JPH06102728B2 - Method for producing polyester ether copolymer - Google Patents
Method for producing polyester ether copolymerInfo
- Publication number
- JPH06102728B2 JPH06102728B2 JP63157605A JP15760588A JPH06102728B2 JP H06102728 B2 JPH06102728 B2 JP H06102728B2 JP 63157605 A JP63157605 A JP 63157605A JP 15760588 A JP15760588 A JP 15760588A JP H06102728 B2 JPH06102728 B2 JP H06102728B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- polyether
- melt
- glycol
- mixing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 title claims description 23
- 229920001577 copolymer Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims description 5
- 229920000570 polyether Polymers 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- -1 phosphorous acid ester Chemical class 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- LFEWXDOYPCWFHR-UHFFFAOYSA-N 4-(4-carboxybenzoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C=C1 LFEWXDOYPCWFHR-UHFFFAOYSA-N 0.000 claims description 2
- OLZBOWFKDWDPKA-UHFFFAOYSA-N 4-[1-(4-carboxyphenyl)ethyl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1C(C)C1=CC=C(C(O)=O)C=C1 OLZBOWFKDWDPKA-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920001519 homopolymer Polymers 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GKMXREIWPASRMP-UHFFFAOYSA-J dipotassium;oxalate;oxygen(2-);titanium(4+) Chemical compound [O-2].[K+].[K+].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GKMXREIWPASRMP-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はポリエステルエーテル共重合体の製造方法に関
し、更に詳しくは、芳香族カルボン酸又はそのアルキル
エステルとグリコール類より得られたポリエステルと、
ポリエーテル類との共重合体を製造するに際し、一方の
原料であるポリエステルと他方の原料であるポリエーテ
ルとを溶融混合した後、又は溶融混合しながら、所定の
反応条件で重縮合反応を行い共重合体を製造する方法に
関する。TECHNICAL FIELD The present invention relates to a method for producing a polyester ether copolymer, and more specifically, a polyester obtained from an aromatic carboxylic acid or its alkyl ester and glycols,
In producing a copolymer with polyethers, after carrying out melt mixing of polyester which is one raw material and polyether which is the other raw material, or while being melt mixed, a polycondensation reaction is carried out under predetermined reaction conditions. The present invention relates to a method for producing a copolymer.
ポリエステルエーテル共重合体は、その成形加工性と物
性が優れていることから、自動車部品、電気電子部品等
の工業用プラスチックの分野で注目されつつある。その
製造方法は芳香族ジカルボン酸エステルとグリコールと
のエステル交換時にポリエーテルを共存させ、エステル
交換反応の後、重縮合反応を行う方法、特開昭58-19852
7の如く、芳香族ジカルボン酸とグリコールとを直接エ
ステル化反応させたエステル化生成物を予めポリエーテ
ルが仕込んである重縮合槽へ移行し、重縮合反応を行う
方法、或いは特開昭48-19696の如くポリエステルにアル
キレングリコールを加えオリゴエステル化した後、ポリ
エーテルを加え重縮合反応を行う方法等が報告されてい
る。しかしこれらの方法は、複雑な行程とそれに伴う設
備を要する、反応時間の長いことからジエチレングリコ
ールの如き副生ポリエーテルが生じ、これによる品質の
低下や操業性の低下が避けられない、等の問題点を内包
している。BACKGROUND ART Polyester ether copolymers are attracting attention in the field of industrial plastics such as automobile parts and electric / electronic parts because of their excellent moldability and physical properties. The production method is a method in which a polyether is allowed to coexist during the transesterification of an aromatic dicarboxylic acid ester with a glycol, and a polycondensation reaction is carried out after the transesterification reaction.
As described in 7, a method in which an esterification product obtained by directly esterifying an aromatic dicarboxylic acid and a glycol is transferred to a polycondensation tank in which a polyether is charged in advance to carry out a polycondensation reaction, or JP-A-48- As in 19696, a method has been reported in which alkylene glycol is added to polyester to form an oligoester, and then polyether is added to carry out a polycondensation reaction. However, these methods require a complicated process and accompanying equipment, and by the long reaction time, a by-product polyether such as diethylene glycol is produced, and deterioration in quality and operability due to this are unavoidable. It contains points.
