JPH011723A - heat resistant polyester - Google Patents
heat resistant polyesterInfo
- Publication number
- JPH011723A JPH011723A JP62-155349A JP15534987A JPH011723A JP H011723 A JPH011723 A JP H011723A JP 15534987 A JP15534987 A JP 15534987A JP H011723 A JPH011723 A JP H011723A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- component
- polyester
- heat
- molar ratio
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims description 31
- 239000000203 mixture Substances 0.000 claims description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 26
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 11
- 239000001361 adipic acid Substances 0.000 description 10
- 235000011037 adipic acid Nutrition 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000002076 thermal analysis method Methods 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
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic carboxylic acids Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- XCIZDMWWICZWIR-UHFFFAOYSA-N 2-ethyl-4-[1-(3-ethyl-4-hydroxyphenyl)-9H-fluoren-2-yl]phenol Chemical compound C(C)C=1C=C(C=CC=1O)C1=C(C=2CC3=CC=CC=C3C=2C=C1)C1=CC(=C(C=C1)O)CC XCIZDMWWICZWIR-UHFFFAOYSA-N 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 1
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- MGIAHHJRDZCTHG-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 MGIAHHJRDZCTHG-UHFFFAOYSA-N 0.000 description 1
- GZQVSHDBWIXGOC-UHFFFAOYSA-N benzene-1,4-dicarbonyl chloride;hexanedioyl dichloride Chemical compound ClC(=O)CCCCC(Cl)=O.ClC(=O)C1=CC=C(C(Cl)=O)C=C1 GZQVSHDBWIXGOC-UHFFFAOYSA-N 0.000 description 1
- IRXBNHGNHKNOJI-UHFFFAOYSA-N butanedioyl dichloride Chemical compound ClC(=O)CCC(Cl)=O IRXBNHGNHKNOJI-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LVIMBOHJGMDKEJ-UHFFFAOYSA-N heptanedioyl dichloride Chemical compound ClC(=O)CCCCCC(Cl)=O LVIMBOHJGMDKEJ-UHFFFAOYSA-N 0.000 description 1
- MMHWNKSVQDCUDE-UHFFFAOYSA-N hexanedioic acid;terephthalic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 MMHWNKSVQDCUDE-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、新規な耐熱ポリエステル成形材ネ１に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel heat-resistant polyester molding material.
従来の技術
９．９−ビス（４−ヒドロキシフェニル）フルオレンを
原料としたポリエステルは、従来からいろいろ提案され
ている。Prior Art 9. Various polyesters made from 9-bis(4-hydroxyphenyl)fluorene have been proposed in the past.
たとえば、９・、９−ビス（４−ヒドロキシフェニル）
フルオレンとテレフタル酸またはイソフタル酸とのポリ
エステルはマクロモルキュール３．５３６ （１９７０
年）に、また、９．９−ビス（４−と）′ロキシフェニ
ル）フルオレンとテレフタル酸−イソフタル酸混合（３
ニア〜７：３）のポリエステルは特開昭５７−１９２４
３２号公報に報告されている。For example, 9.,9-bis(4-hydroxyphenyl)
Polyesters of fluorene and terephthalic acid or isophthalic acid are macromolecules 3.536 (1970
In addition, 9,9-bis(4- and)'roxyphenyl)fluorene and terephthalic acid-isophthalic acid mixture (3
The polyester of near to 7:3) was published in Japanese Patent Application Laid-Open No. 57-1924.
It is reported in Publication No. 32.
また９、９−ビス（４−ヒドロキシフェニル）フルオレ
ンとインクタル酸あるいは脂肪酸との単独ポリエステル
は、米国特許第３，５４６，１６５号に報１１？されて
いる。前記特許には、可溶性耐熱ポリエステルとして、
テレフタル酸／イソフタル酸（モル比２０／８０） 、
テレフタル酸／セバシン酸（モル比ｆ３０／ ４０）を
用いた場合が記載されているが、いずれもフィルム成形
はなされていない。Further, a single polyester of 9,9-bis(4-hydroxyphenyl)fluorene and inctaric acid or fatty acid is reported in US Pat. No. 3,546,165. has been done. The patent states that as a soluble heat-resistant polyester,
Terephthalic acid/isophthalic acid (molar ratio 20/80),
A case using terephthalic acid/sebacic acid (molar ratio f30/40) is described, but film formation is not performed in either case.
