures used in example 5 were repeated except for changing the polyphenylene ether compound used in the reaction to 33.7g (0.1 mol) of phenol resin B (dicyclopentadiene phenol resin, phenol amount 337 g/mol), to obtain 81.8g of a product (yield 90% based on the dicyclopentadiene phenol resin). The residual chloromethylstyrene content in the obtained product was less than 0.1%, and the hydrolyzable chlorine content was 234 ppm.
Comparative example 1
The same procedures as in example 5 were carried out except that the kind and amount of the solvent used in the reaction were 221g of toluene and 94.8g of isopropyl alcohol, to obtain 345g of a product (yield 95% based on the polyphenylene ether compound). The resulting product had a residual chloromethylstyrene content of 1.0%, a hydrolyzable chlorine content of 2290ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
Comparative example 2
167g of toluene was added to 100g of the product synthesized in comparative example 1 to dilute the product. The diluted solution was put into methanol (1000g) and reprecipitated to obtain a resin powder. The mixture was washed 4 times with 200g of a water/methanol (mass ratio 80/20) mixed solvent. This was dried in a vacuum oven (100 ℃ C., 20mmHg) for 24 hours to obtain 45g (yield 90% based on the polyphenylene ether compound) of a yellow powder. The obtained product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 200ppm, a number average molecular weight of 2,200, and a weight average molecular weight of 3,800.
Comparative example 3
The same operation as in comparative example 1 was carried out, except that the chloromethylstyrene used in the reaction was changed to 0.0% in the content of the dichloro compound and 0.9% in the content of bis (chloromethyl) styrene, to obtain 345g (95% yield based on the polyphenylene ether compound) of a product. The residual chloromethylstyrene content in the obtained product was 0.9%, the hydrolyzable chlorine content was 1800ppm, the number-average molecular weight was 2,180, and the weight-average molecular weight was 3,650.
Comparative example 4
The same operations as in example 1 were carried out except that the chloromethylstyrene used in the reaction was changed to 3.9% in the content of the dichloro compound and 0.0% in the content of bis (chloromethyl) styrene, to obtain 345g (95% yield based on the polyphenylene ether compound) of a product. The resulting product had a residual chloromethylstyrene content of less than 0.1%, a hydrolyzable chlorine content of 2132ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,650.
The reaction products, solvents, and the presence or absence of purification of the above examples and comparative examples are shown in Table 1 together with the residual chloromethylstyrene amount and the hydrolyzable chlorine amount of the obtained product.
[ Table 1]
In examples 1 to 13, the amount of residual chloromethylstyrene and the amount of hydrolyzable chlorine in the poly (vinylbenzyl) ether compound can be reduced without going through a purification step by reprecipitation. In example 5, the same effect as in comparative example 2 can be obtained by comparing comparative examples 1 and 2, in which the content of the dihalide compound in halogenated methylstyrene is not more than a predetermined value but the reaction solvent does not contain an aprotic polar solvent, with example 5, in which comparative example 2 is an example in which a purification step by reprecipitation is added to the compound obtained in comparative example 1.
In addition, from a comparison of example 1 with example 2, it can be seen that: among the by-products contained in halogenated methylstyrene, bis (chloromethyl) styrene does not greatly affect the hydrolyzable chlorine amount, and the dichloro compound as the dihalide compound affects the hydrolyzable chlorine amount.
Comparative example 3 is an example in which the content of the dihalide compound in halogenated methylstyrene is a predetermined value or less but the reaction solvent does not contain an aprotic polar solvent, and an effect of reducing the amount of hydrolyzable chlorine in the poly (vinylbenzyl) ether compound cannot be obtained only by increasing the purity of halogenated methylstyrene.
In comparative example 4, the aprotic polar solvent was contained in the reaction solvent, but the content of the dihalide compound in the halogenated methylstyrene was not less than the predetermined value, and the effect of reducing the amount of hydrolyzable chlorine could not be obtained by only containing the aprotic polar solvent in the reaction solvent.
Fig. 1 to 3 show the results of gas chromatography measurement of chloromethylstyrene used in examples 1, 5, 4, and 7 to 13.
As shown in fig. 1, the halogenated methylstyrene used in example 1 detected peaks indicating bis (chloromethyl) styrene at positions where the retention time was 10.377 minutes (min) and 10.595 minutes, and no dihalide compound was detected.
On the other hand, as shown in fig. 2, the halogenated methylstyrene used in example 5 detected the peak indicating the dihalide compound at the position where the holding time was 8.130 minutes or 8.322 minutes, and as shown in fig. 3, the halogenated methylstyrene used in example 4 or example 7 to example 13 detected the peak indicating the dihalide compound at the position of 8.132 minutes or 8.325 minutes. Thereafter, further verification was performed, and as a result, it was found that: a dihalide compound having a short retention time (8.130 minutes or 8.132 minutes) is highly likely to affect the production of a halogen compound or a halide ion in a poly (vinylbenzyl) ether compound, and a lower content thereof is more preferable.
