JPH01153719A - Production of copolymerized polyester - Google Patents
Production of copolymerized polyesterInfo
- Publication number
- JPH01153719A JPH01153719A JP31350887A JP31350887A JPH01153719A JP H01153719 A JPH01153719 A JP H01153719A JP 31350887 A JP31350887 A JP 31350887A JP 31350887 A JP31350887 A JP 31350887A JP H01153719 A JPH01153719 A JP H01153719A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- dicarboxylic acid
- acid
- reaction
- aromatic dicarboxylic
- 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 abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 45
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 38
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001634 Copolyester Polymers 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 238000006640 acetylation reaction Methods 0.000 abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 3
- 150000008065 acid anhydrides Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000004075 acetic anhydrides Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- HQCVEGNPQFRFPC-UHFFFAOYSA-N carboxy acetate Chemical compound CC(=O)OC(O)=O HQCVEGNPQFRFPC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は溶融重合のみで合成が可能で、低価格の原料を
用いて、耐熱性の良好な成形品を与えることができる共
重合ポリエステルの製造方法に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to a copolyester that can be synthesized only by melt polymerization and that can give molded products with good heat resistance using low-cost raw materials. This relates to a manufacturing method.
〈従来の技術〉
芳香族ヒドロキシカルボン酸から生成するポリエステル
単位、芳香族ジオールと芳香族ジカルボン酸から生成す
るポリエステル単位およびアルキレングリコールおよび
芳香族ジカルボン酸から生成するポリエステル単位から
なる共重合ポリエステルは特開昭51−8395号公報
、特開昭58−84821号公報などに開示されている
。<Prior art> A copolymerized polyester consisting of a polyester unit produced from an aromatic hydroxycarboxylic acid, a polyester unit produced from an aromatic diol and an aromatic dicarboxylic acid, and a polyester unit produced from an alkylene glycol and an aromatic dicarboxylic acid is disclosed in Japanese Patent Publication No. It is disclosed in Japanese Patent Application Laid-Open No. 58-84821, etc.
特開昭51−8395号公報および特開昭58−848
21号公報に開示された共重合ポリエステルは、a、芳
香族ヒドロキシカルボン酸のアセチル化物、b、芳香族
ジカルボン酸とアルキレングリコールを縮合してなるポ
リエステル、C1芳香族ジオールのアセチル化物、と、
d、芳蕃族ジカルボン酸を仕込み縮合させる第1の工程
とその反応系を減圧にして高分子量とする第2の工程か
らなる方法で製造することが記載されている。JP-A-51-8395 and JP-A-58-848
The copolymerized polyester disclosed in Publication No. 21 includes a, an acetylated aromatic hydroxycarboxylic acid, b, a polyester obtained by condensing an aromatic dicarboxylic acid and an alkylene glycol, and an acetylated C1 aromatic diol;
d. It is described that it is produced by a method consisting of a first step of charging and condensing an aromatic dicarboxylic acid, and a second step of reducing the pressure of the reaction system to obtain a high molecular weight.
また、時開11g62−41220号公報には(i)芳
香族ヒドロキシカルボン酸、(it)芳香族ジカルボン
酸とアルキレングリコールを縮合してなるポリエステル
と(tit)掻く少量の芳香族ジオールと(iv)無水
酢酸を用い、(it)と、(i)とを反応させた後、(
tit)を加え、(iv)によりアセチル化することを
必須として製造する共重合ポリエステルの製造方法が開
示されている。Additionally, Jikai No. 11g62-41220 discloses (i) an aromatic hydroxycarboxylic acid, (it) a polyester obtained by condensing an aromatic dicarboxylic acid and an alkylene glycol, (tit) a small amount of an aromatic diol, and (iv) After reacting (it) and (i) using acetic anhydride, (
Disclosed is a method for producing a copolymerized polyester which essentially includes addition of titanium titanium titanium chloride titanium titanium chloride titanium titanium chloride titanium titanium chloride titanium chloride titanium chloride titanium titanium titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride titanium chloride chloride titanium chloride acetylated 100 chloride chloride acetylated by 100% chloride (iv).