発明が解決しようとする問題点
本発明者らは、これらの追試を行ったところ、いずれも
重合度が低く、溶剤に溶解した際に一部町溶であるもの
の白濁した溶液しか得られず、またフィルムにキャスト
した際きれいな良質のフィルムが得られなかった。Problems to be Solved by the Invention When the present inventors conducted supplementary tests on these, they all had a low degree of polymerization, and when dissolved in a solvent, only a cloudy solution was obtained, although some of it was dissolved in a solvent. Also, when cast on film, a clean, high-quality film could not be obtained.
さらに射出、押出、圧縮などの成形加工をする場合、加
工温度を高めなければ成形はできず、高７１１１ａにす
ると、分解するなど加工性に問題があり、４′＃に射出
成形に適用することは困難であった。Furthermore, when performing molding processes such as injection, extrusion, and compression, molding cannot be performed unless the processing temperature is raised, and if the height is 7111a, there will be problems with workability such as decomposition, so 4'# should not be applied to injection molding. was difficult.
本発明は、これらの問題点を解決したもので、ジオール
成分とフタル酸と脂肪酸の混合酸成分を含有させること
により、加工性に優れたＩ耐熱性ポリエステルを提供す
ることを０（ｒ！Ｊとするものである。The present invention solves these problems, and aims to provide a heat-resistant polyester with excellent processability by containing a diol component and a mixed acid component of phthalic acid and fatty acid. That is.
問題点を解決するためのｆ段
すなわら、本発明は一般式（Ｉ）で示される構造を有し
、
−ＧＸ−Ｙ）７晶−−−−一−→〔Ｘ−Ｚｈ参ｅ・（１
）（ただし、式中Ｘは
Ｚ ＋ｆ−ＯＣ（ＣＨ７）ｔｃ Ｏ”’Ｑアリ、Ｘ中（
７）ＲはＨ１ＣＨ３、Ｃ，Ｈ，のいずれかの基であり、
立は２〜６の整数、ｍ、ｎは繰り返し数を示す、）
Ｙ成分とＺ成分のモル比が１／８９〜９９／１であるポ
リエステルであり、かつ前記ポリエステル０．５ｇを８
０屯稙％のフェノールと４０重量％の１，１，２．２−
テトラクロロエタンの混合液１０（ｌｄに溶解した溶液
の３０℃で測定したインヘレント粘度（η１ｎｈ）が少
なくとも０．８ｄＪｌ ／ｇである耐熱性ポリエステル
である。In order to solve the problem, the present invention has a structure represented by the general formula (I), -GX-Y) 7 crystals - - - -> [X-Zh (1
) (However, in the formula, X is Z +f-OC(CH7)tc O"'Q ant,
7) R is any group of H1CH3, C, H,
is an integer of 2 to 6, m and n indicate the number of repetitions) A polyester in which the molar ratio of the Y component and the Z component is 1/89 to 99/1, and 0.5 g of the polyester is
0 tonne% phenol and 40% by weight 1,1,2.2-
A heat-resistant polyester having an inherent viscosity (η1nh) of at least 0.8 dJl/g measured at 30°C in a solution dissolved in a mixture of tetrachloroethane 10 (ld).
以下さらに本発明の詳細な説明する。The present invention will be further explained in detail below.
本発明のポリエステルは、ジオール成分と、テレフタル
酸および／又はイソフタル酸および脂肪酸からなる酸混
合成分を含有するものであり、フタル酸成分と脂肪酸成
分のモル比が１７９９〜９９／１のものである。この中
でも、特にテレフタル酸とアジピン酸との割合がそれぞ
れモル比で１／９９〜θ０／４０のものは好ましい特性
を示す。The polyester of the present invention contains a diol component and an acid mixture component consisting of terephthalic acid and/or isophthalic acid and fatty acid, and has a molar ratio of phthalic acid component to fatty acid component of 1799 to 99/1. . Among these, those having a molar ratio of terephthalic acid and adipic acid of 1/99 to θ0/40 exhibit particularly preferable characteristics.
