JP7385509B2 - Method for producing aromatic polyether - Google Patents
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- JP7385509B2 JP7385509B2 JP2020048064A JP2020048064A JP7385509B2 JP 7385509 B2 JP7385509 B2 JP 7385509B2 JP 2020048064 A JP2020048064 A JP 2020048064A JP 2020048064 A JP2020048064 A JP 2020048064A JP 7385509 B2 JP7385509 B2 JP 7385509B2
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- 125000003118 aryl group Chemical group 0.000 title claims description 37
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 229920000570 polyether Polymers 0.000 title claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 41
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- 229920001955 polyphenylene ether Polymers 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 4
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 229960002447 thiram Drugs 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000005259 measurement Methods 0.000 description 12
- 239000002184 metal Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- -1 azo compound Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000005181 nitrobenzenes Chemical class 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- 238000000434 field desorption mass spectrometry Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- HGBNJJLRWOEGCM-UHFFFAOYSA-N 2-sulfanyl-3h-1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN(S)NC2=C1 HGBNJJLRWOEGCM-UHFFFAOYSA-N 0.000 description 2
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JIVYEUNBDFYQRD-UHFFFAOYSA-N 1,3-diiodo-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(I)=CC(I)=C1 JIVYEUNBDFYQRD-UHFFFAOYSA-N 0.000 description 1
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 1
- VALABLHQPAMOBO-UHFFFAOYSA-N 2,4-diiodo-1-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1I VALABLHQPAMOBO-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UVGTXNPVQOQFQW-UHFFFAOYSA-N Disophenol Chemical compound OC1=C(I)C=C([N+]([O-])=O)C=C1I UVGTXNPVQOQFQW-UHFFFAOYSA-N 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
本発明は、芳香族ポリエーテルの新規製造方法に関する。 The present invention relates to a novel method for producing aromatic polyethers.
芳香族ポリエーテルであるポリフェニレンエーテルは誘電率や誘電正接等の誘電特性に優れるため、電子材料用途における使用が検討されている。 Polyphenylene ether, which is an aromatic polyether, has excellent dielectric properties such as dielectric constant and dielectric loss tangent, so its use in electronic material applications is being considered.
フェノール性化合物を酸化重合させることにより、ポリフェニレンエーテルを調製できることが知られている（特許文献１）。 It is known that polyphenylene ether can be prepared by oxidative polymerization of a phenolic compound (Patent Document 1).
特許文献１に記載されるような酸化重合は金属触媒を用いる必要があり、得られるポリフェニレンエーテルにも不純物として金属が含まれるという課題がある。かかる不純物は洗浄工程を必要とし、製造プロセスの煩雑さに繋がる。 Oxidative polymerization as described in Patent Document 1 requires the use of a metal catalyst, and there is a problem that the obtained polyphenylene ether also contains metal as an impurity. Such impurities require a cleaning step and complicate the manufacturing process.
本発明者等は鋭意検討を重ねた結果、キノイド構造を有する化合物と、重合助剤とを反応させる工程を含む製造方法が、上記課題を解決することを見出した。すなわち、本発明は以下の芳香族ポリエーテルの新規製造方法に関する。 As a result of intensive studies, the present inventors have found that a manufacturing method including a step of reacting a compound having a quinoid structure with a polymerization aid solves the above problems. That is, the present invention relates to the following novel method for producing aromatic polyether.
