JP2019157015A - Method for producing poly (vinylbenzyl) ether compound - Google Patents
Method for producing poly (vinylbenzyl) ether compound Download PDFInfo
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- JP2019157015A JP2019157015A JP2018047443A JP2018047443A JP2019157015A JP 2019157015 A JP2019157015 A JP 2019157015A JP 2018047443 A JP2018047443 A JP 2018047443A JP 2018047443 A JP2018047443 A JP 2018047443A JP 2019157015 A JP2019157015 A JP 2019157015A
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- ether compound
- vinylbenzyl
- poly
- compound
- solvent
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- -1 poly (vinylbenzyl) ether compound Chemical class 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 239000000460 chlorine Substances 0.000 claims abstract description 37
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 37
- 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 28
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 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 19
- 239000002798 polar solvent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 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 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 45
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000005011 phenolic resin Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 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
- 150000003505 terpenes Chemical class 0.000 claims description 5
- 235000007586 terpenes Nutrition 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 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
- 150000002366 halogen compounds Chemical class 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 38
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 32
- 229920001955 polyphenylene ether Polymers 0.000 description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 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
- 238000005406 washing Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 6
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000001226 reprecipitation Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 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
- 230000014759 maintenance of location Effects 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
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- 230000000694 effects Effects 0.000 description 2
- 239000012776 electronic material Substances 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 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
- 239000001294 propane Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 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
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- ZUZSFMQBICMDEZ-UHFFFAOYSA-N prop-1-enylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC=CC1=CC=CC=C1 ZUZSFMQBICMDEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012086 standard solution 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
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
Description
本発明は、ポリ（ビニルベンジル）エーテル化合物の製造方法に関する。 The present invention relates to a method for producing a poly (vinylbenzyl) ether compound.
ポリ（ビニルベンジル）エーテル化合物は、誘電特性や耐吸湿熱性に優れているため、高周波信号を扱う電子機器の材料として用いられている。 Poly (vinyl benzyl) ether compounds are used as materials for electronic devices that handle high-frequency signals because they are excellent in dielectric properties and heat absorption resistance.
一般に電子材料用途では、製品の耐久性、信頼性の観点から、吸湿により加水分解を受け塩素イオンを遊離する、ハロゲン系化合物及びハロゲン化物イオンの残存量を極力少なくする必要があり、また、製造工程、製品コストの面からは、ハロゲン系化合物、ハロゲン化物イオンの除去を簡便な方法で実施することが望まれている。 In general, for electronic material applications, from the viewpoint of product durability and reliability, it is necessary to minimize the residual amount of halogenated compounds and halide ions that are hydrolyzed by moisture absorption to liberate chlorine ions and are manufactured. From the viewpoint of process and product cost, it is desired to remove the halogen-based compounds and halide ions by a simple method.
ポリ（ビニルベンジル）エーテル化合物の製造方法としては、例えばポリフェニレンエーテル化合物とハロゲン化メチルスチレン（ビニルベンジルハライド）とをアルカリ金属水酸化物の存在下、トルエン溶液中で反応させ、続いて、この反応溶液を酸で中和、洗浄後、多量のメタノールで再沈殿する方法が開示されている（特許文献１）。 As a method for producing a poly (vinylbenzyl) ether compound, for example, a polyphenylene ether compound and a halogenated methylstyrene (vinylbenzyl halide) are reacted in a toluene solution in the presence of an alkali metal hydroxide, followed by this reaction. A method is disclosed in which a solution is neutralized with an acid, washed, and then reprecipitated with a large amount of methanol (Patent Document 1).
しかしながら、特許文献１の製造方法では、ハロゲン系化合物及びハロゲン化物イオンの除去は可能であるが、再沈殿による精製工程を含むことにより、収率が低下し、工程時間が長くなるため、製造コスト面での改善が望まれている。 However, in the production method of Patent Document 1, it is possible to remove the halogen-based compound and halide ions, but since the purification step by reprecipitation is included, the yield decreases and the process time becomes long, so the production cost Improvement in terms is desired.
また、未反応原料由来のハロゲン系化合物（エピクロロヒドリン：沸点約１１８℃）を除去する方法としては、例えば特許文献２の実施例に記載されているように減圧留去が用いられているが、本発明で使用するハロゲン化メチルスチレン（クロロメチルスチレン）の沸点は２２９〜２４０℃であるので、減圧留去による除去は困難である。 Further, as a method for removing a halogen-based compound (epichlorohydrin: boiling point: about 118 ° C.) derived from unreacted raw materials, vacuum distillation is used as described in the example of Patent Document 2, for example. However, since the boiling point of halogenated methylstyrene (chloromethylstyrene) used in the present invention is 229 to 240 ° C., it is difficult to remove it by distillation under reduced pressure.
また、特許文献３に記載のビニルベンジル化ポリフェニレンエーテル化合物の製造方法では、精製工程として、反応工程で得られた反応液を、相間移動触媒の存在下に、アルカリ金属水酸化物水溶液で処理することにより未反応のビニルベンジルハライドを除去する除去工程を有するものであり、収率や製造コストについて、さらなる改善の余地があった。 Further, in the method for producing a vinylbenzylated polyphenylene ether compound described in Patent Document 3, as a purification step, the reaction solution obtained in the reaction step is treated with an alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst. This has a removal step of removing unreacted vinyl benzyl halide, and there is room for further improvement in yield and production cost.
本発明は、上記問題点に鑑みなされたものであって、ポリ（ビニルベンジル）エーテル化合物の製造方法であって、ハロゲン系化合物及びハロゲン化物イオンの残存量を低減しつつ、製造コストを削減可能な製造方法を提供することを目的とする。 The present invention has been made in view of the above problems, and is a method for producing a poly (vinylbenzyl) ether compound, which can reduce the production cost while reducing the residual amount of halogen-based compounds and halide ions. It is an object to provide a simple manufacturing method.
本発明者は、鋭意検討の結果、ハロゲン化メチルスチレンとして、特定の副生成物の含有量が少ないものを使用し、かつ所定の処方の溶媒中において反応工程を行うことにより、再沈殿などの精製工程を経ることなく、ハロゲン系化合物及びハロゲン化物イオンの残存量を低減することができることを見出した。 As a result of intensive studies, the present inventor used a halogenated methylstyrene having a low content of a specific by-product, and performing a reaction step in a solvent having a predetermined formulation, thereby allowing reprecipitation and the like. It has been found that the remaining amount of halogen compounds and halide ions can be reduced without going through a purification step.
