JPH01161015A - Manufacture of polyester - Google Patents
Manufacture of polyesterInfo
- Publication number
- JPH01161015A JPH01161015A JP32075387A JP32075387A JPH01161015A JP H01161015 A JPH01161015 A JP H01161015A JP 32075387 A JP32075387 A JP 32075387A JP 32075387 A JP32075387 A JP 32075387A JP H01161015 A JPH01161015 A JP H01161015A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polyester
- aromatic
- molecular weight
- dicarboxylic acid
- 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 37
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 42
- 125000003118 aryl group Chemical group 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 27
- 238000010438 heat treatment Methods 0.000 abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 235000011054 acetic acid Nutrition 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 238000006640 acetylation reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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
- 238000003756 stirring Methods 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
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 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
- 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical group 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000003365 glass fiber Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 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
- 239000006082 mold release agent Substances 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
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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、熱処理による分子量低下が少ない、耐熱性の良
好な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 provides a method for producing polyester that can be synthesized only by melt polymerization, uses low-cost raw materials, and has good heat resistance with little molecular weight reduction due to heat treatment. It is related to.
〈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
リエステルとC2芳香族ジオールのアセチル化物とd、
芳香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か記載されている。JP-A-51-8395 and JP-A-58-848
The copolymerized polyester disclosed in Publication No. 21 includes a, an acetylated product of an aromatic hydroxycarboxylic acid, b, an acetylated product of a polyester obtained by condensing an aromatic dicarboxylic acid and an alkylene glycol, and a C2 aromatic diol, and 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、特開昭62−41220号公報には(i)芳香族
ヒドロキシカルボン酸、(if)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(
iii)ai<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、(i
v)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。−〈発
明が解決しようとする問題点〉
しかしなから、特開昭51−8395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Xまた。特開昭62−
44220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
不十分なポリマしか得られていない、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、反応が繁雑とな
る。Furthermore, JP-A-62-41220 discloses (i) an aromatic hydroxycarboxylic acid, (if) a polyester formed by condensing an aromatic dicarboxylic acid and an alkylene glycol;
iii) ai < After reacting (it) with (i) using a small amount of aromatic diol and (iv) acetic anhydride, (i)
A method for producing a copolymerized polyester is disclosed that requires acetylation by step v). -〈Problems to be solved by the invention〉 However, in the production methods described in JP-A-51-8395 and JP-A-58-84821, the aromatic hydroxycarboxylic acid and the aromatic diol are prepared in advance. Also, it is necessary to induce the acetylated product in a separate process, and the polymer cannot be obtained at low cost. Unexamined Japanese Patent Publication 1986-
In the production method described in Publication No. 44220, (1) aromatic dicarboxylic acid is not copolymerized, resulting in a polymer with low heat resistance and insufficient molecular weight; and (iv)
Since acetic anhydride is added later, it is necessary to cool the reaction system midway through, which makes the reaction time long and the reaction complicated.
本発明はアセチル化されていないモノマを使用し、なお
かつ熱処理による分子量低下が少ないなど、耐熱性が良
好でi械的物性の高い共重合ポリエステルを製造するこ
とを課題とする。An object of the present invention is to use non-acetylated monomers and to produce a copolymerized polyester that has good heat resistance and high mechanical properties, such as a small decrease in molecular weight due to heat treatment.
く問題点を解決するための手段〉
すなわち、本発明は■下記式(I)で示される■芳香族
ヒドロキシカルボン酸と■下記構造単位(II)で示さ
れ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と■下記式(I[I)で示される
芳香族ジオールと■下記式(TV)で示される芳香族ジ
カルボン酸と■無水酢酸を反応させてポリエステルを製
造するに際し、初期反応系に低分子量モノカルボン酸を
加えることを′4徴とする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) aromatic hydroxycarboxylic acid represented by the following formula (I), (2) aromatic dicarboxylic acid represented by the following structural unit (II), and alkylene glycol. When producing a polyester by reacting an aromatic diol represented by the following formula (I[I), an aromatic dicarboxylic acid represented by the following formula (TV), and an acetic anhydride, the initial reaction system This is a method for producing polyester, which involves adding a low molecular weight monocarboxylic acid to the polyester.
