CN111133017A - Process for producing novolak polymer - Google Patents
Process for producing novolak polymer Download PDFInfo
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- CN111133017A CN111133017A CN201880059466.5A CN201880059466A CN111133017A CN 111133017 A CN111133017 A CN 111133017A CN 201880059466 A CN201880059466 A CN 201880059466A CN 111133017 A CN111133017 A CN 111133017A
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- novolak
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- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 229920003986 novolac Polymers 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 11
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 239000006227 byproduct Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 5
- 229940078552 o-xylene Drugs 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000010992 reflux Methods 0.000 description 15
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 3
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 3
- SEVSMVUOKAMPDO-UHFFFAOYSA-N 4-acetoxy benzaldehyde Chemical compound CC(=O)OC1=CC=C(C=O)C=C1 SEVSMVUOKAMPDO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000005259 triarylamine group Chemical group 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 102100036782 Serine/threonine-protein phosphatase 2A activator Human genes 0.000 description 2
- 101710196539 Serine/threonine-protein phosphatase 2A activator Proteins 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000327 poly(triphenylamine) polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- 125000006002 1,1-difluoroethyl group Chemical group 0.000 description 1
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000005999 2-bromoethyl group Chemical group 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- NMTUHPSKJJYGML-UHFFFAOYSA-N 3-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=CC(C=O)=C1 NMTUHPSKJJYGML-UHFFFAOYSA-N 0.000 description 1
- UHDNUPHSDMOGCR-UHFFFAOYSA-N 3-Formylbenzoic acid Chemical compound OC(=O)C1=CC=CC(C=O)=C1 UHDNUPHSDMOGCR-UHFFFAOYSA-N 0.000 description 1
- RBIGKSZIQCTIJF-UHFFFAOYSA-N 3-formylthiophene Chemical compound O=CC=1C=CSC=1 RBIGKSZIQCTIJF-UHFFFAOYSA-N 0.000 description 1
- KFKSIUOALVIACE-UHFFFAOYSA-N 3-phenylbenzaldehyde Chemical compound O=CC1=CC=CC(C=2C=CC=CC=2)=C1 KFKSIUOALVIACE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- UESSERYYFWCTBU-UHFFFAOYSA-N 4-(n-phenylanilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UESSERYYFWCTBU-UHFFFAOYSA-N 0.000 description 1
- BEOBZEOPTQQELP-UHFFFAOYSA-N 4-(trifluoromethyl)benzaldehyde Chemical compound FC(F)(F)C1=CC=C(C=O)C=C1 BEOBZEOPTQQELP-UHFFFAOYSA-N 0.000 description 1
- KTFKRVMXIVSARW-UHFFFAOYSA-N 4-acetylbenzaldehyde Chemical compound CC(=O)C1=CC=C(C=O)C=C1 KTFKRVMXIVSARW-UHFFFAOYSA-N 0.000 description 1
- OVRKATYHWPCGPZ-UHFFFAOYSA-N 4-methyloxane Chemical compound CC1CCOCC1 OVRKATYHWPCGPZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- YMNKUHIVVMFOFO-UHFFFAOYSA-N anthracene-9-carbaldehyde Chemical compound C1=CC=C2C(C=O)=C(C=CC=C3)C3=CC2=C1 YMNKUHIVVMFOFO-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000005266 diarylamine group Chemical group 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- YRMODRRGEUGHTF-UHFFFAOYSA-N methyl 2-formylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C=O YRMODRRGEUGHTF-UHFFFAOYSA-N 0.000 description 1
- UVSBCUAQEZINCQ-UHFFFAOYSA-N methyl 3-formylbenzoate Chemical compound COC(=O)C1=CC=CC(C=O)=C1 UVSBCUAQEZINCQ-UHFFFAOYSA-N 0.000 description 1
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The present invention provides a method for producing a novolak polymer, wherein an aromatic amine compound and an aldehyde compound are polymerized in the presence of a catalyst in an organic solvent while removing water as a by-product.