［１］キノイド構造を有する化合物と、重合助剤とを反応させる工程を含む、芳香族ポリエーテルの製造方法。
［２］前記キノイド構造を有する化合物が、一般式（I）で表される骨格を有する化合物である、上記［１］に記載の芳香族ポリエーテルの製造方法。
［式（I）中、ＡはＣ－Ｃ二重結合、酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ1で示されるＲ1基を有する。Ｑは酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ2で示されるＲ2基を有する。Ｒ1及びＲ2はそれぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数３～１５のシクロアルキル基、炭素数５～１５のシクロアルキレン基、アリール基又はヘテロアリール基を示す。ｐは１～５の整数を示す。］
［３］前記重合助剤が、（１）窒素－炭素－硫黄結合を有する化合物、（２）ニトロベンゼン誘導体、及び（３）アゾ化合物又は過酸化物からなる群から選択される少なくとも１種である、上記［１］又は［２］に記載の芳香族ポリエーテルの製造方法。
［４］前記キノイド構造を有する化合物と、前記重合助剤との合計量１００質量％中、前記重合助剤量が０．０１～１０質量％となるよう添加する、上記［１］～［３］のいずれか１つに記載の芳香族ポリエーテルの製造方法。
［５］前記芳香族ポリエーテルがポリフェニレンエーテルである、上記［１］～［４］のいずれか１つに記載の芳香族ポリエーテルの製造方法。
[1] A method for producing an aromatic polyether, including a step of reacting a compound having a quinoid structure with a polymerization aid.
[2] The method for producing an aromatic polyether according to [1] above, wherein the compound having a quinoid structure is a compound having a skeleton represented by general formula (I).
[In formula (I), A represents a C--C double bond, an oxygen atom, a sulfur atom, or a nitrogen atom, and the nitrogen atom has an R 1 group represented by NR 1 . Q represents an oxygen atom, a sulfur atom or a nitrogen atom, and the nitrogen atom has an R 2 group represented by NR 2 . R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an aryl group, or a heteroaryl group. . p represents an integer from 1 to 5. ]
[3] The polymerization aid is at least one selected from the group consisting of (1) a compound having a nitrogen-carbon-sulfur bond, (2) a nitrobenzene derivative, and (3) an azo compound or a peroxide. , the method for producing an aromatic polyether according to [1] or [2] above.
[4] The above [1] to [3], which is added so that the amount of the polymerization aid is 0.01 to 10% by mass out of the total amount of 100% by mass of the compound having a quinoid structure and the polymerization aid. ] The method for producing an aromatic polyether according to any one of the above.
[5] The method for producing an aromatic polyether according to any one of [1] to [4] above, wherein the aromatic polyether is polyphenylene ether.
本発明によれば、芳香族ポリエーテルの新規製造方法を提供することができる。本発明の製法は金属触媒を必要としないため、実質的にメタルフリーである芳香族ポリエーテルを製造することができる。 According to the present invention, a novel method for producing aromatic polyether can be provided. Since the production method of the present invention does not require a metal catalyst, it is possible to produce a substantially metal-free aromatic polyether.
本発明の製造方法は、キノイド構造を有する化合物と、重合助剤とを反応させる工程を含む。
以下、本発明の製造方法について説明する。本明細書において、好ましいとされている規定は任意に採用することができ、好ましいもの同士の組み合わせはより好ましいといえる。本明細書において、「ＸＸ～ＹＹ」の記載は、「ＸＸ以上ＹＹ以下」を意味する。
The production method of the present invention includes a step of reacting a compound having a quinoid structure with a polymerization aid.
The manufacturing method of the present invention will be explained below. In this specification, the preferred provisions can be arbitrarily adopted, and combinations of preferred provisions can be said to be more preferred. In this specification, the description "XX to YY" means "XX or more and YY or less".
＜キノイド構造を有する化合物＞
本発明の製造方法に用いられるキノイド構造を有する化合物（以下、「キノイド化合物」とも称する。）は特に限定されない。キノイド化合物としては、以下の一般式（I）で表される骨格を有する化合物を用いることができる。
［式（I）中、ＡはＣ－Ｃ二重結合、酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ1で示されるＲ1基を有する。Ｑは酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ2で示されるＲ2基を有する。Ｒ1及びＲ2はそれぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数３～１５のシクロアルキル基、炭素数５～１５のシクロアルキレン基、アリール基又はヘテロアリール基を示す。ｐは１～５の整数を示す。］
<Compound with quinoid structure>
The compound having a quinoid structure (hereinafter also referred to as "quinoid compound") used in the production method of the present invention is not particularly limited. As the quinoid compound, a compound having a skeleton represented by the following general formula (I) can be used.