〈発明が解決しようとする問題点〉
しかしながら、特開昭5 i −8395”号公報およ
び特開昭58−84821号公報記載の製造方法では■
芳香族ヒドロキシカルボン酸と■芳香族ジオールをあら
かじめ別工程でアセチル化物に誘導することが必要であ
り、ポリマを安価に得ることができない。また、特開昭
62−41220号公報記載の製造方法では■芳香族ジ
カルボン酸を共重合していないため、耐熱性が低く、分
子量の不十分なポリマ1か得られていない。さらに、(
iv)無水酢酸を後から添加するため、反応系を途中で
冷却する必要が生じるため、反応時間が長く、反応操作
が繁雑となる。<Problems to be solved by the invention> However, the manufacturing methods described in Japanese Patent Application Laid-open No. 5 i-8395" and Japanese Patent Application Laid-open No. 58-84821 have the following problems:
It is necessary to induce the aromatic hydroxycarboxylic acid and the aromatic diol into an acetylated product in separate steps in advance, and the polymer cannot be obtained at low cost. In addition, in the production method described in JP-A-62-41220, (1) the aromatic dicarboxylic acid is not copolymerized, resulting in Polymer 1 having low heat resistance and insufficient molecular weight. moreover,(
iv) Since acetic anhydride is added later, it is necessary to cool the reaction system midway through the reaction, resulting in a long reaction time and complicated reaction operation.
本発明はアセチル化されていないモノマを使用し、なお
かつ耐熱性が良好で熱安定性の高い共重合ポリエステル
を安価に得ることを課題とする。An object of the present invention is to use a non-acetylated monomer to obtain a copolyester having good heat resistance and high thermal stability at a low cost.
〈問題点を解決するための手段〉
すなわち、本発明は■下記構造単位(I>を有する芳香
族ヒドロキシカルボン酸、■下記構造単位(n)を有す
る芳香族ジカルボン酸とアルキレングリコールを縮合し
てなるポリエステル、■下記構造単位(DI)を有する
芳香族ジオールおよび■下記構造単位(IV)を有する
芳香族ジカルボン酸と■無水酢酸とから共重合ポリエス
テルを製造する際に、■下記構造単位(IV)を有する
芳香族ジカルボン酸の一部または全部を反応系に100
〜290℃で後添加することを特徴とする共重合ポリエ
ステルの製造方法である。<Means for Solving the Problems> That is, the present invention condenses (1) an aromatic hydroxycarboxylic acid having the following structural unit (I>), (2) an aromatic dicarboxylic acid having the following structural unit (n), and an alkylene glycol. When producing a copolymerized polyester from ■ an aromatic diol having the following structural unit (DI), ■ an aromatic dicarboxylic acid having the following structural unit (IV), and ■ acetic anhydride, ■ the following structural unit (IV ) to the reaction system.
This is a method for producing a copolyester characterized by post-addition at ~290°C.
HOA、 r t COOH(I )+OROCAr
4 coh n(If>HOA r 20 H(DI
)
HOOC−Ar −COOH(IV)(ただしAr
〜Ar は2価の芳香族基、R□は2価のアルキレ
ン基であり、Ar 〜Ar4は互いに同一であっても
異なっていてもよい。)本発明で製造する共重合ポリエ
ステルは上記(I)、(II)、(1)および(IV)
から誘導される。Ar 〜A r 4’は2価の芳香
族基であり、互いに同一で゛も異なっていてもよく、混
在するこlls
挙げられ、特に4.4−一ビフェニレン基やp −フェ
ニレン基および両者の混合物などが好ましい。HOA, r t COOH (I ) + OROCAr
4 coh n(If>HOA r 20 H(DI
) HOOC-Ar -COOH(IV) (However, Ar
~Ar represents a divalent aromatic group, R□ represents a divalent alkylene group, and Ar~Ar4 may be the same or different from each other. ) The copolymerized polyester produced in the present invention is the above-mentioned (I), (II), (1) and (IV).
derived from. Ar to Ar 4' are divalent aromatic groups, which may be the same or different from each other, and may be a mixture thereof, particularly 4.4-monobiphenylene group, p-phenylene group, and both. Mixtures and the like are preferred.
また、好ましく用いられるArsおよびA r 4又は
水素原子または塩素原子を表わす)などが挙げられ、い
ずれもパラフェニレン基かパラフェニレン基と他の基と
の共存が特に好ましい。Further, preferred examples include Ars and Ar (representing a hydrogen atom or a chlorine atom), which are particularly preferably paraphenylene groups or the coexistence of paraphenylene groups and other groups.