Description
Technical Field
The present invention relates to a method for producing a novolak polymer.
Background
In the production of a novolak polymer, the risk of gelation is an issue when the polymer is converted to a super high molecular weight. The present problem arises from the presence of unreacted aldehyde compounds, and a general method of controlling the molecular weight of the fed aldehyde compounds to an appropriate value, that is, avoiding gelation, is to completely react the fed aldehyde compounds (that is, reduce the amount of unreacted aldehyde compounds) by adjusting the feed amounts of the aromatic amine compounds and the aldehyde compounds.
In order to reduce the unreacted aldehyde compounds, a method is known in which the aldehyde compounds are added to the reaction system one by one to increase the concentration of the reaction system. However, in these methods, it is difficult to completely react the aldehyde compound, and when the concentration is increased, the viscosity of the reaction system inevitably increases, which may cause damage to the stirring blades of the reactor. In addition, there are cases where the polymer precipitates and sticks to the inner wall of the reactor due to the by-produced water, and in such cases, the workability of cleaning and the like of the reactor becomes a problem. These are common problems in the production of novolak polymers.
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a novolak polymer, which can avoid all the production problems such as gelation, high viscosity, and wall adhesion.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found the following conditions: the present inventors have completed the present invention by carrying out the polymerization reaction while removing by-product water to thereby prevent the formation of wall-fixed substances, and by removing water from the reaction system to thereby rapidly carry out the polymerization, thereby enabling the reaction system to achieve an ultrahigh molecular weight even at a low concentration, and by controlling the molecular weight to an appropriate level without leaving unreacted aldehyde compounds, which cause gelation, in the reaction system.
Namely, the present invention provides the following method for producing a novolak polymer.
1. A process for producing a novolak polymer, which comprises polymerizing an aromatic amine compound and an aldehyde compound in the presence of a catalyst in an organic solvent while removing water as a by-product.
2.1A method for producing a novolak polymer, wherein water is removed azeotropically.
3.1 or 2, wherein the organic solvent is azeotropable with water, has a specific gravity smaller than that of water, and is not mixed with water.
4.1 to 3, wherein the organic solvent is toluene, o-xylene, m-xylene, p-xylene, or a mixed solvent thereof.
5.1 to 4, wherein the catalyst is an acid catalyst.
The method for producing a novolak polymer according to 6.5, wherein the acid catalyst is sulfuric acid or sulfonic acid.
7.1 to 6, wherein the organic solvent is used in an amount of 1 to 50 by mass relative to the aromatic amine compound.
8.1 to 7, wherein the aromatic amine compound is a triarylamine compound.
9.1 to 8, wherein the aldehyde compound is an aromatic aldehyde compound.
10.1 to 9, wherein the novolak polymer is a hyperbranched polymer.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the method for producing a novolak polymer of the present invention, all production problems such as gelation, high viscosity, and wall adhesion can be avoided, and a novolak polymer having a high molecular weight can be produced.
Drawings
FIG. 1 is a photograph of the reaction vessel after the completion of the reaction (toluene solution of polymer) in example 1.
Fig. 2 is a photograph of the reaction vessel after the reaction in comparative example 1 was completed (in the case of using 1 equivalent or more of aldehyde and reacting in a dioxane solvent).
Fig. 3 is a photograph of the reaction vessel in the reaction solution (high concentration condition (dioxane solvent)) having a high viscosity in comparative example 2.
Detailed Description
The method for producing a novolak polymer of the present invention is a method for polymerizing an aromatic amine compound and an aldehyde compound in the presence of a catalyst in an organic solvent while removing water as a by-product.
In the production method of the present invention, the aromatic amine compound is not particularly limited, and monoarylamine compounds, diarylamine compounds, and triarylamine compounds can be used, but triarylamine compounds are preferable, and triarylamine compounds represented by the following formula (a) are particularly preferable.
[ solution 1]
In the formula (A), Ar1～Ar3Each independently represents a 2-valent organic group represented by any one of the formulae (A-1) to (A-5), and a group represented by the formula (A-1) is particularly preferred.
