JPS6315939B2 - - Google Patents
Info
- Publication number
- JPS6315939B2 JPS6315939B2 JP2685280A JP2685280A JPS6315939B2 JP S6315939 B2 JPS6315939 B2 JP S6315939B2 JP 2685280 A JP2685280 A JP 2685280A JP 2685280 A JP2685280 A JP 2685280A JP S6315939 B2 JPS6315939 B2 JP S6315939B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- catalyst
- polymerization
- polymer
- basic nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 28
- -1 2,6-disubstituted phenol Chemical class 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
- 125000005647 linker group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical group 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001955 polyphenylene ether Polymers 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PZVZGDBCMQBRMA-UHFFFAOYSA-N 3-pyridin-4-ylpropan-1-ol Chemical compound OCCCC1=CC=NC=C1 PZVZGDBCMQBRMA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- NJWIMFZLESWFIM-UHFFFAOYSA-N 2-(chloromethyl)pyridine Chemical compound ClCC1=CC=CC=N1 NJWIMFZLESWFIM-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- IRJGZWIEFFOYJN-UHFFFAOYSA-N copper;pyridine Chemical class [Cu].C1=CC=NC=C1 IRJGZWIEFFOYJN-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 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
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HHDPJRSXPOGIOP-UHFFFAOYSA-L manganese(2+);dibromide;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[Br-].[Br-] HHDPJRSXPOGIOP-UHFFFAOYSA-L 0.000 description 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
Description
【発明の詳細な説明】
本発明はポリフエニレンエーテルの製造法に関
するものである。従来、２，６−ジ置換フエノー
ルを酸素存在下で重合させてポリフエニレンエー
テルを製造する触媒としては、銅−ピリジン錯体
など各種の金属錯体が知られている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyphenylene ether. Conventionally, various metal complexes such as copper-pyridine complexes have been known as catalysts for producing polyphenylene ether by polymerizing 2,6-disubstituted phenols in the presence of oxygen.
本発明者らは、先にポリフエニレンエーテルを
製造する触媒として、遷移金属イオンと、ポリ
（４−ビニルピリジン）樹脂、ポリ（Ｎ−ビニル
イミダゾール）樹脂、ポリエチレンイミン樹脂、
アミノメチル化ポリスチレン樹脂のような塩基性
含窒素樹脂とから形成された錯体触媒が有効であ
ることを見い出した。 The present inventors first used transition metal ions, poly(4-vinylpyridine) resin, poly(N-vinylimidazole) resin, polyethyleneimine resin,
It has been found that a complex catalyst formed from a basic nitrogen-containing resin such as an aminomethylated polystyrene resin is effective.
このような錯体触媒は配位子樹脂の性質に帰因
する次のような特性を有する。重合溶媒に不溶
な配位子樹脂を使用することにより、触媒は容易
に回収、再使用ができ、例えば固定床流通法によ
る反応も可能となる。錯体触媒としての安定性
が向上し、広い条件範囲（溶媒、濃度、PH、温
度）で使用可能となる。この反面、樹脂内部の
錯体触媒点には２，６−ジ置換フエノールは配位
活性化し得ず、その結果有効な触媒活性点となつ
ているのは樹脂表層部で錯形成している金属イオ
ンのみであつて、触媒効率が低く留まる。生長
途中のオリゴフエニレンエーテルが樹脂の立体障
害により、たとえ樹脂表層部にある錯体触媒点で
あつても、そこへの配位が困難となるため、生成
ポリフエニレンエーテルの分子量が高くなり得な
い、という欠点があるため利用範囲が限られてい
た。 Such a complex catalyst has the following properties due to the properties of the ligand resin. By using a ligand resin that is insoluble in the polymerization solvent, the catalyst can be easily recovered and reused, and the reaction can be carried out, for example, by a fixed bed flow method. It has improved stability as a complex catalyst and can be used under a wide range of conditions (solvent, concentration, pH, temperature). On the other hand, 2,6-disubstituted phenols cannot coordinate and activate the complex catalytic sites inside the resin, and as a result, the effective catalytic active sites are metal ions complexed on the surface of the resin. However, the catalyst efficiency remains low. Due to the steric hindrance of the resin, the oligophenylene ether that is growing becomes difficult to coordinate to the complex catalyst site even if it is on the surface of the resin, so the molecular weight of the polyphenylene ether produced can become high. The range of use was limited due to the drawback that
本発明者らは前記錯体触媒に関して更に研究を
進めたところ、このような塩基性含窒素樹脂につ
き、塩基性含窒素配位子部位を長い連結基を介し
て樹脂表層に位置せしめるという改良を加えるこ
とにより上記、の欠点を解決し、一段と活性
が高くなることを見い出し本発明に到達した。 The present inventors conducted further research on the complex catalyst, and found that they made an improvement to the basic nitrogen-containing resin by locating the basic nitrogen-containing ligand moiety on the surface layer of the resin via a long linking group. The present inventors have discovered that the above-mentioned drawbacks can be solved and the activity can be further increased by doing so, and the present invention has been achieved.
