JP4909516B2 - Method for producing ester group-containing acid dianhydride derivative - Google Patents
Method for producing ester group-containing acid dianhydride derivative Download PDFInfo
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- JP4909516B2 JP4909516B2 JP2005019768A JP2005019768A JP4909516B2 JP 4909516 B2 JP4909516 B2 JP 4909516B2 JP 2005019768 A JP2005019768 A JP 2005019768A JP 2005019768 A JP2005019768 A JP 2005019768A JP 4909516 B2 JP4909516 B2 JP 4909516B2
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- acid dianhydride
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- 239000002253 acid Substances 0.000 title claims description 28
- 125000004185 ester group Chemical group 0.000 title claims description 17
- 125000006159 dianhydride group Chemical class 0.000 title claims 2
- 238000004519 manufacturing process Methods 0.000 title description 6
- -1 aromatic diol Chemical class 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 150000004714 phosphonium salts Chemical class 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical class CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 15
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 7
- 229920003055 poly(ester-imide) Polymers 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- AKOGNYJNGMLDOA-UHFFFAOYSA-N (4-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C=C1 AKOGNYJNGMLDOA-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920006015 heat resistant resin Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000005183 environmental health Effects 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 2
- KUZVIVNLNXNLAQ-UHFFFAOYSA-N (4-acetyloxy-3-methylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C(C)=C1 KUZVIVNLNXNLAQ-UHFFFAOYSA-N 0.000 description 1
- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 0 O=C(c(cc1C(O2)=O)ccc1C2=O)O*OC(c(cc1)cc(C(O2)=O)c1C2=O)=O Chemical compound O=C(c(cc1C(O2)=O)ccc1C2=O)O*OC(c(cc1)cc(C(O2)=O)c1C2=O)=O 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RQMBBMQDXFZFCC-UHFFFAOYSA-N [4-(4-acetyloxyphenyl)phenyl] acetate Chemical group C1=CC(OC(=O)C)=CC=C1C1=CC=C(OC(C)=O)C=C1 RQMBBMQDXFZFCC-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002510 isobutyric acid esters Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 150000003151 propanoic acid esters Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- MCOWGUNDBBHKAM-UHFFFAOYSA-N thiohypoiodous acid Chemical compound IS MCOWGUNDBBHKAM-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- VMJFYMAHEGJHFH-UHFFFAOYSA-M triphenylsulfanium;bromide Chemical compound [Br-].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VMJFYMAHEGJHFH-UHFFFAOYSA-M 0.000 description 1
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- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、ポリエステルイミド樹脂等の耐熱樹脂の原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として有用なエステル基含有酸二無水物誘導体の製造方法に関する。 The present invention relates to a method for producing an ester group-containing acid dianhydride derivative that is useful as a raw material for a heat-resistant resin such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier.
エステル基含有酸二無水物誘導体は、ポリエステルイミド樹脂等の耐熱樹脂の原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として有用であり、それを製造する方法として、例えば、（１）ベンゼン、トルエン等の有機溶媒中、無水トリメリット酸クロリドとジオール類との反応による方法（例えば、特許文献１参照。）、トリメリット酸無水物とジオール類の低級アルカン酸エステルとのエステル交換反応において、（２）触媒としてシリカ・アルミナ系化合物等の無機化合物の存在下に行う方法（例えば、特許文献２参照。）または（３）特定の溶媒の存在下に、２７０〜３２０℃の高温領域で加熱することにより行う方法（例えば、特許文献３、非特許文献１参照。）等が知られている。 An ester group-containing acid dianhydride derivative is useful as a raw material for heat-resistant resins such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier. For example, (1) benzene In a transesterification reaction between trimellitic anhydride and a lower alkanoic acid ester of diol in a method of reaction of trimellitic anhydride chloride with a diol in an organic solvent such as toluene (see, for example, Patent Document 1) (2) A method carried out in the presence of an inorganic compound such as a silica / alumina compound as a catalyst (for example, refer to Patent Document 2) or (3) in the presence of a specific solvent in a high temperature region of 270 to 320 ° C. A method (for example, refer to Patent Document 3 and Non-Patent Document 1) performed by heating is known.