[ solution 2]
In the formulae (A-1) to (A-5), R1～R34Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
Among them, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group having 1 to 5 carbon atoms is preferably a straight-chain or branched alkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group.
The alkoxy group having 1 to 5 carbon atoms is preferably a straight-chain or branched alkoxy group, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, and a n-pentoxy group.
Examples of the preferable triarylamine compound include triphenylamine and derivatives thereof.
The aldehyde compound used in the present invention is not particularly limited, and an aldehyde compound represented by the following formula (B) is preferable.
[ solution 3]
In the formula (B), R is independently a hydrogen atom, an alkyl group having 1-5 carbon atoms, or a 1-valent organic group represented by any one of the following formulas (B-1) to (B-4).
[ solution 4]
In the formulae (B-1) to (B-4), R35～R58Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a phenyl group, -OR59、-COR60、-NR61R62or-COOR63，R59～R62Each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms or a phenyl group, R63Is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a phenyl group.
Examples of the haloalkyl group having 1 to 5 carbon atoms include a linear or branched haloalkyl group, such as a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1, 1-difluoroethyl group, a 2,2, 2-trifluoroethyl group, a 1,1,2, 2-tetrafluoroethyl group, a 2-chloro-1, 1, 2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3, 3-tetrafluoropropyl group, a 1,1,2,3,3, 3-hexafluoropropyl group, a 1,1,1,3,3, 3-hexafluoropropane-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group. Examples of the halogen atom and the alkyl group having 1 to 5 carbon atoms include the same groups as those described above.
As the above aldehyde compound, an aromatic aldehyde compound is preferable. Specifically, among the aldehyde compounds represented by the formula (B), preferred are aldehyde compounds in which R is a group represented by any one of the formulae (B-1) to (B-4), preferred are aldehyde compounds in which R is 2-or 3-thienyl, or a group represented by the formula (B-1), more preferred are aldehyde compounds in which R is 2-or 3-thienyl, or R in a group represented by the formula (B-1)37An aldehyde compound which is a phenyl group or a methoxy group, further preferably R is a 2-or 3-thienyl group, or R in the group represented by the formula (B-1)37An aldehyde compound which is a phenyl group.
Preferred examples of the aldehyde compound include benzaldehyde, 4-methylbenzaldehyde, 3-trifluoromethylbenzaldehyde, 4-trifluoromethylbenzaldehyde, 3-phenylbenzaldehyde, 4-phenylbenzaldehyde, salicylaldehyde, anisaldehyde, 4-acetoxybenzaldehyde, 4-acetylbenzaldehyde, 2-formylbenzoic acid, and 3-formylbenzoic acid, aromatic aldehyde compounds such as 4-formylbenzoic acid, methyl 2-formylbenzoate, methyl 3-formylbenzoate, methyl 4-formylbenzoate, 4-aminobenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 1-naphthaldehyde, 2-thiophenecarboxaldehyde, 3-thiophenecarboxaldehyde, and 9-anthracenealdehyde.
The novolak-type hyperbranched polymer containing a repeating unit represented by the following formula (C) can be synthesized by polymerizing an aromatic amine compound represented by the formula (a) and an aldehyde compound represented by the formula (B) in the presence of an acid catalyst.
[ solution 5]
(wherein Ar is1～Ar3And R is the same as above. )
The novolac-type hyperbranched polymer is preferably a novolac-type hyperbranched polymer having a repeating unit represented by the following formula, but is not limited thereto.
[ solution 6]
In the production method of the present invention, the amount of the aldehyde compound represented by the formula (B) to be used is preferably 0.1 to 1.0 equivalent, more preferably 0.7 to 0.95 equivalent, to 1 equivalent of the aromatic amine compound represented by the formula (a).
The average molecular weight of the novolak polymer is not particularly limited, but the weight average molecular weight (Mw) is preferably 1,000 to 2,000,000, more preferably 2,000 to 200,000. In the present invention, Mw is a polystyrene-equivalent measured value obtained by Gel Permeation Chromatography (GPC).