HO−Ar1−COOH・・・・・・(■)(0−R1
−02C−Ar4−CO)・ (II)HQ−Ar2−
OH・旧・・(■)
HCOO−Ar3−cooH・旧・・(1v)(Ar1
〜Ar4は2価の芳香族基、R1は2価のアルキレン基
であり、A r 1〜A r 4は互いに同一でも異な
っていてもよい。)
本発明で製造するポリエステルは上記■〜■を原料とし
てWIl造されるものである。上記式中A r1〜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、混在することも可能で■
挙げられ、特に4,4゛−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。HO-Ar1-COOH・・・・・・(■)(0-R1
-02C-Ar4-CO) (II) HQ-Ar2-
OH・Old・(■) HCOO-Ar3-cooH・Old・・(1v)(Ar1
~Ar4 is a divalent aromatic group, R1 is a divalent alkylene group, and Ar1 to Ar4 may be the same or different from each other. ) The polyester produced in the present invention is produced using the above-mentioned materials 1 to 2 as raw materials. In the above formula, A r1~A
r and 4 are divalent aromatic groups, which may be the same or different from each other, and may be mixed. is preferred.
また、好ましく用いられるA r 3およびA r 4
X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バラフェニレン基と他の
基との共存が特に好ましい。Furthermore, preferably used A r 3 and A r 4
(X represents a hydrogen atom or a chlorine atom), and in both cases, the coexistence of a paraphenylene group or a paraphenylene group with another group is particularly preferred.
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。Further, R1 is a divalent alkylene group, especially (CH2
)2 is preferred.
本発明で製造するポリエステルは、■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、■芳香族ジオールお
よび■芳香族ジカルボン酸と■無水酢酸とを反応させて
ポリエステルを製造する初期反応系に低分子量モノカル
ボン酸を添加することを必須として製造される。The polyester produced in the present invention includes: (1) an aromatic hydroxycarboxylic acid, (2) a polyester obtained by condensing an aromatic dicarboxylic acid with an alkylene glycol, (2) a polyester obtained by reacting an aromatic diol, (1) an aromatic dicarboxylic acid, and (2) acetic anhydride. It is manufactured by adding a low molecular weight monocarboxylic acid to the initial reaction system for manufacturing.
■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アセチル化合物
を形成し、■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相当する
ポリエステルフラグメントを形成し、これらと■芳香族
ジカルボン酸はいずれも脱酢酸反応により、逐次的に反
応し、最終的に高分子量ポリマとなる。■Aromatic hydroxycarboxylic acid and ■Aromatic diol■
The corresponding acetyl compound is formed through acylation with acetic anhydride, and the polyester formed by condensing aromatic dicarboxylic acid and alkylene glycol forms the corresponding polyester fragment through acid decomposition, and these and ■ aromatic dicarboxylic acid are Both react sequentially by deacetic acid reaction, and finally become high molecular weight polymers.
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[■±■コは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 100 mol% of and ■, [■±■ 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 charged in a range of 9 to 1.1 moles.
ただし、■は繰返し単位の平均を特徴とする特に、■が
ポリエチレンテレフタレートの場合、分子1は192.
17として換算するのが好ましい。However, ■ is characterized by the average of repeating units. In particular, when ■ is polyethylene terephthalate, molecule 1 is 192.
It is preferable to convert as 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倍モル用いちれ+ 1.05〜1,2倍モ
ルが好ましい。In addition, acetic anhydride has 1
.. Preferably, 0 to 1.5 times the mole is used, and 1.05 to 1.2 times the mole.
本発明の特徴は前記■〜■の原料に加えて、初期反応系
に低分子量モノカルボン酸を加えることである。A feature of the present invention is that in addition to the above raw materials (1) to (4), a low molecular weight monocarboxylic acid is added to the initial reaction system.