すなわち、本発明のポリ（ビニルベンジル）エーテル化合物の製造方法は、フェノール性水酸基を有する化合物とハロゲン化メチルスチレンとを反応させることによりポリ（ビニルベンジル）エーテル化合物を製造する方法であって、フェノール性水酸基を有する化合物と、下記一般式（１）で表されるハロゲン化メチルスチレンとを、アルカリ金属水酸化物水溶液の存在下、芳香族炭化水素、及び非プロトン性極性溶媒を含む溶媒中で反応させる反応工程を含み、上記ハロゲン化メチルスチレン中の、一般式：Ｃ９Ｈ８Ｘ２（Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す）で表されるジハライド化合物の含有量が１．５質量％以下であり、上記溶媒中の非プロトン性極性溶媒の含有量が５質量％以上であるものとする。 That is, 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 halogenated methylstyrene, In a solvent containing an aromatic hydrocarbon and an aprotic polar solvent in the presence of an aqueous alkali metal hydroxide solution, a compound having a protic hydroxyl group and a halogenated methylstyrene represented by the following general formula (1): Including a dihalide compound represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine) in the halogenated methylstyrene, including a reaction step of reacting The amount is 1.5% by mass or less, and the content of the aprotic polar solvent in the solvent is 5% by mass or more.
式（１）中、Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す。 In the formula (1), X represents any atom selected from chlorine and bromine.
上記フェノール性水酸基を有する化合物は、式（２）又は（３）で示される繰り返し単位を有し、かつ、その末端にフェノール性水酸基を有するポリフェニレンエーテル化合物、テルペンフェノール樹脂、ジシクロペンタジエンフェノール樹脂及びポリビニルフェノール樹脂からなる群より選択された少なくとも１種であるものとすることができる。 The compound having a phenolic hydroxyl group has a repeating unit represented by the formula (2) or (3) and has a phenolic hydroxyl group at its terminal, a terpene phenol resin, a dicyclopentadiene phenol resin, and It can be at least one selected from the group consisting of polyvinylphenol resins.
式（２）中、Ｒ１〜Ｒ１６はそれぞれ独立して選択される水素原子又は炭素数１〜５の炭化水素基であり、Ａは、炭素数２０以下の直鎖状、分岐状または環状の２価の炭化水素基を示し、ｍ、ｎは少なくともいずれか一方が０でない、０〜１００の整数を示す。 In formula (2), R 1 to R 16 are independently selected hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and A is linear, branched or cyclic having 20 or less carbon atoms. And m and n each represents an integer of 0 to 100, at least one of which is not 0.
式（３）中、Ｒ１７〜Ｒ２０はそれぞれ独立して選択される水素原子又は炭素数１〜５の炭化水素基を示し、ｏは繰り返し単位数の平均値であり、１〜１００の整数を示す。 In the formula (3), R 17 to R 20 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, o is an average value of the number of repeating units, and is an integer of 1 to 100 Indicates.
上記アルカリ金属水酸化物水溶液の濃度は、１．０〜５０．０質量％であるものとすることができる。 The density | concentration of the said alkali metal hydroxide aqueous solution shall be 1.0-50.0 mass%.
上記芳香族炭化水素は、トルエン及びキシレンからなる群より選択された１種又は２種であるものとすることができる。 The aromatic hydrocarbon may be one or two selected from the group consisting of toluene and xylene.
上記溶媒中に、さらに炭素数３〜６の脂肪族アルコールからなる群より選択された１種又は２種以上の混合物を含有するものとすることができる。 In the said solvent, the 1 type, or 2 or more types of mixture selected from the group which consists of C3-C6 aliphatic alcohol shall be contained.
上記非プロトン性極性溶媒は、ジメチルスルホキシド、ジメチルホルムアミド、アセトニトリル、Ｎ−メチルピロリドン及び炭酸プロピレンからなる群より選択された１種又は２種以上の混合物であるものとすることができる。 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.
本発明によれば、再沈殿などの精製工程を経る必要がないため、製造コストを削減することができ、高純度、かつ、低ハロゲン系化合物及びハロゲン化物イオン濃度のポリ（ビニルベンジル）エーテル化合物を得ることができる。 According to the present invention, since it is not necessary to go through a refining step such as reprecipitation, the production cost can be reduced, and the poly (vinylbenzyl) ether compound has a high purity, a low halogen compound, and a halide ion concentration. Can be obtained.
以下に、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
本発明のポリ（ビニルベンジル）エーテル化合物の製造方法は、フェノール性水酸基を有する化合物とハロゲン化メチルスチレンとを反応させることによりポリ（ビニルベンジル）エーテル化合物を製造する方法であって、フェノール性水酸基を有する化合物と、下記一般式（１）で表されるハロゲン化メチルスチレンとを、アルカリ金属水酸化物水溶液の存在下、芳香族炭化水素及び非プロトン性極性溶媒を含む溶媒中で反応させる反応工程を含み、上記ハロゲン化メチルスチレン中に反応副生成物として通常含まれる、一般式：Ｃ９Ｈ８Ｘ２（Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す）で表されるジハライド化合物の含有量が１．５質量％以下であり、上記反応溶媒中の非プロトン性極性溶媒が、５質量％以上であるものとする。なお、本明細書において、単にジハライド化合物と言った場合、一般式：Ｃ９Ｈ８Ｘ２（Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す）で表されるジハロゲン化有機化合物を示し、Ｘが塩素である場合、ジクロロ化合物ということもある。 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 comprises a phenolic hydroxyl group. A reaction in which a compound having a hydrogen atom and a halogenated methylstyrene represented by the following general formula (1) are reacted in a solvent containing an aromatic hydrocarbon and an aprotic polar solvent in the presence of an aqueous alkali metal hydroxide solution Represented by the general formula: C 9 H 8 X 2 (wherein X represents any atom selected from chlorine and bromine), which is usually included as a reaction by-product in the halogenated methylstyrene. The dihalide compound content is 1.5% by mass or less, and the aprotic polar solvent in the reaction solvent is 5% by mass or more. And the. In the present specification, when simply referred to as a dihalide compound, a dihalogenated organic compound represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine) When X is chlorine, it may be a dichloro compound.
式（１）中、Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す。 In the formula (1), X represents any atom selected from chlorine and bromine.
ハロゲン化メチルスチレンを公知の方法で製造した場合、一般式（１）で示される（モノ）ハロゲン化メチルスチレンと副生成物との混合物として得られ、副生成物の詳細は定かではないが、イソプロペニルハロゲン化ベンゼン、後述するジハライド化合物、ジ（ハロゲン化メチル）スチレン等が含まれていると考えられる。本明細書で単に「ハロゲン化メチルスチレン」というときは、これらの副生成物も含む概念とする。 When halogenated methylstyrene is produced by a known method, it is obtained as a mixture of (mono) halogenated methylstyrene represented by general formula (1) and a by-product, and details of the by-product are not clear, It is considered that isopropenyl halogenated benzene, a dihalide compound described later, di (methyl halide) styrene and the like are contained. In the present specification, the term “halogenated methylstyrene” is a concept including these by-products.
一般式（１）で示されるハロゲン化メチルスチレンの具体例としては、例えば、ｏ−クロロメチルスチレン、ｍ−クロロメチルスチレン、ｐ−クロロメチルスチレン、ｏ−ブロモメチルスチレン、ｍ−ブロモメチルスチレン、ｐ−ブロモメチルスチレンなどが挙げられ、これらから選択される２種以上の混合物であってもそのまま使用することができる。 Specific examples of the halogenated methylstyrene represented by the general formula (1) include, for example, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, Examples thereof include p-bromomethylstyrene. Even a mixture of two or more selected from these can be used as it is.