また、R1は2価のアルキレン基であり、特に+cH2
+2が好ましい。Moreover, R1 is a divalent alkylene group, especially +cH2
+2 is preferred.
本発明で製造する共重合ポリエステルは、■芳香族ヒド
ロキシカルボン酸、■芳香族ジカルボン酸とアルキレン
グリコールを縮合してなるポリエステルと■芳香族ジオ
ールからなるポリエステル原料、または、上記■〜■お
よび■芳香族ジカルボン酸のうちの一部からなるポリエ
ステル原料と■無水酢酸とを反応させ、■下記構造単位
(IV)を有する芳香族ジカルボン酸の一部または全部
を反応系に100〜290℃で後添加することを必須と
して製造される。The copolymerized polyester produced in the present invention is a polyester raw material consisting of (1) an aromatic hydroxycarboxylic acid, (2) a polyester formed by condensing an aromatic dicarboxylic acid and an alkylene glycol, and (2) an aromatic diol, or the above-mentioned (1) to (2) and (4) aromatic. A polyester raw material consisting of a part of group dicarboxylic acids is reacted with ■acetic anhydride, and part or all of an aromatic dicarboxylic acid having the following structural unit (IV) is post-added to the reaction system at 100 to 290°C. Manufactured as required.
■芳香族ヒドロキシカルボン酸と■芳香族ジオールは■
無水酢酸によるアシル化を経て相当する芳香族アセトキ
シカルボン酸および芳香族ジアセトキシ化合物となり、
一方、■芳香族ジカルボン酸とアルキレングリコールを
縮合してなるポリエステルは酸分解を経てポリエステル
フラグメントに誘導される。これらと芳香族ジカルボン
酸との脱酢酸反応により、逐次的に反応し、最終的に高
分子量ポリマとなると考えられる。■Aromatic hydroxycarboxylic acid and ■Aromatic diol■
After acylation with acetic anhydride, it becomes the corresponding aromatic acetoxycarboxylic acid and aromatic diacetoxy compound,
On the other hand, (2) a polyester formed by condensing an aromatic dicarboxylic acid and an alkylene glycol is induced into polyester fragments through acid decomposition. It is thought that these react with the aromatic dicarboxylic acid in a sequential manner through the deacetic acid reaction, and finally become a high molecular weight polymer.
本発明の製造方法において、■〜■の原料は通常、■、
■および■の合計100モル%に対して■は5〜95モ
ル%、■は5〜95モル%、■は5〜95モル%の範囲
、■は■に対して0.7〜1.3モル倍量の範囲で好ま
しく仕込まれる。In the production method of the present invention, the raw materials (■) to (■) are usually ■,
■ is in the range of 5 to 95 mol%, ■ is in the range of 5 to 95 mol%, ■ is in the range of 5 to 95 mol%, and ■ is in the range of 0.7 to 1.3 with respect to the total of 100 mol% of ■ and ■. It is preferably charged within the molar amount range.
製造するポリエステルの耐熱性の点から、特に、■、■
および■の合計100モル%に対して[■十■]は77
〜95モル%、■は5〜23モル%の範囲、■/■のモ
ル比は75/25〜9515の範囲、■は■に対して0
.9〜1,1モル倍量の範囲で好ましく仕込まれる。From the point of view of the heat resistance of the polyester to be manufactured, in particular,
For the total of 100 mol% of and ■, [■10■] is 77
~95 mol%, ■ is in the range of 5 to 23 mol%, ■/■ molar ratio is in the range of 75/25 to 9515, ■ is 0 relative to ■
.. It is preferably used in a range of 9 to 1.1 moles.
ただし、■は繰返し単位の平均を分子量とする。However, ■ indicates the average of the repeating units as the molecular weight.
特に■がポリエチレンテレフタレートの場合、分子量は
192.17とする。In particular, when ■ is polyethylene terephthalate, the molecular weight is 192.17.
また、無水酢酸は出発原料の全ヒドロキシ基に対して1
.0〜1.5倍モル用いられ、1.05〜1.2倍モル
が好ましい。In addition, acetic anhydride has 1
.. It is used in an amount of 0 to 1.5 times by mole, preferably 1.05 to 1.2 times by mole.