本発明の製造方法で用いる低分子量モノカルボン酸は、
通常、その化学構造中に炭素原子を1〜10個有し、カ
ルボキシル基を1個有する化合物である。例えは、蟻酸
、酢酸、プロピオン酸、石炭酸などが挙げられるが、酢
酸が入手が容易である点で好ましい。The low molecular weight monocarboxylic acid used in the production method of the present invention is
Generally, it is a compound having 1 to 10 carbon atoms and one carboxyl group in its chemical structure. Examples include formic acid, acetic acid, propionic acid, and carbolic acid, but acetic acid is preferred because it is easily available.
本発明の方法においては、低分子量モノカルボン酸と無
水酢酸のモル比が0.01〜2:1となるように添加す
るのが好ましく、特に0.03〜1:1となる割合で添
加するのが好ましい。In the method of the present invention, it is preferable to add the low molecular weight monocarboxylic acid and acetic anhydride in a molar ratio of 0.01 to 2:1, particularly 0.03 to 1:1. is preferable.
本発明の製造方法において、初期反応系に上記低分子量
モノカルボン酸を添加することにより、ポリマの加熱時
の熱安定性が向上し、なおかつ初期反応がより速く進行
するのである。In the production method of the present invention, by adding the above-mentioned low molecular weight monocarboxylic acid to the initial reaction system, the thermal stability during heating of the polymer is improved, and the initial reaction proceeds more quickly.
その理由は明らかではないが、以下のように考えられる
。Although the reason is not clear, it is thought to be as follows.
■と■のヒドロキシ基が無水酢酸と反応し、アセチル体
となる際に低分子量モノカルボン酸が酸触媒として働き
、反応を加速させる。さらに、過剰の無水酢酸は■芳香
族ジカルボン酸と反応し、酸無水物結合を生じさせ、さ
らに酸無水物交換反応を繰り返すことにより、ポリマ鉗
中に酸無水物結合が形成されると考えられるが、反応系
に低分子量モノカルボン酸を存在させることにより、無
水酢酸と芳香族ジカルボン酸との反応を低減させること
ができるものと考えられる。When the hydroxyl groups of ■ and ■ react with acetic anhydride to form an acetyl compound, the low molecular weight monocarboxylic acid acts as an acid catalyst and accelerates the reaction. Furthermore, excess acetic anhydride reacts with the aromatic dicarboxylic acid to form an acid anhydride bond, and by repeating the acid anhydride exchange reaction, it is thought that an acid anhydride bond is formed in the polymer core. However, it is considered that the presence of a low molecular weight monocarboxylic acid in the reaction system can reduce the reaction between acetic anhydride and aromatic dicarboxylic acid.
本発明においては初期反応系に低分子量モノカルボン酸
を添加すること以外は特に制限はないが、原料の■〜■
および低分子量モノカルボン酸のうち、初期の反応系に
は少なくとも■、■、■および低分子量モノカルボン酸
を存在させるのが好ましい、このとき■と■は初期の反
応系に存在していてもよいし、反応をある程度の段階、
好ましくは反応温度がそれぞれ150°C以上、290
’C以下の段階で加えてもよい、■を後から添加する
ことにより〜特に多量の反応を行なう場合にポリエステ
ルが′a集し、撹拌が不能になるという大量重合時に生
じやすい工程上の欠点を回避することができる。また、
■を後から添加することにより、酸無水物結合がポリマ
鎖中に生じる要因である化合物がその反応の機会を失う
ため、生成したポリマの加熱時における熱安定性を向上
させる利点がある。In the present invention, there are no particular limitations other than adding a low molecular weight monocarboxylic acid to the initial reaction system.
and low molecular weight monocarboxylic acids, it is preferable that at least ■, ■, ■, and low molecular weight monocarboxylic acids are present in the initial reaction system. In this case, even if ■ and ■ are present in the initial reaction system, Good, the reaction takes a certain stage,
Preferably, the reaction temperature is 150°C or higher and 290°C or higher, respectively.
By adding (■) later, which may be added at the stage below 'C', the polyester aggregates 'a' and becomes impossible to stir, which is a process disadvantage that tends to occur during large-scale polymerization, especially when a large amount of reaction is carried out. can be avoided. Also,
By adding (2) later, the compound that causes acid anhydride bonds to form in the polymer chain loses the opportunity to react, which has the advantage of improving the thermal stability of the resulting polymer during heating.