本発明のポリエステルはガラス転移温度（Ｔｇ）１７０
〜３２０℃、インヘレント粘度が０．６ｄ文／ｇ以−ヒ
で高徹合度である。−船釣に加熱して成形物をつくる場
合、分解温度（Ｔｄ） 、ガラス転移温度の差が約５０
℃以上必要である０本ポリエステルはこの条ヂＩを満た
すとともに、さらにカルボン酸の混合＋”ｆＪ Ｗを変
化させ、Ｔｇを制御しうることは射出成形材料として好
ましいものである。また、電気的特性なども優れている
ことから、たとえばソケット、電ｒ−レンジなどの電気
部品などの分野に好適に使用することができ、さらに耐
熱性接着剤として使用も可能であるが、これらに限られ
るものではない。The polyester of the present invention has a glass transition temperature (Tg) of 170
~320°C, the inherent viscosity is 0.6 dm/g or more, and the degree of purity is high. - When making molded products by heating on a boat, the difference in decomposition temperature (Td) and glass transition temperature is approximately 50
℃ or higher, polyester is preferable as an injection molding material because it satisfies this condition I and can further control Tg by changing the carboxylic acid mixture + fJW. Due to its excellent properties, it can be suitably used in the field of electrical parts such as sockets and microwave ovens, and can also be used as a heat-resistant adhesive, but it is limited to these applications. isn't it.
まず、本発明に用いられるジオール類としては次式で示
されるものである。First, the diols used in the present invention are represented by the following formula.
但し、ＲはＨ、ＣＨ３、Ｃ２Ｈ５のいずれかの基である
。これらのジオール類としては９．９−ビス（４−ヒド
ロキシフェニル）フルオレン、９．９＝ビス（３−メチ
ル−４−ヒドロキシフェニル）フルオレン及び９，９−
ビス（３−エチル−４−ヒドロキシフェニル）フルオレ
ン等が挙ケられる。However, R is any one of H, CH3, and C2H5. These diols include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, and 9,9-
Examples include bis(3-ethyl-4-hydroxyphenyl)fluorene.
また、カルボン酸成分の芳香族カルボン酸としてはフタ
ル酸および／またはイソフタル酸が挙げられ、脂肪族カ
ルボン酸、ＨＯＯＣ（−ＣＲ２）えＣ０ＯＨとして、文
＝２〜６のコハク酩、グルタル酸、アジピン酸、ビメル
酸およびスヘル酸等が挙げられ、なかでもアジピン酸が
好適である。In addition, aromatic carboxylic acids of the carboxylic acid component include phthalic acid and/or isophthalic acid, and aliphatic carboxylic acids, HOOC(-CR2) and C0OH, succinic acid with sentence = 2 to 6, glutaric acid, adipine Examples include bimeric acid and schelic acid, among which adipic acid is preferred.
これは、分解温度をできる限り高く維持しガラス転移温
度を制御するには脂肪族カルボン酸の脂肪鎖が長すぎて
は分解温度が下がってしまい、また脂肪鎖が１０かすぎ
てはガラス温度が下がりきらないからである。This is because in order to maintain the decomposition temperature as high as possible and control the glass transition temperature, if the fatty chain of the aliphatic carboxylic acid is too long, the decomposition temperature will drop, and if the fatty chain is too long, the glass temperature will decrease. This is because it cannot go down completely.
さらに、芳香族カルボン酸と脂肪族カルボン酸の割合に
ついてであるが、本発明においては、テレフタル酸およ
び／またはイソフタル酸に脂肪酸を特定が含有させＴｇ
を下げることによって成形（射出、押出、圧縮など）可
能とすることも一つの目的である。脂肪酸成分を含有さ
せると、Ｔｇは下がるが、ＴｄはＴｇと傾向が異なり、
Ｔｄは下がらない。また脂肪酸成分の導入によりフィル
ム化した場合柔軟性も増し、ＪｎＲ剤として使用する場
合、Ｉａ Ｉｔ力取り扱い易さも増す。本発明者はこの
ＴｇとＴｄとの傾向のＸｉ異を見出し、これを巧みに利
用した耐熱性ポリエステルとして利用するようにしたも
のである。Furthermore, regarding the ratio of aromatic carboxylic acid and aliphatic carboxylic acid, in the present invention, terephthalic acid and/or isophthalic acid contain a specific fatty acid, and Tg
One of the purposes is to enable molding (injection, extrusion, compression, etc.) by lowering the temperature. When fatty acid components are included, Tg decreases, but Td has a different tendency from Tg.
Td does not decrease. In addition, the introduction of fatty acid components increases flexibility when formed into a film, and when used as a JnR agent, increases ease of handling. The inventor of the present invention discovered this difference in the tendency of Xi between Tg and Td, and skillfully utilized this as a heat-resistant polyester.