本発明者らはかかる実情に鑑み、上記の如き問題点を解
消すべく鋭意研究の結果、本発明を提供するに至ったも
のである。In view of such circumstances, the inventors of the present invention have provided the present invention as a result of intensive research to solve the above problems.
即ち、本発明は固有粘度が0.5〔dl/g〕以上のポリエス
テルと、末端にヒドロキシ基を有し、且つ分子量が200
以上のポリエーテル類とを溶融混合した後、又は溶融混
合しながら、減圧下で重縮合反応を行うことを特徴とす
るポリエステルエーテル共重合体の製造方法を内容とす
るものである。That is, the present invention has a polyester having an intrinsic viscosity of 0.5 [dl / g] or more, a hydroxy group at the terminal, and a molecular weight of 200.
It is intended to provide a method for producing a polyester ether copolymer, which is characterized in that a polycondensation reaction is carried out under reduced pressure after melt mixing with the above polyethers or while melt mixing.
本発明で用いられるポリエステルとしては、芳香族ジカ
ルボン酸又はそのアルキルエステル、例えばテレフタル
酸、イソフタル酸、２、６−ナフタレンジカルボン酸、
４、４′−ジカルボキシルジフェニル、４、４′−ジカ
ルボキシルベンゾフェノン、ビス（４−カルボキシルフ
ェニル）エタン等、もしくはこれらのメチル、エチル、
プロピル等のアルキルエステルを単独又は２種以上、一
方、グリコールとしてはエチレングリコール、プロピレ
ングリコール、１、４−ブタンジオール、ネオペンチル
グリコール、ジクロヘキサンジメタノール等を単独又は
２種以上より合成されるホモポリマー及び／又は共重合
ポリマーが挙げられる。The polyester used in the present invention includes aromatic dicarboxylic acids or alkyl esters thereof, such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,
4,4'-dicarboxyldiphenyl, 4,4'-dicarboxylbenzophenone, bis (4-carboxylphenyl) ethane, etc., or their methyl, ethyl,
Alkyl esters such as propyl are used alone or in combination of two or more, while as glycols, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, dichlorohexanedimethanol, etc. are used alone or in combination of two or more. Polymers and / or copolymers may be mentioned.
本発明で用いられるポリエーテルとしては、一般式
（Ｉ）及び（II） （Ｉ）HOＲ・ＯＬＨ R:C2〜C5のアルキレン基 （式中、ｌ個のＲは同じものである必要はない） R1，R2：C2〜C5のアルキレン基 〔式中、（ｍ＋ｎ）個のR1，R2は同じものである必要は
ない〕 で示される少なくとも１種が好適に用いられる。これら
の中で、ビスフェノールＡ、ビスフェノールＳ等のポリ
アルキレンオキシド付加物等の如く、分子鎖中に芳香環
を有するものが、比較的高温で溶融混合できるので特に
好適である。ポリエーテルの分子量は200以上、好まし
くは200〜1000である。200未満では生成したポリマーの
融点が低下して好ましくない。又、10000を越えると、
相溶性が悪く均一な品質の製品が得難くなる。ポリエー
テル量は１〜60重量部、好ましくは５〜35重量部であ
る。ポリエーテル量が１重量部未満では目的とするポリ
マーの物性が得られず好ましくない。又、60重量部を越
えるとポリテーテルの劣化が激しく、品質は低下する為
好ましくない。ポリエステルの固有粘度は0.5〔dl/g〕
以上である。固有粘度が0.5〔dl/g〕未満の場合には、
重縮合反応時間が長くなり、また結晶化特性が悪くな
る。The polyether used in the present invention, the general formula (I) and (II) (I) HOR · O L H R: an alkylene group (wherein the C 2 -C 5, l number of R is the same No need) R 1 , R 2 : C 2 -C 5 alkylene group (wherein (m + n) R 1 , R 2 do not have to be the same) At least one kind represented by is preferably used. Among these, those having an aromatic ring in the molecular chain, such as polyalkylene oxide adducts of bisphenol A, bisphenol S, etc., are particularly preferable because they can be melt-mixed at a relatively high temperature. The polyether has a molecular weight of 200 or more, preferably 200 to 1000. If it is less than 200, the melting point of the produced polymer is lowered, which is not preferable. Also, when it exceeds 10,000,
Poor compatibility makes it difficult to obtain products of uniform quality. The amount of polyether is 1 to 60 parts by weight, preferably 5 to 35 parts by weight. If the amount of polyether is less than 1 part by weight, the desired physical properties of the polymer cannot be obtained, which is not preferable. On the other hand, if it exceeds 60 parts by weight, the polytheter deteriorates sharply and the quality deteriorates, which is not preferable. The intrinsic viscosity of polyester is 0.5 [dl / g]
That is all. When the intrinsic viscosity is less than 0.5 [dl / g],
The polycondensation reaction time becomes long and the crystallization characteristics deteriorate.