すなわち本発明の要旨は、重合溶媒中で触媒の
存在下に２，６−ジ置換フエノールを重合してポ
リフエニレンエーテルを製造する方法において、
触媒としてイミダゾール類、またはピリジン類か
ら成る塩基性含窒素配位子が、アルキレン基を含
みかつその部分の炭素数が２以上の連結基を介し
て重合溶媒に不溶のスチレンまたはアクリル酸グ
リシジルエステルを含むビニル重合体の骨格に結
合した高分子化合物と、銅イオン、マンガンイオ
ン、または鉄イオンから選ばれる金属イオンとか
ら形成された錯体触媒を使用することを特徴とす
る方法に存する。 That is, the gist of the present invention is a method for producing polyphenylene ether by polymerizing 2,6-disubstituted phenol in the presence of a catalyst in a polymerization solvent,
A basic nitrogen-containing ligand consisting of imidazoles or pyridines as a catalyst binds styrene or acrylic acid glycidyl ester, which is insoluble in the polymerization solvent, through a linking group containing an alkylene group and having 2 or more carbon atoms. The method is characterized by using a complex catalyst formed from a polymer compound bonded to the skeleton of a vinyl polymer containing a metal ion selected from a copper ion, a manganese ion, or an iron ion.
以下に本発明を詳細に説明する。 The present invention will be explained in detail below.
本発明方法で使用する触媒の一方の成分である
重合溶媒に不溶な高分子化合物は、通常ビニル重
合体であり、それらの中ではスチレン−ジビニル
ベンゼン架橋共重合体などのスチレンを含む重合
体やアクリル酸グリシジルエステルを含む重合体
が塩基性含窒素配位子を結合させ易いので好都合
である。 The polymer compound insoluble in the polymerization solvent, which is one component of the catalyst used in the method of the present invention, is usually a vinyl polymer, and among these, styrene-containing polymers such as styrene-divinylbenzene crosslinked copolymers, Polymers containing acrylic acid glycidyl ester are advantageous because they facilitate binding of basic nitrogen-containing ligands.
この高分子化合物の骨格と塩基性含窒素配位子
との間に介在する連結基は、アルキレン基を含
み、かつその部分の炭素数が２以上であることが
必要である。連結基はアルキレン基だけから成つ
ていてもよく、また芳香族炭化水素やエーテル結
合等を含んでいてもよい。アミド結合やエステル
結合等も連結基に含ませることができるが、これ
らの結合は酸やアルカリにより分解され易い。 The linking group interposed between the skeleton of the polymer compound and the basic nitrogen-containing ligand needs to contain an alkylene group and have 2 or more carbon atoms. The linking group may consist only of an alkylene group, or may contain an aromatic hydrocarbon, an ether bond, or the like. Although amide bonds, ester bonds, etc. can also be included in the linking group, these bonds are easily decomposed by acids and alkalis.
塩基性含窒素配位子としてはイミダゾール類ま
たはピリジン類が使用される。 Imidazoles or pyridines are used as the basic nitrogen-containing ligand.
高分子化合物の骨格に上記の連結基を介して塩
基性含窒素配位子を結合させるのは、従来有機化
学で常用されている方法を用いればよい。このよ
うな方法としては、例えば以下に述べる様な方法
がある。 A basic nitrogen-containing ligand may be bonded to the skeleton of a polymer compound via the above-mentioned linking group by a method conventionally used in organic chemistry. Examples of such methods include the following methods.