本発明の製造方法においては■芳香族ジカルボン酸は通
常、その5重量%以上、好ましくは50重量%以上を後
添加するのが好ましく、100重1%、すなわち全てを
後添加するのが最も好ましい。In the production method of the present invention, it is preferable that the aromatic dicarboxylic acid is usually post-added in an amount of 5% by weight or more, preferably 50% by weight or more, and most preferably 1% by weight, that is, the entire amount is post-added. .
本発明の特徴は前記■〜■のうち、■の一部または全部
を後で反応系に添加することにより、前記■〜■を一括
して仕込む場合に比較して共重合ポリエステルの加熱時
の熱安定性に対して極めて高い改善効果を示すことにあ
る。The feature of the present invention is that among the above-mentioned ■ to ■, by adding part or all of ■ to the reaction system later, the heating time of the copolymerized polyester is The purpose is to show an extremely high improvement effect on thermal stability.
その理由は■〜■を一括して仕込む場合は■および■の
芳香族ヒドロキシ基が無水酢酸と反応し、アセチル体と
なる際に■の芳香族ジカルボン酸が無水酢酸と酸無水物
交換反応を生じ、さらにこの無水酢酸が系中のカルボキ
シル基と酸無水物交換反応を繰返してポリマ鎖中に酸無
水物結合を生じさせるため、加熱時の安定性が不良にな
るものと思われる。従って、無水酢酸と芳香族ヒドロキ
シル基のアセチル化反応を先に行なった後に■の芳香族
ジカルボン酸を添加して酸無水物交換反応を抑制するこ
とにより熱安定性が向上したものと考えられる。The reason for this is that when ■~■ are charged all at once, the aromatic hydroxyl groups of ■ and ■ react with acetic anhydride, and when the aromatic dicarboxylic acid of ■ becomes an acetyl form, the aromatic dicarboxylic acid of ■ undergoes an acid anhydride exchange reaction with acetic anhydride. Furthermore, this acetic anhydride repeatedly undergoes acid anhydride exchange reactions with carboxyl groups in the system to form acid anhydride bonds in the polymer chain, which is thought to result in poor stability during heating. Therefore, it is considered that the thermal stability was improved by first carrying out the acetylation reaction of the aromatic hydroxyl group with acetic anhydride and then adding the aromatic dicarboxylic acid (2) to suppress the acid anhydride exchange reaction.
本発明の製造方法においては上記操作を必須とすること
以外に特に制限はないが、好ましく製造し得る方法とし
て、■芳香族ヒドロキシカルホン酸と■芳香族ジカルボ
ン酸とアルキレングリコールを縮合してなるポリエステ
ルと■芳香族ジオールと■無水#酸を反応容器に仕込み
、窒素気流下で80℃〜290℃、好ましくは100℃
〜250℃でアセチル化反応および初期重合を行なう。Although there are no particular restrictions on the production method of the present invention other than the above-mentioned operations being essential, a preferred method for production is the condensation of (1) aromatic hydroxycarphonic acid, (2) aromatic dicarboxylic acid, and alkylene glycol. Polyester, aromatic diol, and anhydrous #acid are placed in a reaction vessel and heated at 80°C to 290°C, preferably 100°C under a nitrogen stream.
Acetylation reaction and initial polymerization are carried out at ~250°C.
アセチル化反応および初期重合が進行し、一定量の酢酸
が留出した段階で、100〜290°C2好ましくは1
50〜280℃で■芳香族ジカルボン酸を反応系に投入
する。さらに反応を進行させた後、さらに250〜33
0°C5好ましくは290〜320℃で真空下で重合し
てポリマを得る。なお、この■芳香族ジカルボン酸の一
部、好ましくは50重量%以下を■〜■および■と同様
にあらかじめ反応系に添加せしめることも可能である。At the stage where the acetylation reaction and initial polymerization have proceeded and a certain amount of acetic acid has been distilled out, the temperature is 100-290°C2, preferably 1
(2) Aromatic dicarboxylic acid is introduced into the reaction system at 50 to 280°C. After further reaction, 250 to 33
The polymer is obtained by polymerization under vacuum at 0°C5, preferably 290-320°C. Incidentally, it is also possible to add a part of the aromatic dicarboxylic acid (1), preferably 50% by weight or less, to the reaction system in advance in the same manner as in (1) to (2) and (2).