ポリエステルとポリエーテルとの溶融混合方法は、予め
溶融されているポリエステル中にポリエーテルを添加す
る方法、予めポリエーテルを150〜200℃に安定剤の存在
下で加熱しておき、その中に、ポリエステルがポリエー
テルと均一に馴染むように一括或いは連続的に添加する
方法が挙げられるが、後者の方が容易且つ速やかに溶融
混合されるので好適である。安定剤としては、リン酸エ
ステル、亜リン酸エステル、アミン化合物、チオエーテ
ル類、ヒンダードフェノール類等を単独又は２種以上使
用することができる。就中、リン酸トリフェニルとヒン
ダードフェノール類の併用が好ましい。安定剤の量は0.
01〜５重量部が好ましい。The method of melt-mixing the polyester and the polyether is a method of adding the polyether to the polyester which has been melted in advance, and heating the polyether to 150 to 200 ° C. in the presence of a stabilizer in advance, in which, A method in which the polyester is added all at once or continuously so that the polyester is uniformly blended with the polyether can be mentioned, but the latter method is preferable because it is easily and quickly melt-mixed. As the stabilizer, phosphoric acid ester, phosphorous acid ester, amine compound, thioethers, hindered phenols and the like can be used alone or in combination of two or more kinds. Especially, the combined use of triphenyl phosphate and hindered phenols is preferable. The amount of stabilizer is 0.
01 to 5 parts by weight is preferred.
本発明に於いて、共重合体の製造に際しては、反応を促
進させる為に通常用いられる触媒、即ち金属の酸化物、
炭酸塩、酢酸塩、アルコラート等、単独又は２種以上使
用することができる。それらのうちでも好ましいものと
しては、テトラ−ｎ−ブチルチタネート、蓚酸チタニル
カリウム、三酸化アンチモン、酸化ゲルマニウム等であ
る。In the present invention, in the production of the copolymer, a catalyst usually used for promoting the reaction, that is, a metal oxide,
Carbonates, acetates, alcoholates and the like can be used alone or in combination of two or more. Among them, preferable are tetra-n-butyl titanate, potassium titanyl oxalate, antimony trioxide, germanium oxide and the like.
以下、実施例により本発明を更に具体的に説明するが、
本発明はこれらに限定されるものではない。又、各種の
値は、以下の測定法によった。Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these. Further, various values were measured by the following measuring methods.