本発明では、上記ハロゲン化メチルスチレン中に含まれる副生成物のうち、一般式：Ｃ９Ｈ８Ｘ２（Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す）で表されるジハライド化合物の含有量がハロゲン化メチルスチレン全量中１．５質量％以下であり、１．２質量％以下であることが好ましく、１．０質量％以下であることがより好ましい。ジハライド化合物の具体例としては、ジクロロメチルスチレン、クロロ（クロロメチル）スチレン、ジブロモメチルスチレン、ブロモ（ブロモメチル）スチレンなどが考えられる。ジハライド化合物の含有量が１．５質量％以下であることにより、低ハロゲン系化合物及びハロゲン化物イオン濃度のポリ（ビニルベンジル）エーテル化合物が得られ易い。 In the present invention, among the by-products contained in the halogenated methylstyrene, it is represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine). The content of the dihalide compound is 1.5% by mass or less, preferably 1.2% by mass or less, and more preferably 1.0% by mass or less, based on the total amount of methyl halide styrene. Specific examples of the dihalide compound include dichloromethylstyrene, chloro (chloromethyl) styrene, dibromomethylstyrene, bromo (bromomethyl) styrene, and the like. When the content of the dihalide compound is 1.5% by mass or less, a low halogen compound and a poly (vinylbenzyl) ether compound having a halide ion concentration are easily obtained.
本発明で使用されるハロゲン化メチルスチレンの配合割合は、フェノール性水酸基を有する化合物の水酸基１モルに対して、１．０１〜１．５０モルであることが好ましく、１．０５〜１．３０モルであることがより好ましい。１．０１モル未満であると、反応率が低くなり、残存する水酸基が多くなるため、電子材料用途の材料として使用した際、性能低下の要因となる傾向にあり、１．５モルを越えると、未反応のハロゲン化メチルスチレンの除去工程の時間が長くなる傾向にある。 The blending ratio of the halogenated methylstyrene used in the present invention is preferably 1.01-1.50 mol, preferably 1.05-1.30 mol, based on 1 mol of the hydroxyl group of the compound having a phenolic hydroxyl group. More preferably, it is a mole. When the amount is less than 1.01 mol, the reaction rate decreases and the number of remaining hydroxyl groups increases. Therefore, when used as a material for electronic materials, there is a tendency for performance to deteriorate. The time for removing unreacted methyl styrene styrene tends to be long.
本発明で使用されるフェノール性水酸基を有する化合物としては、特に限定されないが、例えば、下記一般式（２）又は（３）で示される繰り返し単位を有し、かつ、その末端にフェノール性水酸基を有するポリフェニレンエーテル化合物、テルペンフェノール樹脂、ジシクロペンタジエンフェノール樹脂、ポリビニルフェノール樹脂が挙げられる。 Although it does not specifically limit as a compound which has a phenolic hydroxyl group used by this invention, For example, it has a repeating unit shown by the following general formula (2) or (3), and has a phenolic hydroxyl group at the terminal. Examples thereof include polyphenylene ether compounds, terpene phenol resins, dicyclopentadiene phenol resins, and polyvinyl phenol resins.
一般式（２）において、Ｒ１〜Ｒ１６はそれぞれ独立して選択される水素原子又は炭素数１〜５の炭化水素基であり、Ａは、炭素数２０以下の直鎖状、分岐状または環状の２価の炭化水素基を示し、ｍ、ｎは少なくともいずれか一方が０でない、０〜１００の整数を示すものである。 In the general formula (2), R 1 to R 16 are independently selected hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and A is linear, branched or It represents a cyclic divalent hydrocarbon group, and m and n represent an integer of 0 to 100, at least one of which is not 0.
一般式（２）におけるＡは、例えば、メチレン、エチリデン、１−メチルエチリデン、１，１−プロピリデン、１，４−フェニレンビス（１−メチルエチリデン）、１，３−フェニレンビス（１−メチルエチリデン）、シクロヘキシリデン、フェニルメチレン、ナフチルメチレン、１−フェニルエチリデン等の２価の有機基が挙げられるが、これらに限定されるものではない。 A in the general formula (2) is, for example, methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis (1-methylethylidene), 1,3-phenylenebis (1-methylethylidene). ), Cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene and the like, but are not limited thereto.
一般式（２）で示されるポリフェニレンエーテル化合物の具体例としては、２，２−ビス（４−ヒドロキシ−３，５−メチルフェニル）プロパン・２，６−ジメチルフェノール重縮合物、２，２−ビス（４−ヒドロキシ−３，５−メチルフェニル）プロパン・２，３，６−トリメチルフェノール重縮合物、４，４’−メチレンビス（２，６−ジメチルフェノール）・２，６−ジメチルフェノール重縮合物、４，４’−メチレンビス（２，６−ジメチルフェノール）・２，３，６−トリメチルフェノール重縮合物などが挙げられるが、これらに限定されるものではない。これらポリフェニレンエーテル化合物は公知の方法で製造することができ、その製造方法は特に限定されず、また市販されているものを利用することもできる。 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, 2,2- Bis (4-hydroxy-3,5-methylphenyl) propane · 2,3,6-trimethylphenol polycondensate, 4,4'-methylenebis (2,6-dimethylphenol) · 2,6-dimethylphenol polycondensation Products, 4,4′-methylenebis (2,6-dimethylphenol) · 2,3,6-trimethylphenol polycondensate, and the like, but are not limited thereto. These polyphenylene ether compounds can be produced by known methods, and the production method is not particularly limited, and commercially available products can also be used.
また、本発明で使用される一般式（３）で示されるポリフェニレンエーテル化合物は、一般式（３）において、Ｒ１７〜Ｒ２０はそれぞれ独立して選択される水素原子又は炭素数１〜５の炭化水素基を示し、ｏは繰り返し単位数の平均値であり、１〜１００の整数を示すポリフェニレンエーテル化合物であれば、特に限定されない。 The polyphenylene ether compound represented by the general formula (3) used in the present invention is a hydrogen atom or a carbon number of 1 to 5 in which R 17 to R 20 are independently selected in the general formula (3). A hydrocarbon group is shown, o is an average value of the number of repeating units, and is not particularly limited as long as it is a polyphenylene ether compound showing an integer of 1 to 100.
一般式（３）で示されるポリフェニレンエーテル化合物の具体例としては、２，６−ジメチルフェノール重縮合物、２，３，６−トリメチルフェノール重縮合物などが挙げられるが、これらに限定されるものではない。これらポリフェニレンエーテル化合物は公知の方法で製造することができ、その製造方法は特に限定されず、また市販されているものを利用することもできる。 Specific examples of the polyphenylene ether compound represented by the general formula (3) include 2,6-dimethylphenol polycondensate and 2,3,6-trimethylphenol polycondensate, but are not limited thereto. is not. These polyphenylene ether compounds can be produced by known methods, and the production method is not particularly limited, and commercially available products can also be used.