前記背景技術（１）に開示される方法は、高価で且つ環境衛生上取り扱い難い無水トリメリット酸クロリドを使用しなければならない。（２）に開示される製造方法では、使用する無機触媒が除去し難く、得られるエステル基含有酸二無水物誘導体の不純物となりやすい。また（３）に開示される製造方法では、反応が工業的には困難な高温を必要とするといった問題がある。本発明は工業的に利用可能な反応温度で、短時間に効率よく反応させる製造方法を提供するものである。 The method disclosed in the background art (1) must use trimellitic anhydride chloride which is expensive and difficult to handle in terms of environmental hygiene. In the production method disclosed in (2), the inorganic catalyst to be used is difficult to remove and tends to be an impurity of the resulting ester group-containing acid dianhydride derivative. In addition, the production method disclosed in (3) has a problem that the reaction requires a high temperature, which is industrially difficult. The present invention provides a production method in which a reaction is efficiently performed in a short time at an industrially usable reaction temperature.
本発明者は、上記のような問題点を解決するために種々研究を行い、芳香族ジオールの低級アルカン酸エステルとトリメリット酸無水物とを、相間移動触媒の存在下、溶媒中でエステル交換反応を行うことにより、エステル基含有酸二無水物誘導体を効率よく製造し得ることを見出した。 The present inventor conducted various studies in order to solve the above-described problems, and transesterified the lower alkanoic acid ester of aromatic diol and trimellitic anhydride in a solvent in the presence of a phase transfer catalyst. It has been found that an ester group-containing acid dianhydride derivative can be efficiently produced by carrying out the reaction.
本発明のエステル基含有酸二無水物誘導体は、ポリエステルイミド樹脂等の耐熱樹脂の原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として利用される。本発明は、少量の相間移動触媒の存在下で、安価で、環境衛生上の問題も少ない原料から、工業的に利用可能な反応温度で短時間に、目的とするエステル基含有酸二無水物誘導体を、高収率で製造できる点から極めて有用である。 The ester group-containing acid dianhydride derivative of the present invention is used as a heat-resistant resin raw material such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier. The present invention provides a target ester group-containing acid dianhydride in a short time at a reaction temperature that can be industrially used from a raw material that is inexpensive and has few environmental health problems in the presence of a small amount of a phase transfer catalyst. Derivatives are extremely useful in that they can be produced in high yield.
すなわち、本発明は一般式（１）： That is, the present invention relates to the general formula (1):
（式中、Ａｒは、下記式（２）： (In the formula, Ar represents the following formula (2):
で表される群から選ばれる２価の芳香族基を表し、Ｒ1、Ｒ2は、同一または異なって、炭素数１〜３のアルキル基を表し、そしてＲ3は、同一または異なって、水素または炭素数１〜３のアルキル基を表す。）で示される芳香族ジオールの低級アルカン酸エステルと、式（３）： Represents a divalent aromatic group selected from the group represented by: R 1 and R 2 are the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and R 3 is the same or different; Represents hydrogen or an alkyl group having 1 to 3 carbon atoms. A lower alkanoic acid ester of an aromatic diol represented by formula (3):
で示されるトリメリット酸無水物とを、相間移動触媒の存在下、溶媒中で反応させ、式（４）： Is reacted with trimellitic anhydride represented by the formula (4) in a solvent in the presence of a phase transfer catalyst:
で示されるエステル基含有酸二無水物誘導体を製造する方法に関する。 The ester group containing acid dianhydride derivative | guide_body shown by these is related.
本発明の一般式（１）に係る低級アルカン酸エステルとしては、酢酸エステル、プロピオン酸エステル、酪酸またはイソ酪酸エステルが例示されるが、好ましくは酢酸エステルが挙げられる。 Examples of the lower alkanoic acid ester according to the general formula (1) of the present invention include acetic acid ester, propionic acid ester, butyric acid or isobutyric acid ester, preferably acetic acid ester.
本発明の一般式（１）に係る芳香族ジオールとしては、ヒドロキノン、レゾルシノール、ピロカテコール、４，４’−ビフェニルジオール、２，２’−ビフェニルジオール、３，４’−ビフェニルジオール、４，４’−ジヒドロキシジフェニルエーテル、２，２’−ジヒドロキシジフェニルエーテル、あるいはこれらの芳香環が、同一または異なって、メチル基、エチル基、ｎ−もしくはｉｓｏ−プロピル基で置換されたものが例示されるが、好ましくは、ヒドロキノン、レゾルシノール、メチルヒドロキノン、２，２’−ビフェニルジオール等が挙げられる。 Examples of the aromatic diol according to the general formula (1) of the present invention include hydroquinone, resorcinol, pyrocatechol, 4,4′-biphenyldiol, 2,2′-biphenyldiol, 3,4′-biphenyldiol, 4,4 Examples include '-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, or those in which the aromatic rings are the same or different and substituted with a methyl group, an ethyl group, an n- or iso-propyl group. Include hydroquinone, resorcinol, methylhydroquinone, 2,2'-biphenyldiol, and the like.