アルキレングリコールのモノピリジンカルボ
ン酸エステルをスチレン−ジビニルベンゼン−
ビニル安息香酸架橋共重合体と反応させて脱水
し、エステル結合させる方法
ポリオキシアルキレングリコールのモノピリ
ジルメチルエーテルをクロロメチル化スチレン
−ジビニルベンゼン架橋共重合体と反応させて
脱塩化水素し、エーテル結合させる方法
スチレン−ジビニルベンゼン−ビニル安息香
酸架橋共重合体とアルキレングリコールを脱水
反応させてハーフエステルとし、これをピリジ
ンカルボン酸と反応させる方法
クロロメチル化スチレン−ジビニルベンゼン
架橋共重合体とポリオキシアルキレングリコー
ルを脱塩化水素反応させてハーフエーテルと
し、これをクロロメチルピリジンを反応させる
方法
錯体触媒のもう一方の成分である金属原子イオ
ンとしては、銅イオン、マンガンイオン、及び鉄
イオンが適しており、塩化物、臭化物、硫酸塩、
酢酸塩などいずれの形でも使用できる。 Monopyridinecarboxylic acid ester of alkylene glycol is converted into styrene-divinylbenzene-
A method of reacting with a vinylbenzoic acid crosslinked copolymer to dehydrate and form an ester bond A method in which monopyridyl methyl ether of polyoxyalkylene glycol is reacted with a chloromethylated styrene-divinylbenzene crosslinked copolymer to dehydrochlorinate and form an ether bond. A method of dehydrating a styrene-divinylbenzene-vinylbenzoic acid cross-linked copolymer and an alkylene glycol to form a half ester, which is then reacted with pyridinecarboxylic acid A method of reacting a chloromethylated styrene-divinylbenzene cross-linked copolymer with a polyoxyalkylene A method of dehydrochlorinating glycol to form a half ether, which is then reacted with chloromethylpyridine. As the metal atom ion, which is the other component of the complex catalyst, copper ions, manganese ions, and iron ions are suitable. chloride, bromide, sulfate,
It can be used in any form such as acetate.
錯体触媒は、上述の連結基を介して結合した塩
基性含窒素配位子を有する高分子化合物と、上記
金属原子イオンを含む化合物を溶媒中で混合すれ
ば調製することができる。通常塩基性含窒素配位
子に対し１〜1/10倍モルの金属イオンを添加し、
錯平衡に達せしめた後、錯体触媒をロ別、洗浄し
未配位の金属イオンを除去する。低酸化数の金属
塩を使用する場合は、調製の際、充分に空気と接
触するようにする。 The complex catalyst can be prepared by mixing the above-mentioned polymer compound having a basic nitrogen-containing ligand bonded via a linking group with the above-mentioned compound containing a metal atom ion in a solvent. Usually, 1 to 1/10 times the molar amount of metal ions is added to the basic nitrogen-containing ligand,
After reaching complex equilibrium, the complex catalyst is filtered and washed to remove uncoordinated metal ions. When using a metal salt with a low oxidation number, ensure sufficient contact with air during preparation.
この際に用いられる溶媒としては、例えばメタ
ノール、エタノール等の低級アルカノールが好適
である。 As the solvent used in this case, for example, lower alkanols such as methanol and ethanol are suitable.
重合すべき２，６−ジ置換フエノールは、通常
一般式（）
（式中、R1およびR2は炭化水素基またはアルコ
キシ基を表わす。）で示される。 The 2,6-disubstituted phenol to be polymerized usually has the general formula () (In the formula, R 1 and R 2 represent a hydrocarbon group or an alkoxy group.)
一般式（）中で、R1およびR2は例えばメチ
ル、エチル、イソプロピル等の低級アルキル基、
フエニル等のアリール基、ベンジル基のアラルキ
ル基などの炭化水素基またはメトキシ、エトキ
シ、イソプロポキシ等のアルコキシ基であり、
R1とR2は同一であつてもよい。 In the general formula (), R 1 and R 2 are lower alkyl groups such as methyl, ethyl, isopropyl, etc.
An aryl group such as phenyl, a hydrocarbon group such as an aralkyl group such as benzyl group, or an alkoxy group such as methoxy, ethoxy, isopropoxy,
R 1 and R 2 may be the same.