本発明で使用されるアルカリ金属水酸化物水溶液としては、特に限定されるものではないが、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウムおよびこれらの混合物などが挙げられる。 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 a mixture thereof.
アルカリ金属水酸化物水溶液の配合割合は、特に制限されるものではないが、フェノール性水酸基を有する化合物の水酸基１モルに対して、１．２〜４．０モルであることが好ましい。１．２モル以上であると、反応時間が短くなる傾向にあり、４．０モル以下であると未反応のアルカリ化合物が残存しにくい。さらに、アルカリ金属水酸化物水溶液の濃度は、特に制限されるものではないが、反応をより迅速に進行させる観点より、１．０〜５０．０質量％であることが好ましい。 The blending ratio of the alkali metal hydroxide aqueous solution is not particularly limited, but is preferably 1.2 to 4.0 mol with respect to 1 mol of the hydroxyl group of the compound having a phenolic hydroxyl group. When it is 1.2 mol or more, the reaction time tends to be short, and when it is 4.0 mol or less, an unreacted alkali compound hardly remains. Furthermore, the concentration of the aqueous alkali metal hydroxide solution is not particularly limited, but is preferably 1.0 to 50.0% by mass from the viewpoint of allowing the reaction to proceed more rapidly.
本発明で溶媒として使用される芳香族炭化水素としては、例えば、ベンゼン、トルエン、エチルベンゼン、キシレン、エチルトルエン等が挙げられる。これらのうち、容易に入手でき、減圧によって容易に除去できる観点から、トルエンまたはキシレンが好ましい。 Examples of the aromatic hydrocarbon used as a solvent in the present invention include benzene, toluene, ethylbenzene, xylene, ethyltoluene and the like. Of these, toluene or xylene is preferred from the viewpoint of easy availability and easy removal by reduced pressure.
上記芳香族炭化水素の含有量は、特に限定されないが、溶媒全量中５０〜９５質量％であることが好ましく、６０〜９０質量％であることがより好ましい。 Although content of the said aromatic hydrocarbon is not specifically limited, It is preferable that it is 50-95 mass% in the solvent whole quantity, and it is more preferable that it is 60-90 mass%.
本発明で使用される非プロトン性極性溶媒としては、特に限定されないが、例えば、ジメチルスルホキシド、ジメチルホルムアミド、アセトニトリル、Ｎ−メチルピロリドン、炭酸プロピレン等が挙げられ、これらの中でも、取り扱いの容易さや、除去の容易さ等の点からジメチルスルホキシド、ジメチルホルムアルデヒド、アセトニトリルが好適に用いられる。 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. Among these, ease of handling, From the viewpoint of ease of removal, dimethyl sulfoxide, dimethyl formaldehyde, and acetonitrile are preferably used.
非プロトン性極性溶媒の含有量は、溶媒全量中５質量％以上であり、１０質量％以上であることが好ましい。非プロトン性極性溶媒を５質量％以上含有することにより、低ハロゲン系化合物及びハロゲン化物イオン濃度のポリ（ビニルベンジル）エーテル化合物が得られ易い。 The content of the aprotic polar solvent is 5% by mass or more in the total amount of the solvent, and preferably 10% by mass or more. By containing 5% by mass or more of the aprotic polar solvent, a low halogen compound and a poly (vinylbenzyl) ether compound having a halide ion concentration can be easily obtained.
上記溶媒中には、反応を促進させる観点から、上記芳香族炭化水素及び非プロトン性極性溶媒と共に脂肪族アルコールを含んでいても良く、脂肪族アルコールは炭素数３〜６の脂肪族アルコールからなる群より選択された１種又は２種以上の混合物であってもよい。 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 is an aliphatic alcohol having 3 to 6 carbon atoms. It may be one or a mixture of two or more selected from the group.
上記脂肪族アルコールとしては、炭素数３〜６の脂肪族アルコールが好ましく、例えば、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、ｎ−ペンタノール、２−エチルブタノール、ｎ−ヘキサノール等が挙げられる。これらのうち、減圧によって容易に除去できる観点から、炭素数３又は４の脂肪族アルコールが特に好ましい。 As said aliphatic alcohol, a C3-C6 aliphatic alcohol is preferable, for example, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, 2-ethyl Examples include butanol and n-hexanol. Of these, aliphatic alcohols having 3 or 4 carbon atoms are particularly preferred from the viewpoint that they can be easily removed under reduced pressure.
上記脂肪族アルコールを併用する場合、その含有量は、特に限定されないが、溶媒全量中４０質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましい。脂肪族アルコールの含有量を上記範囲とすることにより、原料であるフェノール性水酸基を有する化合物の溶解性を保持することができる。 When the aliphatic alcohol is used in combination, the content is not particularly limited, but is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less in the total amount of the solvent. Is more preferable. 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.
反応時に使用する溶媒の総量は、フェノール性水酸基を有する化合物１００質量部に対して１００〜３００質量部であることが好ましい。上記範囲より小さくなると、反応系の粘度が高くなり、未反応の原料が残りやすくなり、上記範囲より大きいと、ポリ（ビニルベンジル）エーテル化合物の反応釜の容量あたりの収量が低下する傾向にある。 The total amount of the solvent used during 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 it is smaller than the above range, the viscosity of the reaction system becomes high and unreacted raw materials are likely to remain, and if it is larger than the above range, the yield per volume of the reaction vessel of the poly (vinylbenzyl) ether compound tends to decrease. .
その他の反応条件は特に限定されず、従来から用いられている方法に準じて反応を行えばよい。すなわち、例えば、フェノール性水酸基を有する化合物とハロゲン化メチルスチレンと溶媒とを混合、攪拌し、そこへアルカリ金属水酸化物を滴下しながら反応を行うことができる。反応温度は通常６０〜１００℃程度であり、反応時間は２〜１６時間程度である。 Other reaction conditions are not particularly limited, and the reaction may be performed according to a conventionally used method. That is, for example, a compound having a phenolic hydroxyl group, halogenated methylstyrene and a solvent can be mixed and stirred, and the reaction can be carried out while dropping an alkali metal hydroxide thereto. The reaction temperature is usually about 60 to 100 ° C., and the reaction time is about 2 to 16 hours.
上記反応工程で得られた反応溶液は、従来から用いられている方法により中和反応を行うことができる。すなわち、例えば、反応溶液に、トルエンやイソプロパノールなどの有機溶媒と水を加えた後、塩酸などの酸で中和することができる。有機溶媒と水の使用量は、特に限定されないが、水／有機溶媒の質量比が４０／６０〜５／９５であることが好ましく、３０／７０〜１０／９０であることがより好ましい。 The reaction solution obtained in the above reaction step can be neutralized by a conventionally used method. That is, for example, an organic solvent such as toluene or isopropanol and water are added to the reaction solution, and then neutralized with an acid such as hydrochloric acid. Although the usage-amount of an organic solvent and water is not specifically limited, It is preferable that mass ratio of water / organic solvent is 40 / 60-5 / 95, and it is more preferable that it is 30 / 70-10 / 90.
