JPS6026492B2 - Polyester with guaiacyl group - Google Patents
Polyester with guaiacyl groupInfo
- Publication number
- JPS6026492B2 JPS6026492B2 JP7198281A JP7198281A JPS6026492B2 JP S6026492 B2 JPS6026492 B2 JP S6026492B2 JP 7198281 A JP7198281 A JP 7198281A JP 7198281 A JP7198281 A JP 7198281A JP S6026492 B2 JPS6026492 B2 JP S6026492B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- group
- guaiacyl
- pentaerythritol
- present
- 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
- 229920000728 polyester Polymers 0.000 title claims description 10
- -1 polymethylene group Polymers 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- FVTLELNQLQEHGR-UHFFFAOYSA-N 1,5-bis(4-hydroxy-3-methoxyphenyl)-3,3-bis(hydroxymethyl)penta-1,4-diene-2,4-diol Chemical compound C1=C(O)C(OC)=CC(C=C(O)C(CO)(CO)C(O)=CC=2C=C(OC)C(O)=CC=2)=C1 FVTLELNQLQEHGR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
本発明は新規な構造のポリエステル、さらに詳しくは、
一般式（式中、Ｒはポリメチレン基又はアリーレン基で
ある）で表わされる繰返し構造単位を有するグアャシル
基を有するポリエステルに関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester with a novel structure, more specifically,
The present invention relates to a polyester having a guaacyl group having a repeating structural unit represented by the general formula (wherein R is a polymethylene group or an arylene group).
本発明のポリエステルは、従来知られていない新規重合
体であり、その分子内にスピロ結合を有するため、分子
の剛直性は、ベンゼン環、シクロへキサン環の中間に位
置し構造に起因する諸性質もこれに準じたものが期待さ
れる。また、溶剤への溶解性も良好であるなどの特徴を
有し、プラスチック材料、繊維材料、塗膜材料などとし
て利用される。本発明によるポリエステルは、式で表わ
されるビス（４ーヒドロキシ−３−メトキシベンジリデ
ン）ペンタェリトリトールと、一般式ＸＯＣ−Ｒ−ＣＯ
Ｘ
（式中、Ｒはポリメチレン基又はアリーレン基であり、
その炭素数は特に制限されないが、一般には、１〜１２
個である、×は水酸基、ハロゲン原子、アルコール残基
などの反応性基である）で表わされる二価カルポン酸又
はその反応性誘導体を溶媒中で重合反応させることによ
って製造することができる。The polyester of the present invention is a novel polymer that has not been previously known, and since it has a spiro bond in its molecule, the rigidity of the molecule is due to various factors due to the structure of the polyester, which is located between the benzene ring and the cyclohexane ring. It is expected that the properties will be similar to this. Furthermore, it has characteristics such as good solubility in solvents, and is used as a plastic material, fiber material, coating material, etc. The polyester according to the invention comprises bis(4-hydroxy-3-methoxybenzylidene)pentaerythritol of the formula and of the general formula XOC-R-CO
X (wherein R is a polymethylene group or an arylene group,
The number of carbon atoms is not particularly limited, but generally 1 to 12
(x is a reactive group such as a hydroxyl group, a halogen atom, or an alcohol residue) or a reactive derivative thereof can be produced by polymerizing a dicarboxylic acid or a reactive derivative thereof in a solvent.
この場合、反応条件としては、温度０〜３０つ○が採用
され、溶媒としては、ジクロルメタン、クロロホルム、
ジクロムエタンなどのハロゲン化炭化水素が適用される
。本発明により得られるポリエステルは、通常、１０方
〜５０万の分子量を有し、その軟化点は８５〜１２０℃
であり、溶触成形や溶融級糸が可能であり、また、膜成
形を行って各種分離膜として用いることが可能である。In this case, as the reaction conditions, a temperature of 0 to 30 ○ is adopted, and as a solvent, dichloromethane, chloroform,
Halogenated hydrocarbons such as dichromeethane are applied. The polyester obtained by the present invention usually has a molecular weight of 100,000 to 500,000, and a softening point of 85 to 120°C.