上記のようにして調製した錯体触媒を重合溶媒
に懸濁させた後、単量体２，６−ジ置換フエノー
ルを添加し、常法に従つて酸素存在下、０〜100
℃、例えば室温で激しく撹拌すると、容易に重合
が進行してポリフエニレンエーテルが生成する。
触媒量は、（単量体）／（錯体触媒中の金属成分）
＝１〜1000（モル比）が適当である。また金属成
分の１〜３倍モルの水酸化カリウム、水酸化ナト
リウムなどのアルカリ溶液を添加することにより
重合速度は更に大きくなる。重合終了後、触媒を
ロ別し、常法に従つてロ液を塩酸酸性のメタノー
ルに滴下すると白色の重合体沈殿が得られるの
で、これをロ別、洗浄、乾燥すると、ポリ（２，
６−ジ置換フエニレンエーテル）が得られる。ま
た回収触媒は、くり返し使用が可能である。 After suspending the complex catalyst prepared as described above in a polymerization solvent, a monomeric 2,6-disubstituted phenol was added, and a 0-100
When vigorously stirred at a temperature of .degree. C., for example, room temperature, polymerization easily proceeds to produce polyphenylene ether.
The amount of catalyst is (monomer)/(metal component in the complex catalyst)
=1 to 1000 (molar ratio) is appropriate. The polymerization rate can be further increased by adding an alkaline solution such as potassium hydroxide or sodium hydroxide in an amount of 1 to 3 times the mole of the metal component. After the polymerization is completed, the catalyst is separated by filtration and the filtrate is added dropwise to methanol acidified with hydrochloric acid according to a conventional method. A white polymer precipitate is obtained. This is separated by filtration, washed, and dried to obtain poly(2,
6-disubstituted phenylene ether) is obtained. Moreover, the recovered catalyst can be used repeatedly.
重合溶媒としてはメタノール、エタノール、ベ
ンゼン、トルエン、キシレン、クロロホルムなど
が使用できるが、ベンゼン類、ハロゲン化炭化水
素を用いた場合、高分子量の重合体が得られる。 As the polymerization solvent, methanol, ethanol, benzene, toluene, xylene, chloroform, etc. can be used, but when benzenes or halogenated hydrocarbons are used, high molecular weight polymers can be obtained.
次に本発明の実施例を示す。 Next, examples of the present invention will be shown.
実施例 １
４−ピリジンプロパノール13.7ｇをジメチルホ
ルムアミド（DMF）500mlに溶解し2.4ｇの水素
化ナトリウムを加え、１時間撹拌した後、部分ク
ロルメチル化した２％ジビニルベンゼン架橋ポリ
スチレンビーズ（200〜400mesh、クロルメチル
化率50％）（以下樹脂(2)という）12.89を添加し、
窒素気流下50℃で５時間反応させる。反応終了後
生成した樹脂(3)をロ別し、メタノールで洗浄、乾
燥する。収量16.6ｇ、元素分析（Ｃ：84.6、Ｈ：
7.5、Ｎ：3.4、Cl：2.0％）より４−ピリジンプロ
パノールの導入率は約80％である。(3)の赤外吸収
スペクトルはクロルメチル基の吸収（νC−Cl670
cm-1）がほぼ消失し、エーテル結合の生成を示す
νC−Ｏ−Ｃ（1090cm-1）の吸収が認められた。メ
タノール中で塩化第１銅0.60ｇと樹脂(3)10ｇを混
合し、大気下で充分に撹拌した後、錯体樹脂をロ
別、洗浄、乾燥する。収量は10.6ｇであつた。Example 1 13.7 g of 4-pyridine propanol was dissolved in 500 ml of dimethylformamide (DMF), 2.4 g of sodium hydride was added, and after stirring for 1 hour, partially chloromethylated 2% divinylbenzene cross-linked polystyrene beads (200-400 mesh, 12.89 (chloromethylation rate 50%) (hereinafter referred to as resin (2)) was added,
React for 5 hours at 50°C under a nitrogen stream. After the reaction is completed, the resin (3) produced is filtered, washed with methanol, and dried. Yield 16.6g, elemental analysis (C: 84.6, H:
7.5, N: 3.4, Cl: 2.0%), the introduction rate of 4-pyridinepropanol is approximately 80%. The infrared absorption spectrum of (3) is the absorption of chloromethyl group (νC−Cl670
cm -1 ) almost disappeared, and absorption of νC-O-C (1090 cm -1 ) indicating the formation of an ether bond was observed. After mixing 0.60 g of cuprous chloride and 10 g of resin (3) in methanol and thoroughly stirring in the atmosphere, the complex resin is filtered, washed, and dried. The yield was 10.6g.