上記中和工程で得られた中和溶液は、必要に応じて水と脂肪族アルコールとからなる混合液で洗浄することによりハロゲン化物イオン濃度をさらに低減することができる。その洗浄の際に使用する脂肪族アルコールとしては、上述した反応溶媒に使用できるものを使用することができる。脂肪族アルコールを使用することにより、洗浄時の有機層と水層の分離を容易に行なうことができる。その使用量は、水／脂肪族アルコールの質量比が９９／１〜２０／８０であることが好ましく、９０／１０〜３０／７０であることがより好ましい。 The neutralization solution obtained in the neutralization step can be further reduced in halide ion concentration by washing with a mixed solution of water and an aliphatic alcohol as necessary. As the aliphatic alcohol used in the washing, those usable for the reaction solvent described above can be used. By using the aliphatic alcohol, it is possible to easily separate the organic layer and the aqueous layer at the time of washing. The amount of water used is preferably a water / aliphatic alcohol mass ratio of 99/1 to 20/80, more preferably 90/10 to 30/70.
脂肪族アルコールの割合が上記範囲より小さくなると、有機層と水層の分離に長時間を要したり、有機層と水層との間に中間層が生じたりするおそれがある。また、上記範囲より大きいと、洗浄溶媒に生成物が溶解しやすくなり、収率が低下する傾向にある。 If the ratio of the aliphatic alcohol is smaller than the above range, it may take a long time to separate the organic layer and the aqueous layer, or an intermediate layer may be formed between the organic layer and the aqueous layer. Moreover, when larger than the said range, a product will become easy to melt | dissolve in a washing | cleaning solvent, and it exists in the tendency for a yield to fall.
水と脂肪族アルコールとからなる混合液の洗浄１回あたりの使用量は、ポリフェニレンエーテル化合物１００質量部に対して２０〜１５０質量部であることが好ましい。上記範囲より小さくなると、洗浄が不十分になりやすく、上記範囲より大きいと、生成物であるポリ（ビニルベンジル）エーテル化合物の溶解量が多くなり、収率が低下するおそれがある。 It is preferable that the usage-amount per wash of the liquid mixture which consists of water and an aliphatic alcohol is 20-150 mass parts with respect to 100 mass parts of polyphenylene ether compounds. If it is smaller than the above range, the washing tends to be insufficient, and if it is larger than the above range, the amount of the poly (vinylbenzyl) ether compound that is a product increases and the yield may be reduced.
洗浄方法としては常法に従い、液−液分離を行えばよく、洗浄後、脱水、濾過を行うことにより目的物を得ることができる。 As a washing method, liquid-liquid separation may be performed according to a conventional method, and the desired product can be obtained by performing dehydration and filtration after washing.
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例中、「部」および「％」は質量基準である。また、各実施例・比較例における測定は、以下の方法及び条件に従い実施した。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example. In the examples, “parts” and “%” are based on mass. Moreover, the measurement in each Example and a comparative example was implemented according to the following methods and conditions.
［反応率］
反応溶液１ｇを採取し、メタノール４０ｇによって再沈殿を行い、得られた樹脂を真空オーブン（１２０℃、２０ｍｍＨｇ）で３０分間乾燥した。これをＦＴ−ＩＲ（バイオラッド社製：ＦＴＳ−１３５）を用いてＫＢｒ法にて測定した。水酸基の吸収波長である３６１０ｃｍ−１のピーク面積を算出し、次の計算式により反応率を算出した。
反応率（％）＝［１−（Ｘ／Ｂ）］×１００
Ｘ：測定サンプルの３６１０ｃｍ−１のピーク面積
Ｂ：反応開始時の３６１０ｃｍ−１のピーク面積
[Reaction rate]
1 g of the reaction solution was collected, reprecipitated with 40 g of methanol, and the obtained resin was dried in a vacuum oven (120 ° C., 20 mmHg) for 30 minutes. This was measured by KBr method using FT-IR (Bio-Rad: FTS-135). The peak area of 3610 cm −1 , which is the absorption wavelength of the hydroxyl group, was calculated, and the reaction rate was calculated by the following formula.
Reaction rate (%) = [1- (X / B)] × 100
X: peak area of 3610 cm −1 of the measurement sample B: peak area of 3610 cm −1 at the start of the reaction
［残存クロロメチルスチレン量］
以下の条件で、ガラスクロマトグラフィーにより測定し、生成物であるポリ（ビニルベンジル）エーテル化合物中の割合（％）を求めた。
[Residual chloromethylstyrene content]
It measured by the glass chromatography on the following conditions, and calculated | required the ratio (%) in the poly (vinyl benzyl) ether compound which is a product.
〈測定条件〉
・カラム：アジレント・テクノロジー社製「ＤＢ−１」、内径０．３２ｍｍ×長さ３０ｍ、膜厚０．２５μｍ
・測定温度：１００℃で１分間保持した後、−１０℃／分で昇温し、−２８０℃で３分間保持
・注入口温度：３００℃
・検出口温度：３００℃
<Measurement condition>
Column: “DB-1” manufactured by Agilent Technologies, inner diameter 0.32 mm × length 30 m, film thickness 0.25 μm
・ Measurement temperature: held at 100 ° C. for 1 minute, then heated at −10 ° C./minute and held at −280 ° C. for 3 minutes. ・ Inlet temperature: 300 ° C.
-Detection port temperature: 300 ° C
［数平均分子量、重量平均分子量］
ＧＰＣ（ポリスチレン換算）により測定した。
[Number average molecular weight, weight average molecular weight]
It was measured by GPC (polystyrene conversion).
［加水分解性塩素量の測定方法］
サンプルを１．５ｇ秤量し、１５ｇの超純水（電気比抵抗１８ＭΩ・ｃｍ以上の水）を加え、１２５℃で２０時間加水分解させた。上層の抽出水をイオンクロマトグラフィー（ダイオニクス社製ＩＣＳ−１５００、カラム：ＩｏｎＰａｃ ＡＳ１２Ａ、溶離液：２．７ｍｍｏｌ／Ｌ Ｎａ２ＣＯ３／０．３ｍｍｏｌ／Ｌ ＮａＨＣＯ３、流量１．５ｍＬ／ｍｉｎ）にて塩素量を測定した。塩素量の検量線は、陰イオン混合標準液ＩＶ（関東化学株式会社製）を用いて作成した。
[Measurement of hydrolyzable chlorine content]
1.5 g of the sample was weighed, 15 g of ultrapure water (water having an electrical resistivity of 18 MΩ · cm or more) was added, and the sample was hydrolyzed at 125 ° C. for 20 hours. The extracted water of the upper layer was subjected to ion chromatography (ICS-1500, manufactured by Dionics, column: IonPac AS12A, eluent: 2.7 mmol / L Na 2 CO 3 /0.3 mmol / L NaHCO 3 , flow rate 1.5 mL / min). The amount of chlorine was measured. A calibration curve for the amount of chlorine was prepared using an anion mixed standard solution IV (manufactured by Kanto Chemical Co., Inc.).