As the acid catalyst, inorganic acids such as sulfuric acid, phosphoric acid and perchloric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid and camphorsulfonic acid, and organic acids such as carboxylic acids such as formic acid and oxalic acid can be used, and sulfuric acid and sulfonic acid are preferable. The amount of the acid catalyst to be used is appropriately determined depending on the kind thereof, and is usually preferably 0.01 to 0.5 equivalent, more preferably 0.02 to 0.2 equivalent, based on 1 equivalent of the aromatic amine compound.
The novolak polymer is synthesized by condensation polymerization of the aromatic amine compound and an aldehyde compound, and water is generated as a by-product because dehydration occurs at this time. In the production method of the present invention, the polymerization reaction is carried out while removing the by-produced water from the reaction system.
The method for removing the water as the by-product is not particularly limited, and from the viewpoint of mass production, a method of azeotropic removal is preferably employed. As a method for removing water by azeotropy, for example, a method of removing by-produced water by using a Dean-Stark apparatus can be mentioned.
In this case, the organic solvent is preferably an organic solvent which is azeotropic with water, has a smaller specific gravity than water, and is immiscible with water. In the present invention, "not mixed with water" means an organic solvent in which the amount of dissolved water is less than 5.0 mass%. Examples of such organic solvents include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene, aliphatic hydrocarbons such as heptane, hexane, and cyclohexane, ethers such as diethyl ether and cyclopentyl methyl ether, and ketones such as 2-methyltetrahydrofuran, 4-methyltetrahydropyran, and methyl isobutyl ketone. Of these, toluene, o-xylene, m-xylene, p-xylene or a mixture thereof is preferable. The amount of the organic solvent used is preferably 1 to 50 mass%, more preferably 2 to 10 mass%, based on the aromatic amine compound.
The temperature during the polymerization reaction can be suitably set depending on the raw materials and the solvent used, and is usually 40 to 200 ℃. In addition, in the case of removing water by azeotropy using the Dean-Stark apparatus as described above, the reaction is carried out at a reflux temperature, and in this case, in order to sufficiently reflux the reaction, the external temperature is preferably set to be higher than the internal temperature (reflux temperature) by 1 ℃ or more, and preferably set to be higher than the internal temperature by 10 ℃ or more. The upper limit of the external temperature is not particularly limited, but is usually about +20 ℃ as the internal temperature. The reaction time is suitably selected depending on the reaction temperature, and is usually about 1 to 30 hours.
Examples
The present invention will be described in more detail below with reference to synthetic examples and examples, but the present invention is not limited to these examples. GPC measurement is performed under the following conditions.
The device comprises the following steps: SCL-10Avp series manufactured by Shimadzu corporation
Column: shodex KF-805+ KF-804+ KF-803
Eluent: THF (tetrahydrofuran)
Flow rate: 1.3 mL/min
Column temperature: 40 deg.C
A detector: UV (271nm)
And (3) correcting a curve: standard polystyrene
[ example 1]
The polymer PTPA was synthesized according to the reaction shown in the following synthetic scheme.
[ solution 7]
A200 mL beaker having a Dean-Stark apparatus attached thereto was charged with 10g of triphenylamine (manufactured by Zhenjiang Haitong chemical Industry Co.), 6.5g (0.87eq.) of 4-benzaldehyde (manufactured by Beijing Odyssey Chemicals Co.), 0.388g (0.05eq.) of p-toluenesulfonic acid (manufactured by Kanto chemical Co., Ltd.) and 60g of toluene, and the temperature was raised so as to be brought into a reflux state (internal temperature 110 to 115 ℃ C.). The reaction is carried out for 3 hours while maintaining the external temperature at a reflux temperature (internal temperature of 110 to 115 ℃) plus 20 ℃ so that the reaction system is always in a reflux state and removing by-produced water from the reaction system by azeotropic distillation. After 3 hours, it was confirmed by GPC that the Mw of the polymer reached around 35,000 to 45,000, and that all of the 4-phenylbenzaldehyde had disappeared and the polymerization had stopped. To the toluene solution of the obtained polymer, 0.25g (0.06eq.) of triethylamine (manufactured by tokyo chemical industry corporation) was added for quenching. The quenched polymer solution was put into a mixed solvent of 30g of acetone and 270g of water as a poor solvent to precipitate the polymer solution. And (3) filtering and separating the precipitate, repeatedly carrying out liquid-through cleaning on the filtrate by using acetone, and drying at 100 ℃ by using a dryer to obtain the target polymer PTPA.