It can be melt-molded or made into melt-grade yarn, and it can also be formed into membranes and used as various separation membranes.
なお、本発明でモノマーとして用いるピス（４ーヒドロ
キシ−３−メトキシベンジリデン）ペンタェリトールは
、例えば、バニリンとペンタェリトリトールを酸性条件
下で反応させることによって得ることができる。Note that pis(4-hydroxy-3-methoxybenzylidene)pentaerythritol used as a monomer in the present invention can be obtained, for example, by reacting vanillin and pentaerythritol under acidic conditions.
次に本発明を実施例によりさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
参考例〔ビス（４−ヒドロキシ−３一メトキシベンジリ
デン）ペンタェリトリトールの合成〕バニリン７．５夕
、ベンタエリトリトール３．４夕、及びｐートルェンス
ルホン酸０．６夕を加熱蝿枠下にベンゼンに溶解し、４
時間還流した。Reference Example [Synthesis of bis(4-hydroxy-3-methoxybenzylidene)pentaerythritol] 7.5 hours of vanillin, 3.4 hours of pentaerythritol, and 0.6 hours of p-toluenesulfonic acid were heated under a fly frame. Dissolved in benzene, 4
Refluxed for an hour.
生成した水はＤｅａｎ−Ｓｔａｒｋのトラップを用いて
除いた。反応物を室温に冷却後、炭酸カリウム０．３４
夕／水１００の‘のアルカリ性水溶液で洗浄し、さらに
水で洗浄した。ベンゼン層を無水硫酸ナトリウムで乾燥
後、減圧濃縮した。この濃縮液にエチルェーテルを加え
、生成した沈殿を炉別し、トルェンから再結晶した。収
率４．５夕（５０％）、ｍｐ１６９〜１７１０○。実施
例
ビス（４ーヒドロキシー３一メトキシベンジリデン）ペ
ンタェリトリトール０．６０７夕及びトリェチルアミン
０．４５の‘のジクロルメタン溶液１ｏｗ‘に、塩化テ
レフタロィル０．３０５夕のジクロメタン溶液５の‘を
滋梓下に室温で滴下し、その後２岬時間反応させた。The water produced was removed using a Dean-Stark trap. After cooling the reaction to room temperature, potassium carbonate 0.34
Washed with a 100% alkaline aqueous solution in the evening/water, and further washed with water. The benzene layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. Ethyl ether was added to this concentrated solution, and the resulting precipitate was filtered and recrystallized from toluene. Yield 4.5 m (50%), mp 169-1710○. Example Bis(4-hydroxy-3-methoxybenzylidene) A solution of 0.607 g of pentaerythritol and 0.45 g of triethylamine in 1 ow of dichloromethane was added with 5 g of a solution of 0.305 g of terephthaloyl chloride in dichloromethane. It was added dropwise at room temperature, and then reacted for 2 hours.
反応混合物をメタノール４００の【に加え、生じた沈殿
をグラスフィルター上でメタノールを用いて洗浄した。
ｍークレゾールとメタノール系で再沈殿し、精製した。
収率０．７４３夕（９２．７％）また、同様にして、塩
化テレフタロィルの代りにセバシン酸ジクロラィトを用
いて、対応するポリエステルを製造した。このようにし
て得たポリエステルの物性を次に示す。The reaction mixture was added to 400 mL of methanol, and the resulting precipitate was washed on a glass filter with methanol.
It was reprecipitated with a m-cresol and methanol system and purified.
Yield: 0.743 (92.7%) In addition, a corresponding polyester was produced in the same manner using dichlorite sebacate in place of terephthaloyl chloride. The physical properties of the polyester thus obtained are shown below.
表
（注） Ｔｇ・・・ガラス転移点
Ｔｄ・・・分解点
りｉｎｈ…固有粘度、３０ｑ０、ｍークレゾール溶液（
０．１２５夕／ｄ‘）Ｍｎ・・・Ｈ‐Ｚａｈｎらが、「
Ｍａｋｒ。Table (note) Tg...Glass transition point Td...Decomposition point inh...Intrinsic viscosity, 30q0, m-cresol solution (
0.125 evening/d') Mn...H-Zahn et al.