[In formula (I), A represents a C--C double bond, an oxygen atom, a sulfur atom, or a nitrogen atom, and the nitrogen atom has an R 1 group represented by NR 1 . Q represents an oxygen atom, a sulfur atom or a nitrogen atom, and the nitrogen atom has an R 2 group represented by NR 2 . R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an aryl group, or a heteroaryl group. . p represents an integer from 1 to 5. ]
本明細書において、「一般式（I）で表される骨格を有する化合物」とは、該化合物の構造中に上記構造を少なくとも含む化合物を意味する。当該化合物の構造が、一般式（I）で表される構造のみを含んでいても、一般式（I）で表される構造をその一部として含んでいてもよい。 As used herein, "a compound having a skeleton represented by general formula (I)" means a compound that includes at least the above structure in its structure. The structure of the compound may include only the structure represented by general formula (I), or may include the structure represented by general formula (I) as a part thereof.
上記した通り、式（I）中のＱは、酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ2で示されるＲ2基を有する。本発明の一実施形態において、Ｑは酸素原子または硫黄原子である。Ｑが酸素原子である場合には、芳香族ポリエーテルを得ることができる。Ｑが硫黄原子である場合には、チオエーテル結合を有する芳香族系ポリマー又はポリフェニレンスルフィドを得ることができる。 As described above, Q in formula (I) represents an oxygen atom, a sulfur atom, or a nitrogen atom, and the nitrogen atom has an R 2 group represented by NR 2 . In one embodiment of the invention, Q is an oxygen atom or a sulfur atom. When Q is an oxygen atom, an aromatic polyether can be obtained. When Q is a sulfur atom, an aromatic polymer or polyphenylene sulfide having a thioether bond can be obtained.
上記一般式（I）で表される骨格を有する化合物をさらに詳述する。ＡがＣ－Ｃ二重結合を示す場合には、６員環構造骨格を有する化合物となり、具体的にはベンゾキノン、１，４－ナフトキノン及びアントラキノン等及びこれらの少なくとも１つの骨格を有する化合物を挙げることができる。Ａがヘテロ原子を示す場合には、５員環構造骨格を有する化合物となり、例えば、下記構造式を有する化合物及びこれらのキノイド骨格を有する化合物等を挙げることができる。
［式中、Ｒ111は水素原子、又は置換または無置換の炭素数１～２０のアルキル基、炭素数３～１５のシクロアルキル基、炭素数５～１５のシクロアルキレン基、炭素数６～１２のアリール基を示す。］
The compound having the skeleton represented by the above general formula (I) will be explained in further detail. When A represents a C-C double bond, the compound has a 6-membered ring structure skeleton, and specific examples include benzoquinone, 1,4-naphthoquinone, anthraquinone, etc., and compounds having at least one of these skeletons. be able to. When A represents a heteroatom, the compound has a 5-membered ring structure skeleton, and examples thereof include compounds having the following structural formula and compounds having a quinoid skeleton thereof.
[In the formula, R 111 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or a cycloalkylene group having 6 to 12 carbon atoms. represents an aryl group. ]
本発明の製造方法によれば、主鎖にエーテル結合を有する芳香族ポリエーテルを製造することができる。 According to the production method of the present invention, an aromatic polyether having an ether bond in the main chain can be produced.
＜重合助剤＞
本発明の製造方法において用いる重合助剤としては、（１）窒素－炭素－硫黄結合を有する化合物、（２）ニトロベンゼン誘導体、及び（３）アゾ化合物又は過酸化物からなる群から選択される少なくとも１種を挙げることができる。
<Polymerization aid>
The polymerization aid used in the production method of the present invention is at least selected from the group consisting of (1) a compound having a nitrogen-carbon-sulfur bond, (2) a nitrobenzene derivative, and (3) an azo compound or a peroxide. One type can be mentioned.