この錯体樹脂1.8ｇをベンゼン100mlに懸濁さ
せ、これに２，６−ジメチルフエノール1.22ｇを
加え、反応容器内を酸素置換した後、室温で激し
く撹拌する。撹拌と同時に重合が始まり、60分で
反応が完了する。触媒をロ別後、反応液を塩酸酸
性メタノール１に滴下すると白色の沈殿が得ら
れるので、別、洗浄、乾燥する。重合体の収量
は82％であつた。 1.8 g of this complex resin is suspended in 100 ml of benzene, 1.22 g of 2,6-dimethylphenol is added thereto, the inside of the reaction vessel is purged with oxygen, and then vigorously stirred at room temperature. Polymerization begins simultaneously with stirring, and the reaction is completed in 60 minutes. After filtering out the catalyst, the reaction solution is added dropwise to 1 part of methanol acidified with hydrochloric acid to obtain a white precipitate, which is separated, washed, and dried. The yield of polymer was 82%.
生成重合体の赤外吸収スペクトルは原料フエノ
ールの特顛である3400cm-1付近のνOHによる吸
収は全く消失し、ポリエーテルの生成を確認し得
るνC−Ｏ−Ｃ（1180cm-1）の吸収が顕著となり
1600cm-1に芳香核のνC＝Ｃ、830cm-1に芳香核の
隣接２水素によるδC−Ｈ（面外）の吸収が認めら
れた。これらのことから本実施例で得られた重合
体はポリ（２，６−ジメチルフエニレンエーテ
ル）であることを確認した。またベンゼン中25℃
における粘度測定の結果より分子量は、24500で
あつた。 In the infrared absorption spectrum of the produced polymer, the absorption by νOH near 3400 cm -1 , which is a characteristic of the raw material phenol, completely disappeared, and the absorption of νC-O-C (1180 cm -1 ), which can confirm the formation of polyether, was observed. become noticeable
Absorption of νC=C of the aromatic nucleus at 1600 cm -1 and δC-H (out-of-plane) absorption by the adjacent dihydrogen of the aromatic nucleus was observed at 830 cm -1 . From these results, it was confirmed that the polymer obtained in this example was poly(2,6-dimethylphenylene ether). Also in benzene at 25℃
The molecular weight was 24,500 from the results of viscosity measurement.
実施例 ２
実施例１で調製した触媒をベンゼンで充分膨潤
せしめた後、これを10mmφ×400mmのカラムに注
ぎこみ充てんする。２，６−ジメチルフエノール
12.3ｇを含むベンゼン溶液500mlをカラム上部よ
り酸素を吹きこみながら流下速度２ml／minで流
下させる。流出液500mlを1/3に濃縮後、塩酸酸性
メタノール２に滴下すると白色の重合体の沈殿
が得られた。重合体の収率は63％、分子量は8200
であつた。Example 2 After the catalyst prepared in Example 1 was sufficiently swollen with benzene, it was poured into a 10 mmφ×400 mm column and packed. 2,6-dimethylphenol
500 ml of a benzene solution containing 12.3 g is allowed to flow down from the top of the column at a flow rate of 2 ml/min while blowing oxygen. After concentrating 500 ml of the effluent to 1/3, it was added dropwise to 2 methanol acidified with hydrochloric acid to obtain a white polymer precipitate. Polymer yield is 63%, molecular weight is 8200
It was hot.
実施例 ３
臭化第２銅0.22ｇをメタノール100mlに溶解し、
実施例１で合成した樹脂(3)を添加し、充分撹拌し
た後水酸化カリウム0.11ｇを加える。これに２，
６−ジメチルフエノール1.22ｇを含むメタノール
20mlを加え、反応容器内を酸素置換した後、室温
で激しく撹拌する。反応は約30分で終了する。触
媒を除去した後、希塩酸１を添加すると白色の
重合体の沈殿が得られるので、これをロ別、洗
浄、乾燥する。重合体の収量86％、分子量は3900
であつた。Example 3 0.22 g of cupric bromide was dissolved in 100 ml of methanol,
The resin (3) synthesized in Example 1 was added, and after thorough stirring, 0.11 g of potassium hydroxide was added. 2,
Methanol containing 1.22 g of 6-dimethylphenol
After adding 20 ml and replacing the inside of the reaction vessel with oxygen, stir vigorously at room temperature. The reaction completes in about 30 minutes. After removing the catalyst, 1 part of dilute hydrochloric acid is added to obtain a white polymer precipitate, which is filtered, washed and dried. Polymer yield 86%, molecular weight 3900
It was hot.