一般式（１）で示される芳香族ジオールの低級アルカン酸エステルは、例えば、低級アルカン酸無水物と芳香族ジオールとを加熱反応することで容易に得ることができる。このとき、従来公知のｐ−トルエンスルホン酸ナトリウム等のエステル化触媒を使用することもできる。 The lower alkanoic acid ester of the aromatic diol represented by the general formula (1) can be easily obtained by, for example, subjecting a lower alkanoic anhydride to an aromatic diol by heating. At this time, a conventionally known esterification catalyst such as sodium p-toluenesulfonate can also be used.
一般式（１）で示される芳香族ジオールの低級アルカン酸エステルと、トリメリット酸無水物とのエステル交換反応は、相間移動触媒の存在下、溶媒中で行われ、一般式（４）で示されるエステル基含有酸二無水物誘導体を得る。ここでは、トリメリット酸無水物２モルに対し、芳香族ジオールの低級アルカン酸エステルを０.９５〜１．５０モル反応させるのが好ましい。 The transesterification reaction between the lower alkanoic acid ester of the aromatic diol represented by the general formula (1) and trimellitic anhydride is performed in a solvent in the presence of a phase transfer catalyst, and is represented by the general formula (4). An ester group-containing acid dianhydride derivative is obtained. Here, it is preferable to react 0.95-1.50 mol of lower alkanoic acid ester of aromatic diol with respect to 2 mol of trimellitic anhydride.
本発明に係る相間移動触媒としては、本発明の方法において設定される反応温度に耐えうる触媒であればよく、公知のもの、例えば、アンモニウム塩、ホスホニウム塩、スルホニウム塩、クラウンエーテル等が利用できるが、好ましくは、ホスホニウム塩、スルホニウム塩等が利用できる。ホスホニウム塩としては、例えば、臭化テトラフェニルホスホニウム、塩化テトラフェニルホスホニウム、塩化テトラブチルホスホニウム等、スルホニウム塩としては、ヨウ化スルホニウム、臭化トリフェニルスルホニウム等が挙げられる。触媒量は、一般式（１）で示される芳香族ジオールの低級アルカン酸エステルに対し、０.１〜１０重量％、好ましくは０.３〜５重量％である。 The phase transfer catalyst according to the present invention may be any catalyst that can withstand the reaction temperature set in the method of the present invention, and known ones such as ammonium salts, phosphonium salts, sulfonium salts, crown ethers and the like can be used. However, preferably, a phosphonium salt, a sulfonium salt, or the like can be used. The phosphonium salts, for example, bromide tetraphenylphosphonium, tetraphenyl phosphonium chloride, etc. tetrabutylphosphonium chloride, as the sulfonium salt, sulfonium iodide, triphenylsulfonium bromide, and the like. The amount of the catalyst is 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on the lower alkanoic acid ester of the aromatic diol represented by the general formula (1).
反応には、溶媒を用いる。使用する溶媒は、反応温度（１７０〜２５０℃）付近または反応温度を超える沸点を持ち、設定される反応温度に応じ適宜選択されるが、反応に関与しないもの、すなわち芳香族ジオールの低級アルカン酸エステル、トリメリット酸無水物および相間移動触媒等に対し不活性でなければならない。例えば、１，２−ジクロロベンゼン、１，２，４−トリクロロベンゼンのようなポリ塩化ベンゼン、２，３−ジクロロトルエンのようなポリ塩化トルエンが使用可能である。脱水された非プロトン性の極性溶媒、例えばスルホラン、Ｎ−メチルピロリドンも使用可能である。使用量は、一般式（１）で示される芳香族ジオールの低級アルカン酸エステルに対し、５０〜８００重量％、好ましくは１００〜４００重量％である。 A solvent is used for the reaction. The solvent to be used has a boiling point in the vicinity of the reaction temperature (170 to 250 ° C.) or higher than the reaction temperature, and is appropriately selected according to the set reaction temperature, but does not participate in the reaction, that is, a lower alkanoic acid of an aromatic diol. It must be inert to esters, trimellitic anhydride and phase transfer catalysts. For example, polychlorinated benzenes such as 1,2-dichlorobenzene and 1,2,4-trichlorobenzene, and polychlorinated toluenes such as 2,3-dichlorotoluene can be used. Dehydrated aprotic polar solvents such as sulfolane and N-methylpyrrolidone can also be used. The amount used is 50 to 800% by weight, preferably 100 to 400% by weight, based on the lower alkanoic acid ester of the aromatic diol represented by the general formula (1).