（１）窒素－炭素－硫黄結合を有する化合物
この化合物は、窒素－炭素－硫黄結合をこの順で有していれば特に限定されない。例えば、２－メルカプトベンゾチアジアゾール、２，２’－ジベンゾチアゾリルジスルフィド、Ｎ－シクロヘキシル－２－ベンゾチアジアゾリルスルフェンアミド、２－（モルホリノチオ）ベンゾチアゾール、Ｎ，Ｎ’－ジシクロヘキシル－２－ベンゾチアゾールスルフェンアミド、テトラメチルチウラムモノスルフィド及びテトラメチルチウラムジスルフィドからなる群から選択される少なくとも１種を挙げることができる。本発明の一実施形態においては、化合物（１）は、２－メルカプトベンゾチアジアゾール、２，２’－ジベンゾチアゾリルジスルフィド、Ｎ－シクロヘキシル－２－ベンゾチアジアゾリルスルフェンアミド、２－（モルホリノチオ）ベンゾチアゾール、Ｎ，Ｎ’－ジシクロヘキシル－２－ベンゾチアゾールスルフェンアミド、テトラメチルチウラムモノスルフィド及びテトラメチルチウラムジスルフィドからなる群から選択される少なくとも１種である。これらの化合物は１種を単独で用いても、２種以上を組み合わせて用いてもよい。
(1) Compound having nitrogen-carbon-sulfur bonds This compound is not particularly limited as long as it has nitrogen-carbon-sulfur bonds in this order. For example, 2-mercaptobenzothiadiazole, 2,2'-dibenzothiazolyl disulfide, N-cyclohexyl-2-benzothiadiazolyl sulfenamide, 2-(morpholinothio)benzothiazole, N,N'-dicyclohexyl-2 - At least one selected from the group consisting of benzothiazole sulfenamide, tetramethylthiuram monosulfide, and tetramethylthiuram disulfide. In one embodiment of the present invention, compound (1) is 2-mercaptobenzothiadiazole, 2,2'-dibenzothiazolyl disulfide, N-cyclohexyl-2-benzothiadiazolyl sulfenamide, 2-(morpholino thio)benzothiazole, N,N'-dicyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram monosulfide, and tetramethylthiuram disulfide. These compounds may be used alone or in combination of two or more.
（２）ニトロベンゼン誘導体
ニトロベンゼン誘導体としては、例えば、１，３－ジヨード－４－ニトロベンゼン、１－ヨード－４－ニトロベンゼン、２，６－ジヨード－４－ニトロフェノール、及び２，６－ジヨード－４－ニトロベンゼンからなる群から選択される少なくとも１種を挙げることができる。これらの化合物は１種を単独で用いても、２種以上を組み合わせて用いてもよい。
(2) Nitrobenzene derivatives Examples of nitrobenzene derivatives include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, and 2,6-diiodo-4-nitrobenzene. At least one selected from the group consisting of nitrobenzene can be mentioned. These compounds may be used alone or in combination of two or more.
（３）アゾ化合物又は過酸化物
アゾ化合物としては、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）からなる群から選択される少なくとも１種を挙げることができる。過酸化物としては有機過酸化物、例えば過酸化ベンゾイルを挙げることができる。これらの化合物は１種を単独で用いても、２種以上を組み合わせて用いてもよい。
(3) Azo compound or peroxide Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), At least one selected from the group consisting of 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2-methylbutyronitrile) can be mentioned. Peroxides include organic peroxides, such as benzoyl peroxide. These compounds may be used alone or in combination of two or more.