第り図に一例として、本発明のポリエステル（テレフタ
ル酸−アジピン酸）の熱分析結果例を示すものである。As an example, Fig. 1 shows an example of the results of thermal analysis of the polyester (terephthalic acid-adipic acid) of the present invention.
横→１１１にテレフタル酸／アジピン酸の比率、縦軸に
温度をとり、これにガラス転移温度Ａ線図及び分解開始
温度Ｂ線図を示したものである。The terephthalic acid/adipic acid ratio is plotted horizontally at 111, the temperature is plotted on the vertical axis, and the glass transition temperature A diagram and decomposition start temperature B diagram are shown.
図面に示すようにテレフタル酸／アジピン酸のモル比が
大きくなると、ガラス転移温度が直線的に増加すること
、一方分解開始温度はテレフタル酸／アジピン酸のモル
比が８０／２０から１０／９０の間は−・定であるが、
その比が８０／２０をこえると急激にＪ−昇する。As shown in the figure, as the molar ratio of terephthalic acid/adipic acid increases, the glass transition temperature increases linearly, while the decomposition initiation temperature increases as the molar ratio of terephthalic acid/adipic acid increases from 80/20 to 10/90. The interval is -・constant, but
When the ratio exceeds 80/20, J- increases rapidly.
従ってテレフタル酸／アジピン酸のモル比が約Ｇｏ／４
０をこえると射出球形温度が好適とされるガラス転移温
度＋５０℃をこえるので、射出成形時に分解する恐れが
ある。Therefore, the molar ratio of terephthalic acid/adipic acid is approximately Go/4.
If it exceeds 0, the injection spherical temperature exceeds the glass transition temperature +50° C., which is preferable, and there is a risk of decomposition during injection molding.
従ってテレフタル酸／アジピン酸のモル比が１／９９〜
６０／４０、特にＩ／９９〜４０／６０以ｆのものが成
形材料としては好ましい。Therefore, the molar ratio of terephthalic acid/adipic acid is 1/99~
60/40, especially I/99 to 40/60 or less f is preferable as a molding material.
さらに本ポリエステルは成形材料としてだけ有用なので
はなく、耐熱性接着剤としても有用である。接着法、利
用箇所の相違により芳香族カルボン酸と脂肪族カルボン
酸の比をかえたポリエステルを用いることができる。Furthermore, the polyester is useful not only as a molding material, but also as a heat-resistant adhesive. Polyesters with different ratios of aromatic carboxylic acid and aliphatic carboxylic acid can be used depending on the adhesion method and the location of use.
次に本発明のポリエステルの製法について説明する。Next, the method for producing the polyester of the present invention will be explained.
原料となるジオール類にアルカリを添加してアルカリ水
溶液とする。アルカリとしては特に制約されるものはな
いが、苛性ソーダなどが好ましい。アルカリ水溶液の濃
度としては２％以下、好ましくは０．８〜１．５％程度
の水溶液が右利である。An alkali is added to the raw material diols to form an alkaline aqueous solution. There are no particular restrictions on the alkali, but caustic soda and the like are preferred. The concentration of the alkaline aqueous solution is preferably 2% or less, preferably about 0.8 to 1.5%.
このアルカリ水溶液にジオール類を添加し、ジオール類
アルカリ水溶液とする。Diols are added to this alkaline aqueous solution to obtain a diol alkaline aqueous solution.
酸成分として、各々のカルボン酸のクロリドが好適に用
いられる。この酸クロリドは有機／＼ロゲン化合物、た
とえば１．２ジクロロエタン、クロロホルム、トリクロ
ルエタンなどに溶解して酸成分有機溶剤溶液とする。As the acid component, chloride of each carboxylic acid is preferably used. This acid chloride is dissolved in an organic/\rogen compound such as 1.2 dichloroethane, chloroform, trichloroethane, etc. to form an acid component organic solvent solution.
次いでジオール類アルカリ水溶液と酸成分有機溶剤溶液
とを攪拌下、界面重縮合する。Next, the diol alkali aqueous solution and the acid component organic solvent solution are subjected to interfacial polycondensation while stirring.
なお、界面重縮合はその反応が界面で行われるので乳化
しない程度の量の界面活性剤をジオール類アルカリ水溶
液に添加すると反応が促進されるので好ましい。Incidentally, since the interfacial polycondensation reaction takes place at the interface, it is preferable to add a surfactant to the diol alkali aqueous solution in an amount that does not cause emulsification, since this will accelerate the reaction.