Makr.
ｍ。１‐Ｃｈｅｍ．」６４，１８（１９６３）において
ポリエチレンテレフタレートのｍ−クレゾ
ール溶液に関して提案した極限粘
度〔り〕と数平均分子量Ｍｎとのm. 1-Chem. 64, 18 (1963), the relationship between the intrinsic viscosity and the number average molecular weight Mn was proposed for an m-cresol solution of polyethylene terephthalate.
Claims (1)
）で表わされる繰返し構造単位を有するグアヤシル基を
有するポリエステル。[Claims] 1 (1) A polyester having a guaiacyl group having a repeating structural unit represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein R is a polymethylene group or an arylene group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7198281A JPS6026492B2 (en) | 1981-05-13 | 1981-05-13 | Polyester with guaiacyl group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7198281A JPS6026492B2 (en) | 1981-05-13 | 1981-05-13 | Polyester with guaiacyl group |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57187318A JPS57187318A (en) | 1982-11-18 |
| JPS6026492B2 true JPS6026492B2 (en) | 1985-06-24 |
Family
ID=13476172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7198281A Expired JPS6026492B2 (en) | 1981-05-13 | 1981-05-13 | Polyester with guaiacyl group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6026492B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60114182U (en) * | 1983-12-28 | 1985-08-02 | 株式会社 多田野鉄工所 | Boom reduction rope |
-
1981
- 1981-05-13 JP JP7198281A patent/JPS6026492B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60114182U (en) * | 1983-12-28 | 1985-08-02 | 株式会社 多田野鉄工所 | Boom reduction rope |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57187318A (en) | 1982-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3069386A (en) | Thermoplastic aromatic polyformal resins and process for preparing same | |
| EP0172849A1 (en) | OPTICALLY ANISOTROPIC AND MELTABLE POLYMERS. | |
| US3220979A (en) | Preparation of aromatic phenols | |
| US2789971A (en) | Polycarbonates from 4, 4'-bis (beta-hydroxyethyl)-biphenyl-bis | |
| US4226967A (en) | Highly charge-transferable polycondensation polymer and process for preparation | |
| US4356298A (en) | Polyaromatic ether-ketone-sulfones containing 1,3-butadiene units | |
| JPS6026492B2 (en) | Polyester with guaiacyl group | |
| US2968646A (en) | Polyformals of cyclic diols | |
| US5302729A (en) | Dibenzo crown monomers and polymers formed therefrom | |
| US5110993A (en) | 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene and poly(arylene ethers) | |
| JPS62161834A (en) | Production of crosslinked polymer | |
| US4547592A (en) | Thermosetting arylether compounds and their synthesis | |
| US3470235A (en) | Alicyclic bisphenyleneoxydicarboxylic acids,salts and esters | |
| US5241037A (en) | Nadimide-terminated polyarylates and cured polyarylate resins | |
| US5418312A (en) | Difunctional cyclobutabenzene monomers | |
| US5219978A (en) | Poly(arylene ether)from 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene | |
| US3125569A (en) | J-amino-z | |
| US4197394A (en) | Method for making cyclic carbonates and polymers therefrom | |
| US3962191A (en) | Linear isocyanurate polyesters and processes for preparing same | |
| US3412069A (en) | Polyesters with spiro structure | |
| CA1089862A (en) | Dicarboxylic acids and dicarboxylic acid esters containing a 1,1'-methylene-bis-hydantoin radical | |
| JPS6050794B2 (en) | Pentaerythritol derivative | |
| US3793296A (en) | Heterocyclized polymer | |
| US5331098A (en) | Mono- and di(functionally-substituted phenylene) semi-rigid crowns and precursors thereof | |
| US5142068A (en) | Mono- and di(functionally-substituted phenylene) semi-rigid crowns and processes for making |