（１）窒素－炭素－硫黄結合を有する化合物、（２）ニトロベンゼン誘導体、及び（３）アゾ化合物又は過酸化物からなる群から選択される少なくとも１種の重合助剤は、（１）～（３）のいずれかから選択される１種の化合物であってもよいし、（１）及び（２）、（１）及び（３）、（２）及び（３）、（１）と（２）と（３）とからそれぞれ選択される２種以上の化合物の組み合わせであってもよい。金属錯体を用いずとも反応が進行し、目的とする芳香族ポリエーテルを得ることができるという利点を有する。金属錯体を用いないため、得られる芳香族ポリエーテルを高い純度で得られることに加えて、残留する金属不純物の洗浄除去工程、金属不純物廃棄工程、洗浄液の廃液処理工程等が不要となるため、効率的に目的のポリマーを製造することができる。 At least one polymerization aid selected from the group consisting of (1) a compound having a nitrogen-carbon-sulfur bond, (2) a nitrobenzene derivative, and (3) an azo compound or a peroxide, 3), or (1) and (2), (1) and (3), (2) and (3), (1) and (2). It may be a combination of two or more compounds selected from ) and (3). It has the advantage that the reaction proceeds without using a metal complex and the desired aromatic polyether can be obtained. Since no metal complexes are used, the resulting aromatic polyether can be obtained with high purity, and there is no need for a process to wash away residual metal impurities, a process to dispose of metal impurities, a waste liquid treatment process for cleaning liquid, etc. The desired polymer can be efficiently produced.
本発明の製造方法においては、上記重合助剤は、上記キノイド構造を有する化合物と、上記重合助剤との合計量１００質量％中、例えば０．０１～１０質量％、具体的には０．０５～２．５質量％、より具体的には０．１～２質量％となるように添加することができる。上記重合助剤が上記範囲にあれば、芳香族ポリエーテルを効率よく製造することができる。 In the production method of the present invention, the polymerization aid is, for example, 0.01 to 10% by mass, specifically 0.01 to 10% by mass, based on 100% by mass of the compound having a quinoid structure and the polymerization aid. It can be added in an amount of 0.05 to 2.5% by mass, more specifically 0.1 to 2% by mass. When the polymerization aid is within the above range, aromatic polyether can be efficiently produced.
＜反応条件＞
本発明の製造方法における反応温度は、目的生成物（芳香族ポリエーテル）が溶解する温度以上で行うことができる。あるいは、上記キノイド構造を有する化合物の融点以上で行うことができる。反応温度は、二段階以上に分けてもよい。本発明の一実施形態においては、例えば、一段階目として１００～１５０℃未満の反応温度を、二段階目として１５０～２００℃未満の反応温度を、三段階目として、２００～２５０℃の反応温度を選択することができる。一段階目から二段階目の温度領域で上記キノイド構造を有する化合物を溶解させて行うことができる。
<Reaction conditions>
The reaction temperature in the production method of the present invention can be carried out at a temperature higher than the temperature at which the target product (aromatic polyether) dissolves. Alternatively, it can be carried out at a temperature equal to or higher than the melting point of the compound having the quinoid structure. The reaction temperature may be divided into two or more stages. In one embodiment of the present invention, for example, the first step is a reaction temperature of 100 to less than 150°C, the second step is a reaction temperature of 150 to less than 200°C, and the third step is a reaction temperature of 200 to 250°C. Temperature can be selected. This can be carried out by dissolving the compound having the quinoid structure in the temperature range from the first stage to the second stage.
本発明の製造方法における反応雰囲気は特に限定されないが、より効率的に反応を進めるために不活性ガス雰囲気下、例えば窒素雰囲気下で行うことができる。
反応圧力も特に限定されないが、より効率的に行うために常圧もしくは減圧下で行うことができる。
The reaction atmosphere in the production method of the present invention is not particularly limited, but in order to proceed with the reaction more efficiently, the reaction can be carried out under an inert gas atmosphere, for example, a nitrogen atmosphere.