界面活性剤としてはジオール類あるいは酸クロリドと反
応してはならない、またアルカリ水溶液に添加されるの
でアルカリに強いものが好ましい。The surfactant must not react with diols or acid chlorides, and is preferably resistant to alkali since it is added to an aqueous alkali solution.
具体的にはカチオン系のテトラエチルアンモニウム−ク
ロリドなどが挙げられる。その添加量は界面活性剤の種
類などによって変るが、通常界面東金に使用される賃で
十分であり、たとえば５％以下の水溶液、好ましくは２
％以下の水溶液となるような皆である。余り多く使用す
ると乳化し、界面重合困難となるので好ましくない。Specific examples include cationic tetraethylammonium chloride. The amount added varies depending on the type of surfactant, etc., but the amount normally used for interface togane is sufficient, for example, an aqueous solution of 5% or less, preferably 2.
% or less in aqueous solution. If too much is used, emulsification will occur and interfacial polymerization will become difficult, which is not preferable.
反応温度は０〜８０℃、好ましくは２０〜３０℃であり
、反応時間は数蒔間から２４時間程度で十分である。The reaction temperature is 0 to 80°C, preferably 20 to 30°C, and the reaction time is sufficient to range from several sowings to about 24 hours.
反応終了後、得られた水層と油層を分離し、油層性に有
機ハロゲン化合物を添加し、粘度を低下させるとノ（に
水洗をする。After the reaction is completed, the resulting aqueous and oil layers are separated, and an organic halogen compound is added to the oil layer to reduce its viscosity, followed by washing with water.
次いで、これをメタノールやアセトン中に注ぎ、析出物
を濾別し、乾燥すると本発明のポリエステルが得られる
。Next, this is poured into methanol or acetone, and the precipitate is filtered off and dried to obtain the polyester of the present invention.
実施例 以下実施例をあげて、さらに本発明の詳細な説明する。Example The present invention will be further explained in detail with reference to Examples below.
実施例１
（アジピン酸／テレフタル酸モル比＝ ８０／ ２０）
。Example 1 (Adipic acid/terephthalic acid molar ratio = 80/20)
.
テレフタル酸クロリド４．０４ ｇ、アジピン酸クロリ
ド１４．６ｇを１．２−ジクロロエタン３００−に溶解
する。4.04 g of terephthalic acid chloride and 14.6 g of adipic acid chloride are dissolved in 300 g of 1,2-dichloroethane.
木１０００−に苛性ソーダを８〜１５ｇ添加溶解し、こ
れに９，９−ビス（４−ヒドロキシフェニル）フルオレ
ン３５ｇ、テトラエチルアンモニウムクロリド１５ｇを
溶解する。この溶液を前記酸成分有機溶剤溶液に激しく
攪拌しながら−ダｔに加え、１０〜１５時間反応させた
。反Ｉ５後水層を捨て、油層に１．２−ジクロロエタン
２００−を加え、粘度を低下させた。8 to 15 g of caustic soda is added and dissolved in Wood 1000-, and 35 g of 9,9-bis(4-hydroxyphenyl)fluorene and 15 g of tetraethylammonium chloride are dissolved therein. This solution was added to the acid component organic solvent solution with vigorous stirring and allowed to react for 10 to 15 hours. After I5, the aqueous layer was discarded, and 1,2-dichloroethane 200% was added to the oil layer to reduce the viscosity.
これを木５００シで３回洗浄し、これをアセトン中に注
ぎ、析出物を濾別し、乾燥しポリエステルを得た。This was washed three times with a wooden sieve, poured into acetone, the precipitate was filtered off, and dried to obtain a polyester.
また物性試験を行った結果を表１に示す。Table 1 also shows the results of physical property tests.
実施例２
テレフタル酸クロリド−アジピン酸クロリド混合物（酸
モル比でｌ／９９〜９９／１）を１００ミリモルを１．
２−ジクロロエタン３００−に溶解後、実施例１の９．
９−ビス（４−ヒドロキシフェニル）フルオレン水溶液
を加え激しく攪拌した。以下実施例１と同様に行った。Example 2 100 mmol of a terephthalic acid chloride-adipic acid chloride mixture (acid molar ratio 1/99 to 99/1) was mixed with 1.