（１）固有粘度〔dl/g〕：フェノール／テトラクロルエ
タン＝1/1（重量比） ポリマー濃度は0.25g/dlで測定温度は25℃ （２）色調：色測色差計によるｂ値 （３）ジエチレングリコール（DEG）量（wt％）：メタ
ノール／水酸化カリウムで分解の後、 ガスクロマトグラフ法による測定値 （４）加熱重量減少率〔％〕：熱天秤による280℃−60
分ホールドによる測定値 実施例１〜４ 攪拌機、ガス排出口を備えた反応器（約4l）に、第１表
に示すポリエステル以外の原料を仕込んだ後、200℃に
昇温し、次いで常圧、窒素雰囲気下で径が約３φのスト
ランドカットによるペレット状のポリエステルを一括仕
込みし、260℃に加熱溶融せしめ、0.5〜1mmHg・absの真
空下で重縮合反応を行った。得られた共重合体の測定結
果を第３表に示す。(1) Intrinsic viscosity [dl / g]: Phenol / tetrachloroethane = 1/1 (weight ratio) Polymer concentration is 0.25g / dl and measurement temperature is 25 ° C. (2) Color tone: b value by a colorimeter. 3) Diethylene glycol (DEG) amount (wt%): value measured by gas chromatography after decomposition with methanol / potassium hydroxide (4) Heating weight loss rate [%]: 280 ° C-60 by thermobalance
Measured value by minute hold Examples 1 to 4 A reactor (about 4 liters) equipped with a stirrer and a gas outlet was charged with raw materials other than polyester shown in Table 1, heated to 200 ° C, and then subjected to normal pressure. In a nitrogen atmosphere, pellet-shaped polyester with strand cut having a diameter of about 3φ was charged all at once, heated and melted at 260 ° C., and polycondensation reaction was performed under a vacuum of 0.5 to 1 mmHg · abs. The measurement results of the obtained copolymer are shown in Table 3.
実施例５ 実施例１〜４と同様の装置で、径が約３φのストランド
カットによるペレット状ポリエチレンテレフタレート
（固有粘度0.6dl/g）100部（重量部、以下同じ）を仕込
み、260℃に加熱溶融せしめ、次いで内温が240℃を下廻
らないようビスフェノールＡポリエチレンオキシド付加
物（分子量1000）43部、リン酸トリフェニル0.76部、イ
ルガノックス−10101.17部、三酸化アンチモン0.05部を
連続添加した後、260℃に昇温し、0.5〜1mmHg・absの真
空下で重縮合反応を行った。得られた共重合体の測定結
果を第３表に示す。 Example 5 In the same apparatus as in Examples 1 to 4, 100 parts (weight part, the same applies hereinafter) of pelletized polyethylene terephthalate (intrinsic viscosity 0.6 dl / g) prepared by strand cutting having a diameter of about 3φ was charged and heated to 260 ° C. After melting, and then continuously adding 43 parts of bisphenol A polyethylene oxide adduct (molecular weight 1000), 0.76 part of triphenyl phosphate, Irganox-10101.17 parts, and 0.05 parts of antimony trioxide so that the internal temperature does not fall below 240 ° C. The temperature was raised to 260 ° C. and the polycondensation reaction was performed under a vacuum of 0.5 to 1 mmHg · abs. The measurement results of the obtained copolymer are shown in Table 3.
比較例１、４ 実施例と同様の装置で、第２表に示す原料を一括で仕込
み、約200℃で所定量のメタノールを留出せしめ、次い
で260℃に加熱せしめ、0.55mmHg・absの真空下で重縮合
反応を行った。得られた共重合体の測定結果を第４表に
示す。Comparative Examples 1 and 4 Using the same apparatus as in Examples, the raw materials shown in Table 2 were charged all at once, a predetermined amount of methanol was distilled off at about 200 ° C., and then heated to 260 ° C., and a vacuum of 0.55 mmHg · abs was obtained. The polycondensation reaction was carried out below. Table 4 shows the measurement results of the obtained copolymer.
比較例２ 実施例と同様の装置に清留塔を付加した装置で、反応の
一段目としてビスヒドロキシエチルテレフタレート５量
体52.8部に、テレフタル酸36.4部、エチレングリコール
16.4部のスラリーを内温約240℃に保ちつつ約３時間か
けて連続的に加え、精留により所定量の水を留出せしめ
た。次いでビスフェノールＡポリエチレンオキシド（分
子量1000）43部、リン酸トリフェニル0.76部、イルガノ
ックス−10101.17部、三酸化アンチモン0.05部を加え、
260℃に昇温し、0.5mmHg・absの真空下で重縮合反応を
行った。得られた共重合体の測定結果を第４表に示す。 Comparative Example 2 In a device similar to that of the example with a rectification column added, 52.8 parts of bishydroxyethyl terephthalate pentamer, 36.4 parts of terephthalic acid and ethylene glycol were used as the first stage of the reaction.