Although the reaction pressure is not particularly limited, the reaction can be carried out under normal pressure or reduced pressure in order to carry out the reaction more efficiently.
本発明の製造方法における反応時間は特に限定されない。原料の反応性と、転化率とを考慮して具体的に設定することができる。例えば、１～３０時間程度で反応を行うことができる。 The reaction time in the production method of the present invention is not particularly limited. It can be specifically set in consideration of the reactivity of the raw materials and the conversion rate. For example, the reaction can be carried out in about 1 to 30 hours.
本発明の製造方法は、溶媒を実質的に含まない条件下で行うことができる。溶媒を「実質的に含まない」条件とは、キノイド構造を有する化合物と、重合助剤との合計１００質量部に対して、溶媒が好ましくは１０００質量部以下、より好ましくは１００質量部以下、さらにより好ましくは１０質量部以下、さらにより好ましくは５質量部以下、特に好ましくは１質量部以下であり、好ましくは０質量部以上、より好ましくは０．０１質量部以上、さらに好ましくは０．１質量部以上である。本発明の製造方法は溶媒を用いずとも反応が進行するため、溶媒除去工程／回収工程／乾燥工程／廃液処理工程等を省略することが可能であり、効率的に目的とする芳香族ポリエーテルを製造することができる。 The production method of the present invention can be carried out under conditions substantially free of solvent. The condition that the solvent is "substantially free" means that the solvent is preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, based on a total of 100 parts by mass of the compound having a quinoid structure and the polymerization aid. Still more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, particularly preferably 1 part by mass or less, preferably 0 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.01 parts by mass or less. It is 1 part by mass or more. In the production method of the present invention, the reaction proceeds without using a solvent, so it is possible to omit the solvent removal step/recovery step/drying step/waste treatment step, etc., and it is possible to efficiently produce the target aromatic polyether. can be manufactured.
＜芳香族ポリエーテル＞
本発明の製造方法により、芳香族ポリエーテルを製造することができる。
キノイド構造を有する化合物としてベンゾキノンを用いた場合は、主鎖にエーテル基を有するポリフェニレンエーテルを得ることができる。ポリフェニレンエーテルとしては、例えば重量平均分子量（Ｍｗ）が、１，０００～１００，０００程度のものを得ることが可能である。
<Aromatic polyether>
Aromatic polyether can be produced by the production method of the present invention.
When benzoquinone is used as a compound having a quinoid structure, a polyphenylene ether having an ether group in the main chain can be obtained. As the polyphenylene ether, it is possible to obtain, for example, one having a weight average molecular weight (Mw) of about 1,000 to 100,000.
本発明の製造方法は、上述した通り金属錯体を必要としない。従って、得られる芳香族ポリエーテルには、金属系不純物が実質的に残留しない（含まれない）ため、洗浄工程や続く乾燥工程、不純物廃棄処理工程、廃液処理工程等の負担を低減することができる。本明細書において「金属不純物が実質的に残留しない（含まれない）」とは、得られる芳香族ポリエーテル中の金属量が具体的には１００質量ｐｐｍ以下、より具体的には５０質量ｐｐｍ以下であることを意味し、０質量ｐｐｍであることも許容する。 The manufacturing method of the present invention does not require a metal complex as described above. Therefore, the obtained aromatic polyether does not substantially contain (contains) metallic impurities, so it is possible to reduce the burden of washing steps, subsequent drying steps, impurity disposal steps, waste liquid processing steps, etc. can. As used herein, "substantially no metal impurities remain (not included)" means that the amount of metal in the aromatic polyether obtained is specifically 100 mass ppm or less, more specifically 50 mass ppm. 0 mass ppm is also acceptable.