After dissolving in 300% of 2-dichloroethane, 9.
An aqueous solution of 9-bis(4-hydroxyphenyl)fluorene was added and stirred vigorously. The following steps were carried out in the same manner as in Example 1.
実施例３
実施例１におけるテレフタル酸クロリドにかえ、インフ
タル酸クロリドを用いアジピン酸／インフタル酸モル比
＝ ９０／ １０として合成を行った。Example 3 Synthesis was carried out using inphthalic acid chloride instead of terephthalic acid chloride in Example 1, with the adipic acid/inphthalic acid molar ratio being 90/10.
その他は全く同様に行った０分解部度３８０℃、ガラス
転移温度２００℃、インヘレント粘度０．８５ｄＪＬ／
ｇであった。Other conditions were exactly the same. Zero decomposition degree 380℃, glass transition temperature 200℃, inherent viscosity 0.85dJL/
It was g.
実施例４
実施例１におけるアジピン酸クロリドにかえて等モルの
コハク酸クロリド、グルタル酸クロリド、ピメル酸クロ
リド、スペル酸クロリドを各々１２．７ｇ、 １３．８
ｇ、１８．１ｇ、１７．２ｇを用いて、その他は全く同
様に行った。ガラス転移温度は各々２８４°Ｃ１２５９
℃、 ２１０℃、２００℃、分解温度は各々 ４００℃
、 ４００℃、 ３５０℃、３４５℃またインヘレント
粘度は０．７３．０．８０．０．８５．０．８６ｄＫＬ
／ｇであった。Example 4 In place of adipic acid chloride in Example 1, equimolar amounts of succinic acid chloride, glutaric acid chloride, pimelic acid chloride, and superic acid chloride were each used in an amount of 12.7 g and 13.8 g, respectively.
The same procedure was used except that 18.1 g, 18.1 g, and 17.2 g were used. Each glass transition temperature is 284°C1259
℃, 210℃, 200℃, decomposition temperature is 400℃ each
, 400℃, 350℃, 345℃ and the inherent viscosity is 0.73.0.80.0.85.0.86dKL
/g.
表１に示した物性の測定法は次の方法によった。The physical properties shown in Table 1 were measured by the following method.
１、引張強度・・・オートグラフＤＳＳ ２０００ （
島津製作所）を用いて巾１０ｍＪｊさ１００鵬■のフィ
ルムで測定した。1. Tensile strength: Autograph DSS 2000 (
(Shimadzu Corporation) and a film with a width of 10 m and a width of 100 mm.
２、引張弾性率・・・同上
３、引張敲断伸びφ・・同上
４、分解温度−・・メトラー熱分析システムＴＡ３００
０を用いて行った。2. Tensile modulus...Same as above 3. Tensile elongation φ...Same as above 4. Decomposition temperature...Mettler Thermal Analysis System TA300
This was done using 0.
５、ガラス転移温度ｍ−・同」−
８、体積抵抗率φ、 −ＪＩＳ （：２３１８に従って
フィルムにスズ箔をはったものを電極として用い測定し
た。5. Glass transition temperature m-- 8. Volume resistivity φ, - Measured using a film covered with tin foil as an electrode according to JIS (2318).
？、誘’ｉｆｆ率、誘電正接・・・同上８、絶縁破壊強
さ・・・フィルムを空気中ロッド状の電極にはさみ測定
した。? , di'iff constant, dielectric loss tangent... 8, dielectric breakdown strength... The film was sandwiched between rod-shaped electrodes in the air and measured.
９、屈折率・命・アタゴ屈折計により測定した。9.Refractive index and index were measured using an Atago refractometer.
１０、全光線透過率会・・ＪＩＳ Ｋ７１０５に従って
測定した。10. Total light transmittance... Measured according to JIS K7105.
１１、黄色度・・・ＪＩＳ Ｋ７１０３に従って測定し
た。11. Yellowness: Measured according to JIS K7103.
１２、ヘーズ・・拳ＪＩＳ Ｋ７１０５に従って測定し
た。12. Haze: Measured according to Fist JIS K7105.
１３、吸水率・・・ １２０℃１０時間以上乾燥した後
、２３℃２４時間イオン交換水中に浸漬し、測定した。13. Water absorption rate... After drying at 120°C for 10 hours or more, it was immersed in ion exchange water at 23°C for 24 hours and measured.