本発明の好ましい方法を以下に示す。A preferred method of the present invention is shown below.
(a)■〜■と低分子量モノカルボン酸を反応容器に仕
込み、窒素気流下で80〜300℃、好ましくは100
℃〜250℃でアセチル化反応を行なう、さらに250
℃〜330℃、好ましくは290°C〜320°Cで真
空下で重合してポリマを得る。(a) ■~■ and a low molecular weight monocarboxylic acid are charged into a reaction vessel, and heated to 80~300°C, preferably 100°C under a nitrogen stream.
Carry out the acetylation reaction at a temperature between 250 °C and 250 °C.
The polymer is obtained by polymerization under vacuum at a temperature between 290°C and 320°C, preferably between 290°C and 320°C.
(b)■〜■、■と低分子量モノカルボン酸を反応容器
に仕込み、窒素気流下で80〜300°C1好ましくは
100〜250″Cでアセチル化反応を行なう、その後
、■を150〜300℃、好ましくは180〜290℃
で後添加し、さらに250〜330°C1好ましくは2
90〜320°Cで真空下で重合してポリマを得る。(b) Charge ■~■, ■ and a low molecular weight monocarboxylic acid into a reaction vessel, and perform the acetylation reaction at 80~300°C, preferably 100~250''C under a nitrogen stream. °C, preferably 180-290 °C
and then further added at 250 to 330°C, preferably 2
The polymer is obtained by polymerization under vacuum at 90-320°C.
(c)■、■〜■と低分子量モノカルボン酸を反応容器
に仕込み、窒素気流下で80〜300°C1好ましくは
100〜250°Cでアセチル化反応を行なう、その後
、■を150〜300℃、好ましくは200〜250°
Cで後添加し、さら4.:250〜330℃、好ましく
は290〜320°Cで真空下で重合してポリマを得る
。(c) ■, ■~■ and low molecular weight monocarboxylic acids are charged into a reaction vessel, and an acetylation reaction is carried out at 80~300°C, preferably 100~250°C under a nitrogen stream. °C, preferably 200-250°
Post-add with C and further 4. : Polymerization is carried out under vacuum at 250-330°C, preferably 290-320°C to obtain a polymer.
(d)■、■、■と低分子量モノカルボン酸を反応容器
に仕込み、窒素気流下で80〜300’C5好ましくは
100〜250℃でアセチル化反応を行なう、その後、
■を150〜300℃、好ましくは180〜290℃で
、また、■を150〜300℃、好ましくは200〜2
50℃で同時にまたは別個に後添加し、さらに250〜
330℃、好ましくは290〜320℃で真空下で重合
してポリマを得る。(d) Charge ■, ■, ■ and a low molecular weight monocarboxylic acid into a reaction vessel, and perform an acetylation reaction at 80 to 300'C5 preferably 100 to 250°C under a nitrogen stream, then,
(1) at 150-300°C, preferably 180-290°C, and (2) at 150-300°C, preferably 200-290°C.
Post-added simultaneously or separately at 50°C, and further added at 250°C to
The polymer is obtained by polymerization under vacuum at 330°C, preferably 290-320°C.
また、本発明の製造方法においては、無触媒でも反応は
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 production method of the present invention, although the reaction proceeds even without a catalyst, stannous acetate, zinc acetate, antimony acetate,
In some cases, it may be preferable to add metal compounds such as antimony trioxide, tetrabutyl titanate, sodium acetate, potassium acetate, metallic magnesium, and the like.
また、本発明の共重合ポリエステルの溶融粘度は10〜
15,000ボイズが好ましく、特に20〜5.000
ボイズがより好ましい。Moreover, the melt viscosity of the copolymerized polyester of the present invention is 10 to
15,000 boiz is preferred, especially 20-5,000
Boise is more preferred.