［実施例１］
温度調節器、撹拌装置、冷却コンデンサー、滴下ロートを備えた２Ｌ四つ口フラスコに一般式（２）で示されるポリフェニレンエーテル化合物（一般式（２）のＲ１、Ｒ３、Ｒ５、Ｒ７、Ｒ１０、Ｒ１２、Ｒ１４、Ｒ１６がメチル基、Ｒ２、Ｒ４、Ｒ６、Ｒ８、Ｒ９、Ｒ１１、Ｒ１３、Ｒ１５が水素、Ａがイソプロピリデン基、ｍ＋ｎ＝平均１２、数平均分子量１５８０）を１５８ｇ（０．１モル）、トルエン２２１ｇ、ジメチルスルホキシド（以下ＤＭＳＯと記載）９４．８ｇを仕込み、均一溶液にし、続いて、テトラ−ｎ−ブチルアンモニウムブロマイド０．９６ｇ、クロロメチルスチレン（ジクロロ化合物含有量：ＧＣ面積０．０％、ジ（クロロメチル）スチレン体含有量：ＧＣ面積０．９％）３２．７ｇ（０．２１４モル）を加え、６５℃まで昇温した。ここに、４８％水酸化ナトリウム水溶液５３．３ｇ（０．６４モル）を３０分間かけて滴下し、６５℃で８時間反応を行なったところ、反応率は９８％以上であった。
[Example 1]
A polyphenylene ether compound represented by the general formula (2) (R 1 , R 3 , R 5 , R 7 in the general formula (2) is added to a 2 L four-necked flask equipped with a temperature controller, a stirrer, a cooling condenser, and a dropping funnel. , R 10 , R 12 , R 14 , R 16 are methyl groups, R 2 , R 4 , R 6 , R 8 , R 9 , R 11 , R 13 , R 15 are hydrogen, A is isopropylidene group, m + n = An average of 12 and a number average molecular weight of 1580) of 158 g (0.1 mol), 221 g of toluene, and 94.8 g of dimethyl sulfoxide (hereinafter referred to as DMSO) were charged to make a homogeneous solution, followed by tetra-n-butylammonium bromide 96 g, chloromethylstyrene (dichloro compound content: GC area 0.0%, di (chloromethyl) styrene body content: GC area 0.9%) 32.7 g (0. 14 mol) was added and heated to 65 ° C.. 48% sodium hydroxide aqueous solution 53.3g (0.64mol) was dripped here over 30 minutes, and when reaction was performed at 65 degreeC for 8 hours, the reaction rate was 98% or more.
その後、５０℃まで冷却し、トルエン２９５ｇ、イソプロパノール（ＩＰＡ）１２６．４ｇ、水７９ｇを加え、３５質量％の塩酸水溶液４６．７ｇで中和した。反応溶液が２層に分離するまで静置し、下層の水溶液層を除去した。さらに、イソプロパノール１５．８ｇと水６３．２ｇの混合物による洗浄を５回行なった。この有機層を、７０℃、５０ｍｍＨｇで水分を０．０５％以下になるまで除去し、さらにこの溶液を濾過し、ビニルベンジル化ポリフェニレンエーテル化合物の５０％トルエン溶液３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％、以下生成物と記載）を得た。このビニルベンジル化ポリフェニレンエーテル化合物中の残存クロロメチルスチレン量（固形分換算値）は０．１％未満、加水分解性塩素量は７６ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６８０であった。 Then, it cooled to 50 degreeC, 295 g of toluene, 126.4 g of isopropanol (IPA), and 79 g of water were added, and it neutralized with 46.7 g of 35 mass% hydrochloric acid aqueous solution. The reaction solution was allowed to stand until it was separated into two layers, and the lower aqueous solution layer was removed. Further, washing with a mixture of 15.8 g of isopropanol and 63.2 g of water was performed 5 times. The organic layer was removed at 70 ° C. and 50 mmHg until the water content was 0.05% or less. The solution was filtered, and 345 g of a 50% toluene solution of vinylbenzylated polyphenylene ether compound (yield based on polyphenylene ether compound). 95%, hereinafter referred to as product). The vinyl benzylated polyphenylene ether compound has a residual chloromethylstyrene amount (in terms of solid content) of less than 0.1%, a hydrolyzable chlorine amount of 76 ppm, a number average molecular weight of 2,180, and a weight average molecular weight of 3,680. Met.
［実施例２］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が０．１％、ジ（クロロメチル）スチレン体含有量が０．０％のものに変更した以外は実施例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は１０３ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 2]
The same operation as in Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to a dichloro compound content of 0.1% and a di (chloromethyl) styrene content of 0.0%, 345 g of product (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 103 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例３］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が０．３％、ジ（クロロメチル）スチレン体含有量が０．０％のものに変更した以外は実施例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は１６９ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 3]
The same operation as in Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to a dichloro compound content of 0.3% and a di (chloromethyl) styrene content of 0.0%, 345 g of product (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 169 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例４］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が０．８％、ジ（クロロメチル）スチレン体含有量が０．０％のものに変更した以外は実施例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２２７ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 4]
The same operation as in Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to a dichloro compound content of 0.8% and a di (chloromethyl) styrene content of 0.0%, 345 g of product (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 227 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例５］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が１．１％、ジ（クロロメチル）スチレン体含有量０．０％のものに変更した以外は実施例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は４０９ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 5]
The same operation as in Example 1 was carried out except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 1.1% and a di (chloromethyl) styrene content of 0.0%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 409 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例６］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が１．５％、ジ（クロロメチル）スチレン体含有量０．０％のものに変更した以外は実施例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は５９５ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 6]
The same operation as in Example 1 was carried out except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 1.5% and a di (chloromethyl) styrene content of 0.0%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 595 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例７］
反応で使用した溶媒量をトルエン１８９．５ｇ、ＤＭＳＯ１２６．３ｇとした以外は実施例４と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２１０ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 7]
The same operation as in Example 4 was carried out except that the amount of solvent used in the reaction was changed to 189.5 g of toluene and 126.3 g of DMSO to obtain 345 g of product (yield 95% based on polyphenylene ether compound). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 210 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例８］
反応で使用した溶媒種、量をトルエン２２１ｇ、イソプロパノール３１．６ｇ、ＤＭＳＯ６３．２ｇとした以外は実施例４と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．２％、加水分解性塩素量は３１０ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 8]
The same operation as in Example 4 was carried out except that the solvent type and amount used in the reaction were changed to 221 g of toluene, 31.6 g of isopropanol, and 63.2 g of DMSO to obtain 345 g of product (yield 95% based on polyphenylene ether compound). It was. The amount of residual chloromethylstyrene in the obtained product was 0.2%, the amount of hydrolyzable chlorine was 310 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例９］