Fig. 1 shows a photograph of the reaction vessel after the reaction (toluene solution of polymer). Gelation of the polymer, high viscosity of the reaction solution and generation of sticking matter on the inner wall of the reaction vessel were not observed.
Comparative example 1
A200 mL beaker to which a Dimroth condenser (Dimroth condenser) was connected was charged with 10g of triphenylamine (manufactured by Zhenjiang Haitong Chemical Industry Co.), 14.9g (2.0eq.) of 4-phenylbenzaldehyde (manufactured by Beijing Odyssey Chemicals Co.), 1.55g (0.2eq.) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) and 20g of 1, 4-dioxane, and the temperature was raised so that the inner temperature became 85 ℃. Changes in Mw of the polymer over time were confirmed by GPC, and as a result, the Mw increased to 4,350 at 3.5 hours, 14,200 at 5 hours, 48,900 at 6 hours, and gelling at 7 hours. It was confirmed by GPC that a large amount of unreacted 4-phenylbenzaldehyde remained in the reaction solution at the 6 th hour.
Fig. 2 shows a photograph of the reaction vessel after the reaction is completed. Gelling at the end of the reaction.
Comparative example 2
A200 mL beaker having a Dahurian condenser attached thereto was charged with 10g of triphenylamine (manufactured by Zhenjiang Haitong chemical industry Co.), 3.7g (0.5eq.) of 4-benzaldehyde (manufactured by Beijing Odyssey Chemicals Co.), 1.55g (0.2eq.) of p-toluenesulfonic acid (manufactured by Kanto chemical Co., Ltd.) and 10g of 1, 4-dioxane, and the temperature was raised so as to be brought into a reflux state (inner temperature 100 to 106 ℃ C.). The external temperature is maintained at a reflux temperature (internal temperature 100 to 106 ℃) plus 20 ℃ so that the reaction system is always in a reflux state. After 2 hours from the start of reflux, 1.9g (0.25eq.) of 4-phenylbenzaldehyde and 5g of 1, 4-dioxane were added in succession, and further, after 5 hours from the start of reflux, 1.1g (0.15eq.) of 4-phenylbenzaldehyde and 5g of 1, 4-dioxane were added in succession. Mw of the polymer was confirmed by GPC 22 hours after the start of reflux, and as a result, Mw was 30,000 and a large amount of unreacted 4-phenylbenzaldehyde remained. In addition, the reaction solution has a high concentration, and thus has a high viscosity.
Fig. 3 shows a photograph of the reflow. The reaction solution had a high viscosity and was observed to bulge.
Comparative example 3
A200 mL beaker having a Dahurian condenser attached thereto was charged with 10g of triphenylamine (manufactured by Zhenjiang Haitong Chemical industry Co.), 6.5g (0.87eq.) of 4-benzaldehyde (manufactured by Beijing Odyssey Chemical Co.), 0.388g (0.05eq.) of p-toluenesulfonic acid (manufactured by Kanto Chemical Co., Ltd.) and 60g of toluene, and the temperature was raised so as to bring the mixture to a reflux state (internal temperature 110 to 115 ℃). The reaction is carried out while maintaining the external temperature at a reflux temperature (internal temperature of 110 to 115 ℃) plus 20 ℃ so that the reaction system is always in a reflux state. The change in Mw of the polymer with time was confirmed by GPC, and as a result, Mw was 33,900 at the 4 th hour and Mw was 40,300 at the 9 th hour, suggesting that the polymerization proceeded more slowly than when Dean-Stark was used. In addition, when the by-produced water is returned from the deshello condenser to the system, bumping occurs violently on the reaction liquid surface, which is a very dangerous state.