さらに、上述した通り、実質的に溶媒の不存在下で行うことができるため、溶媒除去工程・回収工程・乾燥工程・廃液処理工程等を省略することも可能であり、反応器のサイズも小さくすることができる。
本発明の製造方法によれば、無置換のポリフェニレンエーテルを得ることができる。
Furthermore, as mentioned above, since it can be carried out in the substantial absence of a solvent, it is also possible to omit the solvent removal process, recovery process, drying process, waste liquid treatment process, etc., and the size of the reactor is also small. can do.
According to the production method of the present invention, unsubstituted polyphenylene ether can be obtained.
以下の実施例により、本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples.
実施例１
撹拌機、コンデンサー付きの１００ｍＬの丸底フラスコに、ｐ－ベンゾキノン２５ｇ（特級、富士フイルム和光純薬（株）製）、２，２’－ジベンゾチアゾリルジスルフィド２．５ｇ（純度＞９６％、東京化成工業（株）製）を充填した。フラスコ内を窒素パージした後、窒素雰囲気下にて攪拌しながら１４０℃まで昇温し、３０分で内容物を溶解した。続いて、２００℃に昇温し、５時間加熱した。
フラスコ内反応物を常温まで冷却し、黒色固体として反応物を回収した。反応物のＴＨＦ可溶分については、ＦＤ－ＭＳ分析を行った結果、末端にＯＨ基を有する２量体～６量体に相当するポリフェニレンオキサイドが生成していると推定された。反応物のＧＰＣ、およびＦＴＩＲ測定の結果、Ｍｗ＝１１０００程度の分子量を持つポリフェニレンオキサイドと同定した。以上の結果より、本反応により得られた重合体はＰＰＯと同定することができた。
Example 1
In a 100 mL round bottom flask equipped with a stirrer and a condenser, 25 g of p-benzoquinone (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 2.5 g of 2,2'-dibenzothiazolyl disulfide (purity >96%, (manufactured by Tokyo Kasei Kogyo Co., Ltd.). After purging the inside of the flask with nitrogen, the temperature was raised to 140° C. with stirring under a nitrogen atmosphere, and the contents were dissolved in 30 minutes. Subsequently, the temperature was raised to 200°C and heated for 5 hours.
The reactant in the flask was cooled to room temperature, and the reactant was recovered as a black solid. As a result of FD-MS analysis of the THF-soluble portion of the reaction product, it was estimated that polyphenylene oxide corresponding to a dimer to hexamer having an OH group at the end was produced. As a result of GPC and FTIR measurements of the reaction product, it was identified as polyphenylene oxide having a molecular weight of about Mw=11,000. From the above results, the polymer obtained by this reaction could be identified as PPO.
ＦＤ－ＭＳ測定に用いた装置及び測定条件を以下に示す。
＜ＦＤ－ＭＳ測定＞
装置：JMS-700V（日本電子（株）製）
条件：加速電圧 ８ｋＶ
対向電圧 ０ｋＶ
スキャンレンジ ｍ／ｚ＝５０～３，０００
エミッタ種：カーボン
エミッタ電流：掃引速度２ｍＡ／ｍｉｎにて、０ｍＡから４０ｍＡまで掃引した。
試料溶解溶媒：ＴＨＦ
The apparatus and measurement conditions used for FD-MS measurement are shown below.
<FD-MS measurement>
Equipment: JMS-700V (manufactured by JEOL Ltd.)
Conditions: Acceleration voltage 8kV
Opposing voltage 0kV
Scan range m/z=50-3,000
Emitter type: Carbon Emitter current: Swept from 0 mA to 40 mA at a sweep rate of 2 mA/min.