■芳香族ジカルボン酸の投入は所定量を確実に系内に添
加させる方法であれば特に限定されないが、反応系で融
解、解重合、共重合などするポリエチレンテレフタレー
トのボトルなどのポリマカプセルに封入して添加する方
法が確実であり、より好ましい。■The aromatic dicarboxylic acid is not particularly limited as long as it can be added in a predetermined amount into the system, but it may be sealed in a polymer capsule such as a polyethylene terephthalate bottle that will be melted, depolymerized, or copolymerized in the reaction system. The method of adding it is reliable and more preferable.
また、本発明の方法では、無触媒でも反応が進行するが
、酢酸第1錫、酢酸亜鉛、酢酸アンチモン、三酸化アン
チモン、テトラブチルチタネート、酢酸ナトリウム、酢
酸カリウム、金属マグネシウムなどの金属化合物を添加
したほうが好ましい場合もある。In addition, in the method of the present invention, the reaction proceeds even without a catalyst, but metal compounds such as stannous acetate, zinc acetate, antimony acetate, antimony trioxide, tetrabutyl titanate, sodium acetate, potassium acetate, and metallic magnesium are added. There are times when it is preferable to do so.
また本発明で製造する共重合ポリエステルの溶融粘度は
10〜15,000ポイズが好ましく、特に20〜5,
000ポイズがより好ましい。The melt viscosity of the copolymerized polyester produced in the present invention is preferably 10 to 15,000 poise, particularly 20 to 5,000 poise.
000 poise is more preferred.
なお、この溶融粘度は(液晶開始温度+40℃)でずり
速度1,000 (1/秒)の条件下で高化式フローテ
スターによって測定した値である。−方、この共重合ポ
リニスステルの対数粘度は0゜1 g / d j濃度
、60°Cでペンタフルオロフェノール中で測定可能で
あり、0.5〜5dfJ/gが好ましく、1.0〜3.
0dj/gが特に好ましい。Note that this melt viscosity is a value measured using a Koka type flow tester under the conditions of (liquid crystal starting temperature + 40° C.) and a shear rate of 1,000 (1/sec). - On the other hand, the logarithmic viscosity of this copolymerized polynisester can be measured in pentafluorophenol at a concentration of 0.1 g/dj and 60°C, preferably 0.5 to 5 dfJ/g, preferably 1.0 to 3.
Particularly preferred is 0 dj/g.
なお、本発明で製造する共重合ポリエステルを重縮合す
る際には前記■〜■以外に、アジピン酸、アゼライン酸
、セバシン酸、ドデカンジオン酸などの脂肪族ジカルボ
ン酸、ヘキサヒドロテレフタル酸などの脂環式ジカルボ
ン酸、1,4−ブタンジオール、1,6−ヘキサンジオ
ール、ネオペンチルグリコール、1.4−シクロヘキサ
ンジオール、1.4−シクロヘキサンジメタツールなど
の脂肪族、脂環式ジオールなどを本発明の目的を損なわ
ない程度の少割合の範囲でさらに共重合せしめることが
できる。In addition, when polycondensing the copolymerized polyester produced in the present invention, in addition to the above-mentioned items 1 to 2, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and fats such as hexahydroterephthalic acid are used. Cyclic dicarboxylic acids, aliphatic and alicyclic diols such as 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and 1,4-cyclohexane dimetatool, etc. Further copolymerization may be carried out within a small proportion that does not impair the purpose of the invention.
かくしてなる本発明の共重合ポリエステルは溶融重合法
のみで高重合度ポリマが得られ、良好な光学異方性、機
械的性質および耐熱性を示し、押出成形、射出成形、圧
縮成形、ブロー成形などの通常の溶融成形に供すること
ができ、繊維、フィルム、三次元成形品、容器、ホース
等に加工することが可能である。The copolymerized polyester of the present invention obtained in this manner can be obtained as a polymer with a high degree of polymerization only by melt polymerization, exhibits good optical anisotropy, mechanical properties, and heat resistance, and can be used in extrusion molding, injection molding, compression molding, blow molding, etc. It can be subjected to ordinary melt molding, and can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc.