While maintaining the internal temperature of about 240 ° C., 16.4 parts of the slurry was continuously added over about 3 hours, and a predetermined amount of water was distilled off by rectification. Next, add 43 parts of bisphenol A polyethylene oxide (molecular weight 1000), 0.76 part of triphenyl phosphate, Irganox-10101.17 parts, 0.05 parts of antimony trioxide,
The temperature was raised to 260 ° C. and the polycondensation reaction was performed under a vacuum of 0.5 mmHg · abs. Table 4 shows the measurement results of the obtained copolymer.
比較例３ 実施例と同様の装置にポリエチレンテレフタレートチッ
プ（固有粘度0.6dl/g）100部、エチレングリコール135
部、酢酸亜鉛0.099部を仕込み200℃で１時間エチレング
リコールを還流しつつオリゴエステル化した後、ポリエ
チレングリコール（分子量1500）43部、リン酸トリフェ
ニル0.76部、イルガノックス−10101.17部、三酸化アン
チモン0.05部を仕込み260℃に加熱せしめ、0.5mmHg・ab
sの真空下で重縮合反応を行った。得られた共重合体の
測定結果を第４表に示した。Comparative Example 3 100 parts of polyethylene terephthalate chips (intrinsic viscosity 0.6 dl / g) and ethylene glycol 135 were placed in the same device as in the example.
Parts, zinc acetate 0.099 parts were charged, and ethylene glycol was refluxed at 200 ° C. for 1 hour while being oligoesterified, then polyethylene glycol (molecular weight 1500) 43 parts, triphenyl phosphate 0.76 parts, Irganox-10101.17 parts, antimony trioxide. Charge 0.05 parts and heat to 260 ℃, 0.5mmHg ・ ab
The polycondensation reaction was carried out under vacuum of s. The measurement results of the obtained copolymer are shown in Table 4.
〔作用・効果〕 叙上の通り、本発明によれば、 （１）原料としてポリエステルを用いるため、エステル
化反応、エステル交換反応等の工程が不要である、 （２）ポリエステルとポリエーテルの混合に特別の装置
を必要としない、 （３）反応時間が短縮される為副生ポリエーテル量が少
なく、また、ポリエーテルの熱履歴が小さくなり、従っ
て、生産時のポリマーの劣化が抑制される、 （４）生産時間が飛躍的に短縮され、操業サイクルが速
くなるので生産性が大巾に向上する、 等種々の利点を有し、産業界に寄与するところ大であ
る。 [Operation / Effect] As described above, according to the present invention, (1) since polyester is used as a raw material, steps such as esterification reaction and transesterification reaction are unnecessary. (2) Mixing of polyester and polyether No special equipment is required for (3) the reaction time is shortened, the amount of by-produced polyether is small, and the heat history of the polyether is small, and therefore deterioration of the polymer during production is suppressed. (4) The production time is drastically shortened, and the operation cycle becomes faster, so that the productivity is greatly improved. It has various advantages such as contributing to the industry.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−54428（ＪＰ，Ａ) 特開 昭62−68848（ＪＰ，Ａ) 特開 昭50−139194（ＪＰ，Ａ) 特開 昭49−6084（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-54428 (JP, A) JP-A-62-68848 (JP, A) JP-A-50-139194 (JP, A) JP-A-49- 6084 (JP, A)
Claims (7)
ルと、末端にヒドロキシ基を有し且つ分子量が200以上
のポリエーテル類とを溶融混合した後、又は溶融混合し
ながら、減圧下で重縮合反応を行うことを特徴とするポ
リエステルエーテル共重合体の製造方法。1. Under reduced pressure after melt-mixing a polyester having an intrinsic viscosity of 0.5 [dl / g] or more with a polyether having a hydroxy group at a terminal and having a molecular weight of 200 or more, or while melt-mixing. A method for producing a polyester ether copolymer, which comprises carrying out a polycondensation reaction with.