実施例 ４
１，６−ヘキサンジオール23.6ｇをDMF500ml
に溶解し、水素化ナトリウム4.8ｇを加え、１時
間撹拌する。次に樹脂(2)12.8ｇを添加し、50℃で
10時間反応させる。反応終了後、樹脂をロ別し、
水洗、乾燥する。収量は18.5ｇであり、樹脂中に
ほとんど塩素を含有しないことから１，６−ヘキ
サンジオールの導入率はほぼ100％であつた。こ
のようにして得られた樹脂(4)を再びDMF500mlに
加え、2.4ｇの水素化ナトリウムを加え２時間反
応させる。ついで１−クロル−３−ピリジルプロ
パン15.5ｇを添加して窒素気流下50℃で５時間反
応させる。反応終了後、樹脂(5)をロ別、水洗、乾
燥する。収量は23.1ｇであり元素分析（Ｃ：
81.2、Ｈ：8.3、Ｎ：2.1％）よりピリジン残基の
導入率は約60％であつた。Example 4 23.6g of 1,6-hexanediol in 500ml of DMF
Add 4.8 g of sodium hydride and stir for 1 hour. Next, add 12.8g of resin (2) and heat at 50℃.
Incubate for 10 hours. After the reaction is completed, the resin is separated,
Wash with water and dry. The yield was 18.5 g, and since the resin contained almost no chlorine, the introduction rate of 1,6-hexanediol was almost 100%. The resin (4) thus obtained was again added to 500 ml of DMF, 2.4 g of sodium hydride was added, and the mixture was allowed to react for 2 hours. Then, 15.5 g of 1-chloro-3-pyridylpropane was added and the mixture was reacted at 50° C. for 5 hours under a nitrogen stream. After the reaction is completed, the resin (5) is filtered, washed with water, and dried. The yield was 23.1g, and elemental analysis (C:
81.2, H: 8.3, N: 2.1%), the introduction rate of pyridine residues was approximately 60%.
塩化マンガン４水塩0.74ｇのメタノール溶液に
樹脂(5)10ｇを添加し充分撹拌した後、錯体樹脂を
ロ別、洗浄、乾燥する。収量は10.6ｇであつた。
この錯体樹脂2.9ｇをベンゼン100mlに懸濁させ、
以下実施例１と同様にして重合を行なつた。重合
は90分で終了し、重合体の収率は80％分子量は
14200であつた。 After adding 10 g of resin (5) to a methanol solution of 0.74 g of manganese chloride tetrahydrate and stirring thoroughly, the complex resin is filtered, washed, and dried. The yield was 10.6g.
Suspend 2.9 g of this complex resin in 100 ml of benzene,
Thereafter, polymerization was carried out in the same manner as in Example 1. The polymerization was completed in 90 minutes, and the polymer yield was 80%, and the molecular weight was
It was 14,200.
実施例 ５
塩化チオニル200mlに、実施例４で合成した樹
脂(4)18.5ｇを加え２時間沸点還流する。減圧下で
塩化チオニルを留去せしめた後樹脂をDMF500ml
に懸濁させる。これにジエチルアミン15ｇを加え
窒素気流下50℃で５時間反応させる。反応終了
後、置換(6)をロ別、水洗、乾燥する。収量は21.2
ｇであり元素分析（Ｃ：82.1、Ｈ：9.8、Ｎ：2.9
％）よりアミン残基の導入率は約80％である。Example 5 18.5 g of the resin (4) synthesized in Example 4 was added to 200 ml of thionyl chloride, and the mixture was refluxed at boiling point for 2 hours. After thionyl chloride was distilled off under reduced pressure, the resin was poured into 500 ml of DMF.
Suspend in Add 15 g of diethylamine to this and react at 50° C. for 5 hours under a nitrogen stream. After the reaction is completed, substituted product (6) is filtered, washed with water, and dried. Yield is 21.2
g and elemental analysis (C: 82.1, H: 9.8, N: 2.9
%), the introduction rate of amine residues is approximately 80%.
臭化マンガン４水塩1.5ｇを用いて以下実施例
４と同様にして触媒の調製および２，６−ジメチ
ルフエノールの重合を行なつた。重合は60分で終
了し、重合体収率は81％、分子量は21700であつ
た。 A catalyst was prepared and 2,6-dimethylphenol was polymerized in the same manner as in Example 4 using 1.5 g of manganese bromide tetrahydrate. Polymerization was completed in 60 minutes, with a polymer yield of 81% and a molecular weight of 21,700.