エステル交換反応温度は、１７０〜２５０℃で行われるが、２００〜２４０℃が好ましい。 The transesterification reaction temperature is 170 to 250 ° C, preferably 200 to 240 ° C.
以下に、本発明を具体的に実施例を示すが、本発明は実施例の内容に制限されるものではない。なお、実施例中の高速液体クロマトグラフィーの測定条件は、以下の通りである。
機種：島津製作所製高速液体クロマトグラフィー ＳＰＤ−１０Ａ
カラム：ＯＤＳ−８０Ｔ （３φ×１５０ｍｍ） ４０℃
溶離液：アセトニトリル：水：リン酸＝４００：６００：０．５（容量比）
検出波長：２５４ｎｍ
なお、本明細書において反応率とは、上記高速液体クロマトグラフィーの測定結果から得られる、反応生成物である一般式（４）で示されるエステル基含有酸二無水物のピーク面積に対する全ピーク面積（前記反応生成物、未反応原料および副生成物等のピークを含むが、但し溶媒のピークは除いたもの）の割合を百分率で示したものである。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the contents of the examples. In addition, the measurement conditions of the high performance liquid chromatography in the examples are as follows.
Model: Shimadzu High Performance Liquid Chromatography SPD-10A
Column: ODS-80T (3φ × 150 mm) 40 ° C.
Eluent: acetonitrile: water: phosphoric acid = 400: 600: 0.5 (volume ratio)
Detection wavelength: 254 nm
In this specification, the reaction rate means the total peak area with respect to the peak area of the ester group-containing acid dianhydride represented by the general formula (4), which is a reaction product, obtained from the measurement result of the high performance liquid chromatography. The percentages (including the peaks of the reaction products, unreacted raw materials, by-products, etc., but excluding the solvent peaks) are shown as percentages.
（例１）
撹拌機、温度計、蒸留用冷却管、窒素ガス導入管を付けた１Lの四つ口フラスコに、１，４−ジアセトキシベンゼン１０６.８ｇ（０.５５モル）、トリメリット酸無水物１９２.１ｇ（１.００モル）、１，２，４−トリクロロベンゼン４００ｇ及び臭化テトラフェニルホスホニウム１.１ｇを仕込み、窒素雰囲気下２１０℃で４時間反応させた。この時点で反応液を採取し、高速液体クロマトグラフィー測定した結果、一般式（４）で示されるエステル基含有酸二無水物（式中、Ａｒは、１，４−フェニレンである）の反応率は、８６.３％であった。
(Example 1)
In a 1 L four-necked flask equipped with a stirrer, thermometer, distillation condenser, and nitrogen gas inlet pipe, 106.8 g (0.55 mol) of 1,4-diacetoxybenzene, trimellitic anhydride 192. 1 g (1.00 mol), 400 g of 1,2,4-trichlorobenzene and 1.1 g of tetraphenylphosphonium bromide were charged and reacted at 210 ° C. for 4 hours in a nitrogen atmosphere. The reaction solution was collected at this time and measured by high performance liquid chromatography. As a result, the reaction rate of the ester group-containing acid dianhydride (wherein Ar is 1,4-phenylene) represented by the general formula (4) Was 86.3%.
（例２）
１，４−ジアセトキシベンゼンの代わりに２，５−ジアセトキシトルエン１１４.５ｇ（０.５５モル）を使用し、例１と同様の反応条件で操作を行った。反応液を採取し、高速液体クロマトグラフィー測定した結果、一般式（４）で示されるエステル基含有酸二無水物（式中、Ａｒは、２−メチル−１，４−フェニレンである）の反応率は、８５.８％であった。
(Example 2)
The operation was carried out under the same reaction conditions as in Example 1 except that 114.5 g (0.55 mol) of 2,5-diacetoxytoluene was used instead of 1,4-diacetoxybenzene. As a result of collecting the reaction liquid and measuring by high performance liquid chromatography, the reaction of the ester group-containing acid dianhydride represented by the general formula (4) (wherein Ar is 2-methyl-1,4-phenylene) The rate was 85.8%.