Claims (10)
1. A process for producing a novolak polymer, which comprises polymerizing an aromatic amine compound and an aldehyde compound in the presence of a catalyst in an organic solvent while removing water as a by-product.
2. The method for producing a novolak-type polymer according to claim 1, wherein water is removed azeotropically.
3. The method for producing a novolak-type polymer according to claim 1 or 2, wherein the organic solvent is azeotropic with water, has a lower specific gravity than water, and is not mixed with water.
4. The method for producing the novolak-type polymer according to any one of claims 1 to 3, wherein the organic solvent is toluene, o-xylene, m-xylene, p-xylene, or a mixed solvent thereof.
5. The method for producing the novolak-type polymer according to any one of claims 1 to 4, wherein the catalyst is an acid catalyst.
6. The method for producing the novolak-type polymer according to claim 5, wherein the acid catalyst is sulfuric acid or sulfonic acid.
7. The method for producing the novolak-type polymer according to any one of claims 1 to 6, wherein the organic solvent is used in an amount of 1 to 50 by mass relative to the aromatic amine compound.
8. The method for producing a novolak-type polymer according to any one of claims 1 to 7, wherein the aromatic amine compound is a triarylamine compound.
9. The method for producing the novolak-type polymer according to any one of claims 1 to 8, wherein the aldehyde compound is an aromatic aldehyde compound.
10. The method for producing the novolak-type polymer according to any one of claims 1 to 9, wherein the novolak-type polymer is a hyperbranched polymer.
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| PCT/JP2018/033243 WO2019054299A1 (en) | 2017-09-15 | 2018-09-07 | Method for producing novolac polymer |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1365454A (en) * | 1971-10-07 | 1974-09-04 | Bayer Ag | Process for the preparation od aromatic polyamines |
| JPH08193110A (en) * | 1995-01-13 | 1996-07-30 | Nippon Kayaku Co Ltd | Novolak resin, epoxy resin, epoxy resin composition, and cured article obtained therefrom |
| CN102695557A (en) * | 2009-11-25 | 2012-09-26 | 日产化学工业株式会社 | Carbon nano-tube dispersant |
| CN107001550A (en) * | 2014-11-25 | 2017-08-01 | Dic株式会社 | Novolak phenolics, its manufacture method, photosensitive composite, erosion resistant and film |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3901930A1 (en) * | 1989-01-24 | 1990-07-26 | Hoechst Ag | METHOD FOR PRODUCING NOVOLACES AND THE USE THEREOF |
| JPH06122745A (en) * | 1992-10-13 | 1994-05-06 | Sumitomo Chem Co Ltd | Polyamine and imide compound |
| JP6434258B2 (en) * | 2014-09-05 | 2018-12-05 | 三井化学株式会社 | Resin composition, cured film, method for producing cured film, and alkylated aniline resin |
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- 2018-09-07 WO PCT/JP2018/033243 patent/WO2019054299A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1365454A (en) * | 1971-10-07 | 1974-09-04 | Bayer Ag | Process for the preparation od aromatic polyamines |
| JPH08193110A (en) * | 1995-01-13 | 1996-07-30 | Nippon Kayaku Co Ltd | Novolak resin, epoxy resin, epoxy resin composition, and cured article obtained therefrom |
| CN102695557A (en) * | 2009-11-25 | 2012-09-26 | 日产化学工业株式会社 | Carbon nano-tube dispersant |
| CN107001550A (en) * | 2014-11-25 | 2017-08-01 | Dic株式会社 | Novolak phenolics, its manufacture method, photosensitive composite, erosion resistant and film |
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| JP7131558B2 (en) | 2022-09-06 |
| WO2019054299A1 (en) | 2019-03-21 |
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