Sample dissolution solvent: THF
不溶分についてＫＢｒ法にてＦＴＩＲ測定を行い、図２に示すＦＴＩＲチャートを得た。１，４００～１，７００ｃｍ-1付近に芳香族由来のＣ＝Ｃ結合由来のピークが、１，２００ｃｍ-1付近にＣＯ結合由来のピークが、７００～９００ｃｍ-1付近に芳香族由来のＣＨ結合由来のピークの出現を確認し、ＰＰＯであることを確認した。ＦＴＩＲ測定には、フーリエ変換赤外分光光度計（日本分光（株）製：FT／IR-6200）を用いた。また、ＧＰＣ測定の結果からＭｗ＝１１０００程度の分子量を持つポリマーであることを確認した。 FTIR measurement was performed on the insoluble matter using the KBr method, and the FTIR chart shown in FIG. 2 was obtained. There is a peak derived from aromatic C=C bond at around 1,400 to 1,700 cm -1 , a peak derived from CO bond at around 1,200 cm -1 , and a peak derived from aromatic CH at around 700 to 900 cm -1 The appearance of a peak derived from binding was confirmed, and it was confirmed that it was PPO. For the FTIR measurement, a Fourier transform infrared spectrophotometer (manufactured by JASCO Corporation: FT/IR-6200) was used. Further, from the results of GPC measurement, it was confirmed that the polymer had a molecular weight of about Mw=11,000.
ＧＰＣ測定は標準ポリスチレンを用いた検量線から換算した。ＧＰＣ測定には下記の装置及び測定条件を用いた。
＜ＧＰＣ測定装置＞
機器名：Alliance e2695（Waters製）
カラム：Shodex GPC KF-806M（昭和電工株式会社製、商品名） 2本
カラムサイズ：内径８．０ｍｍ×長さ３００ｍｍ
溶離液：０．０１Ｍ LiBrのＮ－メチル－２－ピロリドン溶液（0.01M LiBr in NMP）
試料濃度：１０ｍｇ／１０ｍＬ
注入量：１００μＬ
流量：０．７ｍＬ／分
カラム温度：６０℃
検出器：ＵＶ
検出波長：２７０ｎｍ
標準試料：ポリスチレン（分子量５００～４，４８０，０００の間で検量線を作成）
GPC measurements were converted from a calibration curve using standard polystyrene. The following equipment and measurement conditions were used for the GPC measurement.
<GPC measurement device>
Equipment name: Alliance e2695 (manufactured by Waters)
Column: 2 Shodex GPC KF-806M (manufactured by Showa Denko K.K., product name) Column size: Inner diameter 8.0 mm x length 300 mm
Eluent: 0.01M LiBr in N-methyl-2-pyrrolidone solution (0.01M LiBr in NMP)
Sample concentration: 10mg/10mL
Injection volume: 100μL
Flow rate: 0.7 mL/min Column temperature: 60°C
Detector: UV
Detection wavelength: 270nm
Standard sample: polystyrene (calibration curve created between molecular weight 500 and 4,480,000)
以上の結果より、本反応により黒色固体として得られた反応物はＴＨＦ可溶分と不溶分のいずれもＰＰＯと同定することができた。 From the above results, both the THF soluble and insoluble components of the reaction product obtained as a black solid in this reaction could be identified as PPO.
Claims (5)
［式（I）中、ＡはＣ－Ｃ二重結合、酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ1で示されるＲ1基を有する。Ｑは酸素原子、硫黄原子又は窒素原子を示し、窒素原子はＮ－Ｒ2で示されるＲ2基を有する。Ｒ1及びＲ2はそれぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数３～１５のシクロアルキル基、炭素数５～１５のシクロアルキレン基、アリール基又はヘテロアリール基を示す。ｐは１～５の整数を示す。］ The method for producing an aromatic polyether according to claim 1, wherein the compound having a quinoid structure is a compound having a skeleton represented by general formula (I).
[In formula (I), A represents a C--C double bond, an oxygen atom, a sulfur atom, or a nitrogen atom, and the nitrogen atom has an R 1 group represented by NR 1 . Q represents an oxygen atom, a sulfur atom or a nitrogen atom, and the nitrogen atom has an R 2 group represented by NR 2 . R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an aryl group, or a heteroaryl group. . p represents an integer from 1 to 5. ]
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