１４、溶解性−φ・Ｉｇのポリマーを５−に溶解させる
ことにより測定した。14. Solubility - Measured by dissolving the polymer of φ·Ig in 5-.
１５、 インヘレント粘度・・・６０重量％のフェノ
ール及ヒ４０重量％の混合液１０〇−中にポリエステル
０．５ｇ含有した溶液の粘度測定値（３０℃）。15. Inherent viscosity: Measured viscosity of a solution containing 0.5 g of polyester in 100% of a mixed solution of 60% by weight of phenol and 40% by weight (at 30°C).
発明の効果
本発明は、ガラス転移温度１７０〜３２０°Ｃ１引張’
ｒｉｌ！ Ｉ隻６ｋｇ／ｌｌｌｆｆ１２以ヒ、インヘレ
ント粘度が０．１３ｔｆＪＪ／ｇ以）−の耐熱ポリエス
テルであって、従来成形加１、が困難であるとされてい
たポリエステルの成形を”ｆ ｉｋとした画期的な材料
である。Effects of the invention The present invention has a glass transition temperature of 170 to 320° C1 tensile
ril! This is a heat-resistant polyester with a weight of 6 kg/lllff12 or higher, an inherent viscosity of 0.13 tfJJ/g or higher, and is a breakthrough in the molding of polyester, which was conventionally considered difficult to mold. It is a typical material.
その利用分野としては現段階で旧市されている各種の機
械部品、電気部品等のプラスチックの成形品に相当する
か、又はこれを上回る成形品を安ｆ＋ＩＩｉ ４こ供給
することができ産業上有意義である。As for its field of use, it is industrially significant because it can supply molded products equivalent to or superior to plastic molded products such as various mechanical parts and electrical parts that are currently available in the old market. It is.
Ｓらに１耐熱性接着剤としても使用可能であり、−層有
意義である。It can also be used as a heat-resistant adhesive, making it a useful layer.
第１図は本発明の実施例のポリエステルの熱分析による
テレフタル酸／アジピン酸モル比とガラス転移温度Ａ、
分解開始温度Ｂの関係図である。
代理人 弁理士 井 上 雌牛FIG. 1 shows the terephthalic acid/adipic acid molar ratio and glass transition temperature A, as determined by thermal analysis of the polyester of the example of the present invention.
It is a relationship diagram of decomposition start temperature B. Agent Patent Attorney Kei Inoue
Claims (4)
化学式、表等があります▼・・・（ I ） （ただし、式中Ｘは Ｙは▲数式、化学式、表等があります▼、 Ｚは−ＯＣ（ＣＨ＿２）＿ｌＣＯ−であり、Ｘ中のＲは
Ｈ、ＣＨ＿３、Ｃ＿２Ｈ＿５のいずれかの基であり、ｌ
は２〜６の整数、ｍ、ｎは繰り返し数を示す。） Ｙ成分とＺ成分のモル比が１／９９〜９９／１であるポ
リエステルであり、かつ前記ポリエステル０．５ｇを６
０重量％のフェノールと４０重量％の１，１，２，２−
テトラクロロエタンの混合液１００ｍｌに溶解した溶液
の３０℃で測定したインヘレント粘度（ηｉｎｈ）が少
なくとも０．６ｄｌ／ｇである耐熱性ポリエステル。(1) Has a structure represented by the general formula (I), ▲ mathematical formula,
There are chemical formulas, tables, etc.▼...(I) (However, in the formula, H, CH_3, C_2H_5, l
is an integer of 2 to 6, and m and n indicate the number of repetitions. ) A polyester in which the molar ratio of the Y component and the Z component is 1/99 to 99/1, and 0.5 g of the polyester is
0 wt% phenol and 40 wt% 1,1,2,2-
A heat-resistant polyester having an inherent viscosity (ηinh) of at least 0.6 dl/g, measured at 30° C. in a solution dissolved in 100 ml of a mixture of tetrachloroethane.
る特許請 求の範囲第１項記載の耐熱性ポリエステル。(2) The heat-resistant polyester according to claim 1, wherein the Y component is ▲a numerical formula, a chemical formula, a table, etc.▼.
Ｚ成分が −ＯＣ（ＣＨ＿２）＿４ＣＯ−である特許請求の範囲第
１項記載の耐熱性ポリエステル。(3) The Y component is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
The heat-resistant polyester according to claim 1, wherein the Z component is -OC(CH_2)_4CO-.