実施例 ６
実施例１でロ別・回収した触媒を溶媒で充分洗
浄した後、再び実施例１と同様にして、２，６−
ジメチルフエノールの重合を行なつた。重合は60
分で終了し、重合体の収量は80％、分子量は
24200であつた。Example 6 After thoroughly washing the catalyst separated and recovered in Example 1 with a solvent, 2,6-
Polymerization of dimethylphenol was carried out. Polymerization is 60
Finished in minutes, polymer yield was 80%, molecular weight was
It was 24200.
Claims (1)
置換フエノールを重合してポリフエニレンエーテ
ルを製造する方法において、触媒としてイミダゾ
ール類、またはピリジン類から成る塩基性含窒素
配位子が、アルキレン基を含みかつその部分の炭
素数が２以上の連結基を介して重合溶媒に不溶の
スチレンまたはアクリル酸グリシジルエステルを
含むビニル重合体の骨格に結合した高分子化合物
と、銅イオン、マンガンイオン、または鉄イオン
から選ばれる金属原子イオンとから形成された錯
体触媒を使用することを特徴とする方法。1 In a method for producing polyphenylene ether by polymerizing 2,6-disubstituted phenol in the presence of a catalyst in a polymerization solvent, a basic nitrogen-containing ligand consisting of imidazoles or pyridines is used as a catalyst. is a polymer compound bonded to the skeleton of a vinyl polymer containing styrene or acrylic acid glycidyl ester, which is insoluble in the polymerization solvent, through a linking group containing an alkylene group and having 2 or more carbon atoms in that part, and a copper ion, A method characterized by using a complex catalyst formed with a metal atom ion selected from manganese ions or iron ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2685280A JPS56122830A (en) | 1980-03-04 | 1980-03-04 | Preparation of polyphenylene ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2685280A JPS56122830A (en) | 1980-03-04 | 1980-03-04 | Preparation of polyphenylene ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56122830A JPS56122830A (en) | 1981-09-26 |
| JPS6315939B2 true JPS6315939B2 (en) | 1988-04-06 |
Family
ID=12204797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2685280A Granted JPS56122830A (en) | 1980-03-04 | 1980-03-04 | Preparation of polyphenylene ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56122830A (en) |
-
1980
- 1980-03-04 JP JP2685280A patent/JPS56122830A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56122830A (en) | 1981-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4297716B2 (en) | Method for forming CC bond | |
| US7772417B2 (en) | Heterogeneous organotin catalysts | |
| JPS60112823A (en) | Manufacture of difunctional polyphenylene oxide | |
| JPH0139426B2 (en) | ||
| JPH046201B2 (en) | ||
| JP2003342287A (en) | Complex compound and method for producing aliphatic polycarbonate using the same | |
| CN101151266A (en) | Method for the catalytic production of hydrocodone, hydromorphone, and derivatives thereof | |
| JPS6315939B2 (en) | ||
| US20070203019A1 (en) | Phase selective polymer supports for catalysis | |
| JPS6315284B2 (en) | ||
| GB1559549A (en) | Manganese vinyl resin complexes and their use as catalyst in a method for preparing polyphenylene oxides | |
| Bochmann et al. | Synthesis of poly (arylene ethyne) s via palladium‐catalyzed cross‐coupling reactions with Cu and Sn reagents | |
| JPH0360326B2 (en) | ||
| JPH0237365B2 (en) | ||
| JPS6315940B2 (en) | ||
| US5049672A (en) | Complex-forming polymers and processes to prepare them | |
| US20100298457A1 (en) | Compounds for use as ligands | |
| US20130158219A1 (en) | Supported ligands having a high local density of coordinating atoms | |
| US4187361A (en) | Method for preparing polyphenylene oxides with manganese-vinyl resin complexes | |
| JP2535756B2 (en) | Method for producing biphenyldicarboxylic acid polyesters | |
| JPS6347733B2 (en) | ||
| CN114276487B (en) | Organic phosphine polymer, catalyst containing same, synthesis method and application thereof | |
| US4582881A (en) | 2-substituted 5-vinylpyrimidines, polymer obtainable therefrom and preparation thereof | |
| Chiellini et al. | Chiral polymeric halogen adducts. Synthesis and reactivity | |
| JPH11309377A (en) | Catalyst carrier and metal complex catalyst |