本発明の共重合ポリエステルに対し、ガラス繊維、炭素
繊維、アスベストなどの強化剤、充填剤、核剤、顔料、
酸化防止剤、安定剤、可塑剤、滑剤、離型剤および離燃
剤などの添加剤や他の熱可塑性樹脂を添加して、所望の
特性を付与することができる。For the copolymerized polyester of the present invention, reinforcing agents such as glass fibers, carbon fibers, and asbestos, fillers, nucleating agents, pigments,
Additives such as antioxidants, stabilizers, plasticizers, lubricants, mold release and flame release agents, and other thermoplastics can be added to impart desired properties.
なお、このようにして得られた成形品は、熱処理によっ
て、強度を増加させることができ、弾性率をも増加させ
ることができることもある。この熱処理は、成形品を不
活性雰囲気(例えば窒素、アルゴン、ヘリウムまたは水
蒸気)、または酸素含有雰囲気(例えば空気)中でポリ
マの融点以下の温度で熱処理することによって行なうこ
とができる。この熱処理は緊張下であってもなくてもよ
く、数十分〜数日の間で行なうことができる。In addition, the molded article obtained in this way can have its strength increased and may also have its elastic modulus increased by heat treatment. This heat treatment can be carried out by heat treating the molded article in an inert atmosphere (eg nitrogen, argon, helium or water vapor) or in an oxygen-containing atmosphere (eg air) at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension, and can be carried out for several tens of minutes to several days.
〈実施例〉 以下に、実施例により本発明をさらに説明する。<Example> The present invention will be further explained below with reference to Examples.
実施例1
撹拌装置を備えた重合用試験官にp−ヒドロキシ安息香
酸51.79g (0,375モル)、4゜4−−ジし
ドロキシビフェニル9.31g(0,05モル)固有粘
度が約0.6のポリエチレンテレフタレート14.41
g(0,075モル)無水酢酸53.34g (0,5
22モル)を仕込み、150℃で1.5時間反応させた
。この間約0゜3ccの酢酸留出が観測された。それか
らテレフタル酸8.31g (0゜050モル)を系中
に投入し、1時間に50℃の速度で昇温し、300℃ま
で昇温させな。250℃付近でテレフタル酸に起因する
ものと考えられる会合物が少量観察された6次に300
℃で1時間かけて0.5fflII+14g間で減圧さ
せ、さらに1時間重合し、反応を完結させた。Example 1 In a polymerization tester equipped with a stirring device, 51.79 g (0.375 mol) of p-hydroxybenzoic acid and 9.31 g (0.05 mol) of 4° 4-di-hydroxybiphenyl were added. about 0.6 polyethylene terephthalate 14.41
g (0,075 mol) acetic anhydride 53.34 g (0,5
22 mol) and reacted at 150°C for 1.5 hours. During this period, about 0.3 cc of acetic acid was observed to be distilled out. Then, 8.31 g (0.050 mol) of terephthalic acid was introduced into the system, and the temperature was raised at a rate of 50°C per hour until it reached 300°C. A small amount of aggregates thought to be caused by terephthalic acid were observed at around 250°C.
The pressure was reduced to 0.5 fflII + 14 g over 1 hour at °C, and polymerization was further carried out for 1 hour to complete the reaction.
得られたポリマのペンタフルオロフェノール中0.1r
/dj濃度、60℃での対数粘度は1゜86dj/gで
あった。このポリマを150’Cのオーブンで120時
間加熱処理を行なったところ対数粘度は1.82d、0
7gとなり、粘度低下は0.04dJ/fと少ながった
。なお、このポリマの理論構造式は下式で示される。0.1r of the obtained polymer in pentafluorophenol
/dj concentration and the logarithmic viscosity at 60°C was 1°86dj/g. When this polymer was heat treated in an oven at 150'C for 120 hours, the logarithmic viscosity was 1.82d, 0.
7 g, and the viscosity decrease was as small as 0.04 dJ/f. The theoretical structural formula of this polymer is shown by the following formula.