反応で使用した溶媒種、量をトルエン２２１ｇ、イソプロパノール６３．２ｇ、ＤＭＳＯ３１．６ｇとした以外は実施例４と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．３％、加水分解性塩素量は３５０ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 9]
The same operation as in Example 4 was carried out except that the solvent type and amount used in the reaction were changed to 221 g of toluene, 63.2 g of isopropanol, and 31.6 g of DMSO to obtain 345 g of product (yield 95% based on polyphenylene ether compound). It was. The amount of residual chloromethylstyrene in the obtained product was 0.3%, the amount of hydrolyzable chlorine was 350 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例１０］
反応で使用した溶媒種をトルエン２２１ｇからキシレン２２１ｇに変更した以外は実施例４と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２２０ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 10]
The same operation as in Example 4 was carried out except that the solvent species used in the reaction was changed from 221 g of toluene to 221 g of xylene to obtain 345 g of product (yield 95% based on polyphenylene ether compound). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 220 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例１１］
反応で使用した溶媒種をＤＭＳＯ９４．８ｇからＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）９４．８ｇに変更した以外は実施例１０と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２３５ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Example 11]
The same operation as in Example 10 was carried out except that the solvent species used in the reaction was changed from 94.8 g of DMSO to 94.8 g of N, N-dimethylformamide (DMF), and 345 g of product (yield 95 based on polyphenylene ether compound). %). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 235 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［実施例１２］
反応で使用したポリフェニレンエーテル化合物をフェノール樹脂Ａ（テルペンフェノール樹脂、フェノール量１，４００ｇ／モル）１４０ｇ（０．１モル）に変更した以外は実施例５と同様の操作を行ない、生成物２７３ｇ（テルペンフェノール樹脂基準で収率９０％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２１２ｐｐｍであった。
[Example 12]
The same operation as in Example 5 was performed except that the polyphenylene ether compound used in the reaction was changed to 140 g (0.1 mol) of phenol resin A (terpene phenol resin, phenol amount 1,400 g / mol), and 273 g of product ( Yield 90% based on terpene phenol resin). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, and the amount of hydrolyzable chlorine was 212 ppm.
［実施例１３］
反応で使用したポリフェニレンエーテル化合物をフェノール樹脂Ｂ（ジシクロペンタジエンフェノール樹脂、フェノール量３３７ｇ／モル）３３．７ｇ（０．１モル）に変更した以外は実施例５と同様の操作を行ない、生成物８１．８ｇ（ジシクロペンタジエンフェノール樹脂基準で収率９０％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２３４ｐｐｍであった。
[Example 13]
The same operation as in Example 5 was carried out except that the polyphenylene ether compound used in the reaction was changed to 33.7 g (0.1 mol) of phenol resin B (dicyclopentadiene phenol resin, phenol amount 337 g / mol). 81.8 g (yield 90% based on dicyclopentadiene phenol resin) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, and the amount of hydrolyzable chlorine was 234 ppm.
［比較例１］
反応で使用した溶媒種、量をトルエン２２１ｇ、イソプロパノール９４．８ｇとした以外は実施例５と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は１．０％、加水分解性塩素量は２２９０ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Comparative Example 1]
The same operation as in Example 5 was carried out except that the solvent species and amount used in the reaction were changed to 221 g of toluene and 94.8 g of isopropanol to obtain 345 g of product (yield 95% based on polyphenylene ether compound). The amount of residual chloromethylstyrene in the obtained product was 1.0%, the amount of hydrolyzable chlorine was 2290 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［比較例２］
比較例１で合成した製品１００ｇにトルエン１６７ｇを加えて希釈した。希釈液をメタノール（１０００ｇ）中に投入し再沈殿を行い、樹脂粉末を得た。これを水／メタノール（質量比８０／２０）混合溶媒２００ｇで４回洗浄した。これを真空オーブン（１００℃、２０ｍｍＨｇ）にて２４時間乾燥し、黄色粉末４５ｇ（ポリフェニレンエーテル化合物基準で収率９０％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２００ｐｐｍ、数平均分子量は２，２００、重量平均分子量は３，８００であった。
[Comparative Example 2]
To 100 g of the product synthesized in Comparative Example 1, 167 g of toluene was added for dilution. The diluted solution was poured into methanol (1000 g) to perform reprecipitation to obtain a resin powder. This was washed four times with 200 g of a mixed solvent of water / methanol (mass ratio 80/20). This was dried in a vacuum oven (100 ° C., 20 mmHg) for 24 hours to obtain 45 g of yellow powder (yield 90% based on polyphenylene ether compound). The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 200 ppm, the number average molecular weight was 2,200, and the weight average molecular weight was 3,800.
［比較例３］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が０．０％、ジ（クロロメチル）スチレン体含有量０．９％のものに変更した以外は比較例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．９％、加水分解性塩素量は１８００ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Comparative Example 3]
The same operation as in Comparative Example 1 was performed except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 0.0% and a di (chloromethyl) styrene content of 0.9%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was 0.9%, the amount of hydrolyzable chlorine was 1800 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
［比較例４］
反応で使用したクロロメチルスチレンを、ジクロロ化合物含有量が３．９％、ジ（クロロメチル）スチレン体含有量０．０％のものに変更した以外は実施例１と同様の操作を行ない、生成物３４５ｇ（ポリフェニレンエーテル化合物基準で収率９５％）を得た。得られた生成物中の残存クロロメチルスチレン量は０．１％未満、加水分解性塩素量は２１３２ｐｐｍ、数平均分子量は２，１８０、重量平均分子量は３，６５０であった。
[Comparative Example 4]
The same operation as in Example 1 was carried out except that the chloromethylstyrene used in the reaction was changed to one having a dichloro compound content of 3.9% and a di (chloromethyl) styrene content of 0.0%. 345 g (yield 95% based on polyphenylene ether compound) was obtained. The amount of residual chloromethylstyrene in the obtained product was less than 0.1%, the amount of hydrolyzable chlorine was 2132 ppm, the number average molecular weight was 2,180, and the weight average molecular weight was 3,650.
上記各実施例及び比較例の反応物、溶媒、精製の有無を、得られた生成物の残存クロロメチルスチレン量及び加水分解性塩素量と共に表１に示す。 The reactants, solvents, and presence / absence of purification in each of the above Examples and Comparative Examples are shown in Table 1 together with the amount of residual chloromethylstyrene and the amount of hydrolyzable chlorine in the obtained product.