（例３）
１，４−ジアセトキシベンゼンの代わりに４，４’−ジアセトキシビフェニル１４８.７ｇ（０.５５モル）、溶媒として１，２，４−トリクロロベンゼン２００ｇ及びＮ−メチルピロリドン２００ｇを使用し、例１と同様の反応条件で操作を行った。反応液を採取し、高速液体クロマトグラフィー測定した結果、一般式（４）で示されるエステル基含有酸二無水物（式中、Ａｒは、ビフェニル−４，４’−ジイルである）の反応率は、８０.１％であった。
(Example 3)
Example using 148.7 g (0.55 mol) of 4,4′-diacetoxybiphenyl instead of 1,4-diacetoxybenzene, 200 g of 1,2,4-trichlorobenzene and 200 g of N-methylpyrrolidone as solvents. The operation was carried out under the same reaction conditions as in 1. As a result of collecting the reaction liquid and performing high performance liquid chromatography measurement, the reaction rate of the ester group-containing acid dianhydride represented by the general formula (4) (wherein Ar is biphenyl-4,4′-diyl) Was 80.1%.
（比較例）
臭化テトラフェニルホスホニウムを使用しない他は、例１と同様の反応条件で操作を行った。反応液を採取し、高速液体クロマトグラフィー測定した結果、一般式（４）で示されるエステル基含有酸二無水物（式中、Ａｒは、１，４−フェニレンである）の反応率は、４５.３％であった。
(Comparative example)
The operation was carried out under the same reaction conditions as in Example 1 except that tetraphenylphosphonium bromide was not used. The reaction solution was collected and measured by high performance liquid chromatography. As a result, the reaction rate of the ester group-containing acid dianhydride represented by the general formula (4) (wherein Ar is 1,4-phenylene) was 45. It was 3%.
本発明の製法で得られるエステル基含有酸二無水物誘導体は、ポリエステルイミド樹脂原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として利用できるが、特に低吸水率ポリエステルイミド原料として有用である。ポリイミドの欠点である吸水率を改善するポリエステルイミドは、高周波対応多層フレキシブルプリント基板等の電子分野向け絶縁材料として極めて有用である。本発明は、その原料であるエステル基含有酸二無水物誘導体を、安価で、環境衛生上の問題の少ない原料から、工業的に利用可能な反応温度で、短時間に効率よく反応させる製造方法を提供するものである。 The ester group-containing acid dianhydride derivative obtained by the production method of the present invention can be used as a polyesterimide resin raw material, a curing agent such as an epoxy resin, or a resin modifier, but is particularly useful as a low water absorption polyesterimide raw material. . Polyesterimide, which improves the water absorption rate, which is a drawback of polyimide, is extremely useful as an insulating material for the electronic field such as a high-frequency compatible multilayer flexible printed circuit board. The present invention provides a method for efficiently reacting an ester group-containing acid dianhydride derivative, which is a raw material, from an inexpensive raw material with few environmental health problems at an industrially usable reaction temperature in a short time. Is to provide.
Claims (2)
（式中、Ａｒは、下記式（２）：
で表される群から選ばれる２価の芳香族基を表し、Ｒ1、Ｒ2は、同一または異なって、炭素数１〜３のアルキル基を表し、そしてＲ3は、同一または異なって、水素または炭素数１〜３のアルキル基を表す。）で示される芳香族ジオールの低級アルカン酸エステルと、式（３）：
で示されるトリメリット酸無水物とを、ホスホニウム塩またはスルホニウム塩から選択される相間移動触媒の存在下、溶媒中、１７０〜２１０℃で反応させ、一般式（４）：
で示されるエステル基含有酸二無水物誘導体を製造する方法。 General formula (1):
(In the formula, Ar represents the following formula (2):
Represents a divalent aromatic group selected from the group represented by: R 1 and R 2 are the same or different and each represents an alkyl group having 1 to 3 carbon atoms, and R 3 is the same or different; Represents hydrogen or an alkyl group having 1 to 3 carbon atoms. A lower alkanoic acid ester of an aromatic diol represented by formula (3):
In the presence of a phase transfer catalyst selected from a phosphonium salt or a sulfonium salt in a solvent at 170 to 210 ° C. to give a general formula (4):
The ester group containing acid dianhydride derivative shown by these is manufactured.
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