実施例2〜3および比較例1〜2
実施例1と同一の原料と反応装置でテレフタル酸の添加
時期を変更するほかは全〈実施例1と同様に反応させた
。これらをまとめて表1に示した。Examples 2 to 3 and Comparative Examples 1 to 2 The reaction was carried out in the same manner as in Example 1, using the same raw materials and reaction apparatus as in Example 1, except that the timing of addition of terephthalic acid was changed. These are summarized in Table 1.
これらはいずれも熱処理による対数粘度低下が伍かであ
った。比較例1は他の原料と一緒にテレフタル酸を仕込
んだ例であり、250’C付近で観測されるテレフタル
酸の会合物も多量であった。また対数粘度低下も大きが
った。比較例2では反応系が300°Cに昇温した時点
でテレフタル酸を添加した。この場合得られたポリマ中
に未反応のテレフタル酸が残っているため不均一なポリ
マしが得られなかった。In all of these, the logarithmic viscosity decreased by heat treatment. Comparative Example 1 is an example in which terephthalic acid was charged together with other raw materials, and a large amount of associated products of terephthalic acid was observed at around 250'C. Moreover, the logarithmic viscosity decrease was also large. In Comparative Example 2, terephthalic acid was added when the reaction system was heated to 300°C. In this case, unreacted terephthalic acid remained in the resulting polymer, so a non-uniform polymer could not be obtained.
表1
上記の結果から、アセチル化反応が進行した後にテレフ
タル酸を添加することで、加熱時の分子量低下の抑制さ
れた共重合ポリエステルが得られることが明らかである
。Table 1 From the above results, it is clear that by adding terephthalic acid after the acetylation reaction has progressed, a copolymerized polyester with suppressed molecular weight reduction during heating can be obtained.
〈発明の効果〉
本発明の方法により、耐熱性が良好なポリマを安価な原
料と簡素化された方法で製造することが可能になった。<Effects of the Invention> The method of the present invention has made it possible to produce a polymer with good heat resistance using inexpensive raw materials and a simplified method.
Claims (1)
カルボン酸、(2)下記構造単位(II)を有する芳香族
ジカルボン酸とアルキレングリコールを縮合してなるポ
リエステル、(3)下記構造単位(III)を有する芳香
族ジオールおよび(4)下記構造単位(IV)を有する芳
香族ジカルボン酸と(5)無水酢酸とから共重合ポリエ
ステルを製造する際に(4)下記構造単位(IV)を有す
る芳香族ジカルボン酸の一部または全部を反応系に10
0〜290℃で後添加することを特徴とする共重合ポリ
エステルの製造方法。 HO−Ar_1−COOH( I ) ▲数式、化学式、表等があります▼(II) HO−Ar_2−OH(III) HOOC−Ar_3−COOH(IV) (ただしAr_1〜Ar_4は2価の芳香族基、R_1
は2価のアルキレン基であり、Ar_1〜Ar_4は互
いに同一であっても異なっていてもよい。)(1) Aromatic hydroxycarboxylic acid having the following structural unit (I), (2) Polyester formed by condensing an aromatic dicarboxylic acid and alkylene glycol having the following structural unit (II), (3) The following structural unit (III) ) and (4) an aromatic dicarboxylic acid having the following structural unit (IV) and (5) acetic anhydride. Part or all of the group dicarboxylic acid is added to the reaction system.
A method for producing a copolyester characterized by post-adding at 0 to 290°C. HO-Ar_1-COOH(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) HO-Ar_2-OH(III) HOOC-Ar_3-COOH(IV) (However, Ar_1 to Ar_4 are divalent aromatic groups, R_1
is a divalent alkylene group, and Ar_1 to Ar_4 may be the same or different from each other. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31350887A JPH01153719A (en) | 1987-12-10 | 1987-12-10 | Production of copolymerized polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31350887A JPH01153719A (en) | 1987-12-10 | 1987-12-10 | Production of copolymerized polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01153719A true JPH01153719A (en) | 1989-06-15 |
JPH0524169B2 JPH0524169B2 (en) | 1993-04-07 |
Family
ID=18042152
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP31350887A Granted JPH01153719A (en) | 1987-12-10 | 1987-12-10 | Production of copolymerized polyester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01153719A (en) |
-
1987
- 1987-12-10 JP JP31350887A patent/JPH01153719A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH0524169B2 (en) | 1993-04-07 |
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