なお、この溶融粘度はく液晶開始温度+40″C)です
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
ポリエステルの対数粘度は(0゜1g/dj濃度、60
℃)でペンタフルオロフェノール中で測定可能であり、
0.5〜5 d j / 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 initiation temperature +40''C) and a slip rate of 1,000 (1/sec). The viscosity is (0゜1g/dj concentration, 60
can be measured in pentafluorophenol at
0.5-5 d j /g is preferable, 1.0-3.
Particularly preferred is 0 dj/g.
なお、本発明の製造方法において、前記■〜■のポリエ
ステル原料の他にアジピン酸、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重合せしめるこ
とができる。In addition, in the production method of the present invention, in addition to the polyester raw materials (1) to (2) above, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, alicyclic carboxylic acids such as hexahydroterephthalic acid, 1.4
- Further polymerization of aliphatic and alicyclic diols such as butanediol, 1,6-hexanediol, neopentyl glycol, and 1,4-cyclohexane dimetatool in a small proportion that does not impair the purpose of the present invention. You can force it.
本発明の製造製造方法は溶融重合のみで高重合度のポリ
エステルが得られ、そのポリエステルは良好な光学異方
性、機械的性質および圧縮成形、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、ホースなどに加工することが可能であ
る。The manufacturing method of the present invention can obtain a polyester with a high degree of polymerization only by melt polymerization, and the polyester has good optical anisotropy, mechanical properties, and can be subjected to ordinary melt molding such as compression molding and blow molding. It can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc.
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 strength of the molded article obtained in this manner can be increased by heat treatment, and the elastic modulus may also be increased. 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.
本発明で製造する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材、充填材、核剤、顔料
、酸化防止剤、安定剤、可塑剤、滑剤、離型剤および難
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。Addition of reinforcing materials such as glass fibers, carbon fibers, and asbestos, fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers, lubricants, mold release agents, and flame retardants to the polyester produced by the present invention. Agents and other thermoplastics can be added to impart desired properties.
〈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管にp−ヒドロキシ安磨、
6酸51.79g <0.375モル)、4゜4−一ジ
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
.41g <0.075モル)、無水酢酸53.34g
(0,522モル)および酢酸2.4g (0,04
モル)を仕込み、150°Cで1.5時間反応させた。Example 1 p-hydroxyammonium was added to a polymerization test tube equipped with a stirring device.
6 acid 51.79g <0.375 mol), 4゜4-di-doxybiphenyl 9.31g <0゜05 mol),
Polyethylene terephthalate 14 with an intrinsic viscosity of about 0.6
.. 41g <0.075 mol), acetic anhydride 53.34g
(0,522 mol) and acetic acid 2.4 g (0,04
mol) and reacted at 150°C for 1.5 hours.
酢酸を加えない場合と比較して反応系のぬれ性およびス
ラリー性が良好であり、酢酸が触媒として働いているこ
とが示された。その後、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思われる会合物が少量観察された。The wettability and slurry properties of the reaction system were better than when acetic acid was not added, indicating that acetic acid was working as a catalyst. Thereafter, the temperature was raised at a rate of 50°C per hour until it reached 300°C, and a small amount of associated material thought to be caused by terephthalic acid was observed at around 250°C.
300℃で1時間かけて0.5gmHgまで減圧し、さ
らに1時間重合し、反応を完結させた。The pressure was reduced to 0.5 gmHg at 300° C. over 1 hour, 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、0.1
g/dj濃度、60℃での対数粘度は1゜85 dJ
/Izであった。このポリマを150℃のオーブンで1
20時間加熱処理を行なったところ、対数粘度は1.7
8dj/gとなり、粘度低下は0.07dj/gと少な
かった。このポリマの理論構造式は以下の式で示される
。In the resulting polymer pentafluorophenol, 0.1
g/dj concentration, logarithmic viscosity at 60°C is 1°85 dJ
/Iz. This polymer was heated in an oven at 150℃ for 1
After 20 hours of heat treatment, the logarithmic viscosity was 1.7.
8 dj/g, and the decrease in viscosity was as small as 0.07 dj/g. The theoretical structural formula of this polymer is shown by the following formula.