項１記載の製造方法。 2. An alkylene group having a main chain of the following general formulas (I) and (II) (I) HOR.O 1 HR: C 2 -C 5 R 1 and R 2 : C 2 to C 5 alkylene group The method according to claim 1, which comprises at least one polyether represented by
イソフタル酸、２、６ナフタレンジカルボン酸、４、
４′−ジカルボキシルジフェニル、４、４′ジカルボキ
シルベンゾフェノン、ビス（４−カルボキシルフェニ
ル）エタンもしくはこれらのメチル、エチル、プロピル
等のアルキルエステルを単独又は２種以上、グリコール
としては、エチレングリコール、プロピレングリコー
ル、１、４−ブタンジオール、ネオペンチルグリコー
ル、ジエチレングリコール、シクロヘキサンジメタノー
ル等を単独又は２種以上より合成されるホモポリマー及
び／又は共重合ポリマーを用いる請求項１記載の製造方
法。3. A terephthalic acid as a raw material polyester,
Isophthalic acid, 2,6 naphthalenedicarboxylic acid, 4,
4'-dicarboxyl diphenyl, 4,4 'dicarboxyl benzophenone, bis (4-carboxylphenyl) ethane or their alkyl esters such as methyl, ethyl, propyl and the like, alone or in combination of 2 or more, and as the glycol, ethylene glycol, propylene The production method according to claim 1, wherein a homopolymer and / or a copolymer polymer synthesized from glycols, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol or the like is used alone or in combination of two or more.
破砕等によって得られるフレーク状又は粉状のものを用
いる請求項１又は３記載の製造方法。4. The production method according to claim 1, wherein the raw material polyester is in the form of pellets, flakes or powder obtained by crushing or the like.
エステルを添加し溶融混合した後、又は溶融混合しなが
ら、重縮合反応を行う請求項１、３又は４記載の製造方
法。5. The production method according to claim 1, 3 or 4, wherein the polycondensation reaction is carried out after the polyester is added to the polyether which has been heated in advance and melt-mixed, or while melt-mixing.
物である請求項１又は２記載の製造方法。6. The method according to claim 1, wherein the polyethers are compounds having a molecular weight of 200 to 10,000.
酸エステル、亜リン酸エステル、アミン化合物、チオエ
ーテル類、ヒンダードフェノール類から選択された少な
くとも１種を用いる請求項１記載の製造方法。7. The method according to claim 1, wherein at least one selected from a phosphoric acid ester, a phosphorous acid ester, an amine compound, thioethers and hindered phenols is used as a stabilizer when heating the polyether.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157605A JPH06102728B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing polyester ether copolymer |
| DE68927165T DE68927165T2 (en) | 1988-06-24 | 1989-06-23 | METHOD FOR PRODUCING POLYESTER ETHER COPOLYMERS |
| EP89907299A EP0383929B1 (en) | 1988-06-24 | 1989-06-23 | Process for producing polyester ether copolymer |
| PCT/JP1989/000626 WO1989012657A1 (en) | 1988-06-24 | 1989-06-23 | Process for producing polyester ether copolymer |
| US07/912,137 US5331066A (en) | 1988-06-24 | 1992-07-09 | Process for producing polyester ether copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63157605A JPH06102728B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing polyester ether copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH026532A JPH026532A (en) | 1990-01-10 |
| JPH06102728B2 true JPH06102728B2 (en) | 1994-12-14 |
Family
ID=15653379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63157605A Expired - Lifetime JPH06102728B2 (en) | 1988-06-24 | 1988-06-24 | Method for producing polyester ether copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06102728B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2210839C2 (en) * | 1972-03-07 | 1982-10-21 | Bayer Ag, 5090 Leverkusen | Process for the production of block copolymers |
| JPS5746450B2 (en) * | 1974-04-25 | 1982-10-04 | ||
| JPS6268848A (en) * | 1985-09-20 | 1987-03-28 | Kanegafuchi Chem Ind Co Ltd | Polyester copolymer composition for injection molding |
| JPH0768354B2 (en) * | 1986-07-14 | 1995-07-26 | ゼネラル・エレクトリック・カンパニイ | Method for producing polyphenylene ether-polyester copolymer |
-
1988
- 1988-06-24 JP JP63157605A patent/JPH06102728B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH026532A (en) | 1990-01-10 |
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