Industrial applicability
According to the production method of the present invention, a poly (vinylbenzyl) ether compound which is reduced in halogen compounds and halide ions in the compound and reduced in production cost and is suitable as a material for electronic devices which process high-frequency signals can be provided.
Claims (6)
1. A method for producing a poly (vinylbenzyl) ether compound, which comprises reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene to produce the poly (vinylbenzyl) ether compound, wherein the method for producing the poly (vinylbenzyl) ether compound comprises:
comprising a reaction step of reacting a compound having a phenolic hydroxyl group with a halogenated methylstyrene represented by the following general formula (1) in the presence of an aqueous alkali metal hydroxide solution in a solvent containing an aromatic hydrocarbon and an aprotic polar solvent,
the halogenated methyl styrene is represented by the general formula: c9H8X2(X represents any atom selected from chlorine and bromine) is 1.5% by mass or less,
the content of the aprotic polar solvent in the solvent is 5% by mass or more.
[ solution 1]
In the formula (1), X represents any atom selected from chlorine and bromine.
2. The method for producing a poly (vinylbenzyl) ether compound according to claim 1, wherein,
the compound having a phenolic hydroxyl group is at least one selected from the group consisting of a polyphenylene ether compound having a repeating unit represented by formula (2) or formula (3) and having a phenolic hydroxyl group at an end thereof, a terpene phenol resin, a dicyclopentadiene phenol resin, and a polyvinyl phenol resin.
[ solution 2]
In the formula (2), R1～R16Independently selected hydrogen atom or C1-5 alkyl, A represents a C20 or less linear, branched or cyclic divalent alkyl group, and m, n represent an integer of 0-100, at least one of which is not 0.
[ solution 3]
In the formula (3), R17～R20Each independently selected hydrogen atom or C1-5 alkyl, o is the average value of the number of repeating units and is an integer of 1-100.
3. The process for producing a poly (vinylbenzyl) ether compound according to claim 1 or 2, wherein,
the concentration of the alkali metal hydroxide aqueous solution is 1.0 to 50.0 mass%.
4. The process for producing a poly (vinylbenzyl) ether compound according to any one of claims 1 to 3, wherein,
the aromatic hydrocarbon is one or two selected from the group consisting of toluene and xylene.
5. The process for producing a poly (vinylbenzyl) ether compound according to any one of claims 1 to 4, wherein,
the solvent also contains one or a mixture of more than two selected from the group consisting of aliphatic alcohols with 3-6 carbon atoms.
6. The method for producing a poly (vinylbenzyl) ether compound according to any one of claims 1 to 5, wherein,
the aprotic polar solvent is one or a mixture of two or more selected from the group consisting of dimethyl sulfoxide, dimethylformamide, acetonitrile, N-methylpyrrolidone and propylene carbonate.
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| PCT/JP2019/009689 WO2019176855A1 (en) | 2018-03-15 | 2019-03-11 | Method for producing poly(vinylbenzyl)ether compound |
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| JP2019157103A (en) * | 2018-05-22 | 2019-09-19 | 第一工業製薬株式会社 | Method for producing poly (vinylbenzyl) ether compound |
| JP2023120458A (en) * | 2020-07-10 | 2023-08-30 | Ａｇｃ株式会社 | Resin composition, prepreg, metallic foil with resin, film with resin, metal-clad laminate, and wiring board, and method for producing modified polyphenylene ether |
| US20230312912A1 (en) * | 2020-08-12 | 2023-10-05 | Mitsubishi Gas Chemical Company, Inc. | Resin, method for producing resin, curable resin composition, and cured product |
| CN116075529A (en) | 2020-09-10 | 2023-05-05 | 日铁化学材料株式会社 | Method for producing aromatic ether compound having vinyl group |
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| JP2011099033A (en) * | 2009-11-05 | 2011-05-19 | Asahi Kasei Chemicals Corp | Method of producing polyphenylene ether |
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| CN114213652A (en) * | 2021-12-31 | 2022-03-22 | 河北健馨生物科技有限公司 | Preparation method of vinyl-terminated polyphenyl ether compound |
| CN114213652B (en) * | 2021-12-31 | 2023-08-08 | 河北健馨生物科技有限公司 | Preparation method of vinyl-terminated polyphenyl ether compound |
Also Published As
| Publication number | Publication date |
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| TWI790358B (en) | 2023-01-21 |
| JP6348244B1 (en) | 2018-06-27 |
| JP2019157015A (en) | 2019-09-19 |
| TW201938640A (en) | 2019-10-01 |
| WO2019176855A1 (en) | 2019-09-19 |
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