J /m、/n=75/ 10/ 15実施例2
酢酸量を4= 8g (0,08モル)とした以外は実
施例1と同様にして行なった。熱処理前の対数粘度は1
.90dll/gであり、熱処理後は1゜84dj/g
であり、粘度低下は0.06d、I!/gと少なかった
。J/m, /n=75/10/15 Example 2 The same procedure as Example 1 was carried out except that the amount of acetic acid was changed to 4=8 g (0.08 mol). Logarithmic viscosity before heat treatment is 1
.. 90 dll/g, and 1°84 dj/g after heat treatment
and the viscosity decrease is 0.06d, I! /g.
比較例1
酢酸を添加しなかった以外は実施例1と同様にして行な
った。実施例例1で行なったときと比して酢酸の留出速
度は遅く、250℃付近で観測されるテレフタル酸に起
因するものと思われる会合物は多量であった。得られた
ポリマの熱処理前の対数粘度は1.85dj/+rであ
り、熱処理後は1.69dj/、であり、粘度低下は0
.16d」・7gと実施例1.2の場合より大幅に大き
かった。Comparative Example 1 The same procedure as Example 1 was carried out except that acetic acid was not added. The distillation rate of acetic acid was slower than that in Example 1, and a large amount of associated substances observed at around 250°C were believed to be caused by terephthalic acid. The logarithmic viscosity of the obtained polymer before heat treatment was 1.85 dj/+r, and after heat treatment it was 1.69 dj/, with a viscosity decrease of 0.
.. 16d''/7g, which was significantly larger than that of Example 1.2.
以上の結果から、本発明の製造方法で製造したポリエス
テルは熱処理による分子量低下の少ないポリエステルが
得られることが明らかである。From the above results, it is clear that the polyester produced by the production method of the present invention can be obtained with less decrease in molecular weight due to heat treatment.
〈発明の効果〉
本発明の製造方法により、耐熱性の良好なポリマを入手
が極めて容易な原料を用いて、繁雑な工程を経ることな
くポリエステルを製造することが可能になった。<Effects of the Invention> According to the production method of the present invention, it has become possible to produce polyester without going through complicated steps using a polymer with good heat resistance and raw materials that are extremely easy to obtain.
Claims (1)
シカルボン酸と[2]下記構造単位(II)で示される芳
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
るポリエステルと[3]下記式(III)で示される芳香
族ジオールと[4]下記式(IV)で示される芳香族ジカ
ルボン酸と[5]無水酢酸を反応させてポリエステルを
製造するに際し、初期反応系に低分子量モノカルボン酸
を加えることを特徴とする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) HCOO−Ar_3−COOH・・・・・・(IV) (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
一でも異なつていてもよい。)[Claims] [1] An aromatic hydroxycarboxylic acid represented by the following formula (I), [2] an aromatic dicarboxylic acid represented by the following structural unit (II), and an alkylene glycol condensed together. When producing a polyester by reacting a polyester, [3] an aromatic diol represented by the following formula (III), [4] an aromatic dicarboxylic acid represented by the following formula (IV), and [5] acetic anhydride, the initial reaction A method for producing polyester, characterized by adding a low molecular weight monocarboxylic acid to the system. HO-Ar_1-COOH・・・・・・(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(II) HO-Ar_2-OH・・・・・・(III) HCOO-Ar_3-COOH・...(IV) (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 |
---|---|---|---|
JP32075387A JPH01161015A (en) | 1987-12-17 | 1987-12-17 | Manufacture of polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32075387A JPH01161015A (en) | 1987-12-17 | 1987-12-17 | Manufacture of polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01161015A true JPH01161015A (en) | 1989-06-23 |
JPH0520453B2 JPH0520453B2 (en) | 1993-03-19 |
Family
ID=18124893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP32075387A Granted JPH01161015A (en) | 1987-12-17 | 1987-12-17 | Manufacture of polyester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01161015A (en) |
-
1987
- 1987-12-17 JP JP32075387A patent/JPH01161015A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH0520453B2 (en) | 1993-03-19 |
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