実施例１〜１３では、再沈殿による精製工程を経ることなく、ポリ（ビニルベンジル）エーテル化合物中の残存クロロメチルスチレン量及び加水分解性塩素量を低減することができた。ハロゲン化メチルスチレン中のジハライド化合物の含有量が所定値以下であるが、反応溶媒が非プロトン性極性溶媒を含有しない例である比較例１，２と、実施例５との対比より、実施例５では、比較例１で得られた化合物を再沈殿による精製工程に付した比較例２と同程度まで低減することができた。 In Examples 1 to 13, the amount of residual chloromethylstyrene and the amount of hydrolyzable chlorine in the poly (vinylbenzyl) ether compound could be reduced without going through a purification step by reprecipitation. In comparison with Example 5 and Comparative Examples 1 and 2, in which the content of the dihalide compound in the halogenated methylstyrene is not more than a predetermined value, the reaction solvent does not contain an aprotic polar solvent. In No. 5, the compound obtained in Comparative Example 1 could be reduced to the same level as in Comparative Example 2 subjected to the purification step by reprecipitation.
また、実施例１と実施例２との対比より、ハロゲン化メチルスチレン中に含まれる副生成物の内、ジ（クロロメチル）スチレンの加水分解性塩素量への影響は大きくなく、ジハライド化合物であるジクロロ化合物が加水分解性塩素量に影響していることがわかる。 Further, from the comparison between Example 1 and Example 2, among the by-products contained in the halogenated methylstyrene, the influence on the hydrolyzable chlorine content of di (chloromethyl) styrene is not significant, and the dihalide compound is used. It can be seen that a certain dichloro compound affects the amount of hydrolyzable chlorine.
比較例３は、ハロゲン化メチルスチレン中のジハライド化合物の含有量が所定値以下であるが、反応溶媒が非プロトン性極性溶媒を含有しない例であり、単にハロゲン化メチルスチレンの純度を高めただけでは、ポリ（ビニルベンジル）エーテル化合物中の加水分解性塩素量の低減効果は得られなかった。 Comparative Example 3 is an example in which the content of the dihalide compound in the halogenated methylstyrene is not more than a predetermined value, but the reaction solvent does not contain an aprotic polar solvent, and the purity of the halogenated methylstyrene is simply increased. However, the effect of reducing the amount of hydrolyzable chlorine in the poly (vinylbenzyl) ether compound was not obtained.
比較例４は、反応溶媒に非プロトン性極性溶媒を含有するが、ハロゲン化メチルスチレン中のジハライド化合物の含有量が所定値以上である例であり、反応溶媒中に非プロトン性極性溶媒を含有するだけでは、加水分解性塩素量の低減効果は得られなかった。 Comparative Example 4 is an example in which an aprotic polar solvent is contained in the reaction solvent, but the dihalide compound content in the halogenated methylstyrene is a predetermined value or more, and the aprotic polar solvent is contained in the reaction solvent. Only by doing, the effect of reducing the amount of hydrolyzable chlorine was not obtained.
また、実施例１、実施例５、実施例４，７〜１３で使用したクロロメチルスチレンについて行った、ガスクロマトグラフィー測定結果を図１〜３に示す。 Moreover, the gas-chromatography measurement result performed about the chloromethylstyrene used in Example 1, Example 5, Example 4, 7-13 is shown to FIGS.
図１に示すように、実施例１で用いたハロゲン化メチルスチレンでは、保持時間が１０．３７７ｍｉｎ、１０．５９５ｍｉｎである位置にジ（クロロメチル）スチレンを示すピークが検出され、ジハライド化合物は検出されなかった。 As shown in FIG. 1, in the halogenated methylstyrene used in Example 1, a peak indicating di (chloromethyl) styrene was detected at a position where the retention times were 10.377 min and 10.595 min, and the dihalide compound was detected. Was not.
一方、図２に示すように、実施例５で用いたハロゲン化メチルスチレンでは、保持時間が８．１３０ｍｉｎ、８．３２２ｍｉｎの位置に、図３に示すように、実施例４，７〜１３で用いたハロゲン化メチルスチレンでは、８．１３２ｍｉｎ、８．３２５ｍｉｎの位置にジハライド化合物を示すピークが検出された。その後さらに検証を行った結果、保持時間の短い方（８．１３０ｍｉｎ、８．１３２ｍｉｎ）のジハライド化合物が、ポリ（ビニルベンジル）エーテル化合物中のハロゲン系化合物並びにハロゲン化物イオンの生成に影響を与えている可能性が高く、この含有量が低いほど好ましいことがわかった。 On the other hand, as shown in FIG. 2, in the halogenated methylstyrene used in Example 5, the retention times were 8.130 min and 8.322 min, as shown in FIG. In the halogenated methylstyrene used, peaks indicating a dihalide compound were detected at positions of 8.132 min and 8.325 min. As a result of further verification, the dihalide compound having the shorter retention time (8.130 min, 8.132 min) affected the generation of halogen compounds and halide ions in the poly (vinylbenzyl) ether compound. It was found that the lower the content, the better.
本発明の製造方法によれば、化合物中のハロゲン系化合物並びにハロゲン化物イオンを低減しつつ、製造コストを削減した、高周波信号を扱う電子機器の材料として好適なポリ（ビニルベンジル）エーテル化合物を提供できる。 According to the production method of the present invention, a poly (vinylbenzyl) ether compound suitable as a material for electronic equipment that handles high-frequency signals is provided with reduced production costs while reducing halogen compounds and halide ions in the compound. it can.
Claims (6)
フェノール性水酸基を有する化合物と、下記一般式（１）で表されるハロゲン化メチルスチレンとを、アルカリ金属水酸化物水溶液の存在下、芳香族炭化水素及び非プロトン性極性溶媒を含む溶媒中で反応させる反応工程を含み、
前記ハロゲン化メチルスチレン中の、一般式：Ｃ９Ｈ８Ｘ２（Ｘは、塩素及び臭素から選ばれたいずれかの原子を示す）で表されるジハライド化合物の含有量が１．５質量％以下であり、
前記溶媒中の非プロトン性極性溶媒の含有量が５質量％以上であることを特徴とする、
ポリ（ビニルベンジル）エーテル化合物の製造方法。
A compound having a phenolic hydroxyl group and a halogenated methylstyrene represented by the following general formula (1) in a solvent containing an aromatic hydrocarbon and an aprotic polar solvent in the presence of an aqueous alkali metal hydroxide solution Including a reaction step of reacting,
In the halogenated methylstyrene, the content of the dihalide compound represented by the general formula: C 9 H 8 X 2 (X represents any atom selected from chlorine and bromine) is 1.5% by mass. And
The content of the aprotic polar solvent in the solvent is 5% by mass or more,
A method for producing a poly (vinylbenzyl) ether compound.
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. 6. The method for producing a poly (vinylbenzyl) ether compound according to any one of 5 above.
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| WO2022034752A1 (en) * | 2020-08-12 | 2022-02-17 | 三菱瓦斯化学株式会社 | Resin, method for producing resin, curable resin composition, and cured object |
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| TWI790358B (en) | 2023-01-21 |
| JP6348244B1 (en) | 2018-06-27 |
| TW201938640A (en) | 2019-10-01 |
| WO2019176855A1 (en) | 2019-09-19 |
| CN111819219A (en) | 2020-10-23 |
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