である特許請求の範囲第１項記載の耐熱性ポリエステル
。(4) The molar ratio of Y component and Z component is 1/99 to 60/40
The heat-resistant polyester according to claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155349A JPS641723A (en) | 1987-06-24 | 1987-06-24 | Heat-resistant polyester |
| US07/210,738 US4810771A (en) | 1987-06-24 | 1988-06-23 | Heat-resistant co-polyester from 9,9-bis(4-hydroxy-phenyl)fluorene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62155349A JPS641723A (en) | 1987-06-24 | 1987-06-24 | Heat-resistant polyester |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JPH011723A true JPH011723A (en) | 1989-01-06 |
| JPS641723A JPS641723A (en) | 1989-01-06 |
| JPH0422931B2 JPH0422931B2 (en) | 1992-04-20 |
Family
ID=15603948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62155349A Granted JPS641723A (en) | 1987-06-24 | 1987-06-24 | Heat-resistant polyester |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4810771A (en) |
| JP (1) | JPS641723A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2221917B (en) * | 1988-05-16 | 1992-10-21 | Nippon Steel Corp | Organic polymer separation membrane having fluorene skeleton and oxygen enrichment device utilizing same |
| US4904755A (en) * | 1989-01-23 | 1990-02-27 | Eastman Kodak Company | Low birefringent polyesters in optical devices |
| US4968331A (en) * | 1989-05-15 | 1990-11-06 | Nippon Steel Corporation | Organic polymer separation membrane having fluorene skeleton and oxygen enrichment device utilizing same |
| US4925913A (en) * | 1989-09-08 | 1990-05-15 | Nippon Steel Corporation | Heat-resistant unsaturated polyester |
| JPH044615A (en) * | 1990-04-23 | 1992-01-09 | Pioneer Electron Corp | Radio receiver |
| US5670603A (en) * | 1993-03-08 | 1997-09-23 | Alliedsignal Inc. | Polymers exhibiting nonlinear optical properties |
| WO1999018141A1 (en) * | 1997-10-03 | 1999-04-15 | Unitika Ltd. | Highly heat-resistant, high-purity polyarylate and film produced from the same |
| US7022772B2 (en) * | 2000-11-14 | 2006-04-04 | Ferraria Technologies S.P.A. | Optical film comprising polyarylates containing bis-(hydroxyphenyl)-fluorene-ortho-disubstituted bisphenols |
| ITSV20000053A1 (en) | 2000-11-14 | 2002-05-14 | Allaix Roberto C O Ferrania S P A Uff Brevetti | OPTICAL FILM INCLUDING POLYARYLATES CONTAINING BISPHENOLS BIS (HYDROXYPHENYL) FLUOREN-ORTHO-BISUBSTITUTED. |
| ITSV20030020A1 (en) * | 2003-04-11 | 2004-10-12 | Allaix Roberto C O Ferrania S P A Uff Brevetti | OPTICAL MEDIUM INCLUDING A FILM OF POLYMERIC MATERIAL. |
| ITSV20030018A1 (en) * | 2003-04-11 | 2004-10-12 | Allaix Roberto C O Ferrania S P A Uff Brevetti | OPTICAL MEDIUM INCLUDING A FILM OF POLYMERIC MATERIAL. |
| US7862856B1 (en) * | 2006-03-10 | 2011-01-04 | The United States Of America As Represented By The Secretary Of The Air Force | Method for making high temperature polymer dielectric compositions incorporating diamond-like hydrocarbon units for capactive energy storage applications |
| EP1936008A1 (en) * | 2006-12-22 | 2008-06-25 | AGC Flat Glass Europe SA | Manufacture of layer by magnetron sputtering |
| JP5225209B2 (en) * | 2009-06-10 | 2013-07-03 | 大阪瓦斯株式会社 | Polyester resin having a fluorene skeleton |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546165A (en) * | 1966-02-01 | 1970-12-08 | Du Pont | Soluble high-melting,thermally stable linear polyesters |
| US3738968A (en) * | 1970-10-15 | 1973-06-12 | Monsanto Co | Copolyamides of 9,9-bis(3-aminopropyl)-fluorene |
-
1987
- 1987-06-24 JP JP62155349A patent/JPS641723A/en active Granted
-
1988
- 1988-06-23 US US07/210,738 patent/US4810771A/en not_active Expired - Fee Related
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