JPH04189822A - Production of aliphatic polyester - Google Patents
Production of aliphatic polyesterInfo
- Publication number
- JPH04189822A JPH04189822A JP31784990A JP31784990A JPH04189822A JP H04189822 A JPH04189822 A JP H04189822A JP 31784990 A JP31784990 A JP 31784990A JP 31784990 A JP31784990 A JP 31784990A JP H04189822 A JPH04189822 A JP H04189822A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- polyester
- diisocyanate
- aliphatic polyester
- 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
- 229920003232 aliphatic polyester Polymers 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 abstract description 30
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 239000001384 succinic acid Substances 0.000 abstract description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001879 gelation Methods 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 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 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IBAHLNWTOIHLKE-UHFFFAOYSA-N cyano cyanate Chemical compound N#COC#N IBAHLNWTOIHLKE-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 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、末端基が実質的にヒドロキシル基である高分
子量飽和ポリエステルを、更に一段と高分子量化して各
種用途に有用なポリエステルを合成する方法に関するも
のである。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for synthesizing a polyester useful for various uses by further increasing the molecular weight of a high molecular weight saturated polyester whose terminal groups are essentially hydroxyl groups. It is related to.
飽和ポリエステル、特にテレフタル酸を一成分とする系
統のものは、フィルム、成形品、ガラス繊維強化プラス
チックスとして、頗る多方面な用途に利用されているこ
とはよく知られている。It is well known that saturated polyesters, especially those containing terephthalic acid as one component, are used in a wide variety of applications as films, molded products, and glass fiber reinforced plastics.
また、接着剤、塗料のベース樹脂としても有用で、近年
開発が進められてもいる。It is also useful as a base resin for adhesives and paints, and its development has been progressing in recent years.
本発明はポリエチレンテレフタレートのような比較的融
点の高いポリエステルよりも、塗料、接着剤に用いられ
る比較的低融点のポリエステル、或はフィルム形成性が
十分でない脂肪族ポリエステルなどのポリエステルの分
子量を増大させて実用上十分な性質を付与する方法に関
する。The present invention increases the molecular weight of polyesters such as polyesters with relatively low melting points used in paints and adhesives, or aliphatic polyesters that do not have sufficient film-forming properties, than polyesters with relatively high melting points such as polyethylene terephthalate. The present invention relates to a method for imparting practically sufficient properties to a material.
周知のように、高分子量（ここでいう高分子量は数平均
分子量で約１０．０ＯＯ１，’ｌ十、とする）ポリエス
テルを合成する方法は、末端ヒドロキシル基の低分子量
ポリエステルの脱グリコール反応によっている。As is well known, the method for synthesizing high molecular weight polyesters (high molecular weight here is defined as a number average molecular weight of approximately 10.0OO1,'10) is by deglycol reaction of low molecular weight polyesters with terminal hydroxyl groups. .
従って、分子量が増大するにつれて末端基濃度は著しく
減少し、エステル交換時の温度による分解反応も加わっ
て分子量に限界を生ずるようになる。Therefore, as the molecular weight increases, the terminal group concentration decreases markedly, and the decomposition reaction due to the temperature during transesterification is also added, and a limit is placed on the molecular weight.
特に、脂肪族ポリエステルにその傾向が著しくみられる
。例乙ば、第１図に示すように、従来の減圧下の脱グリ
コール反応により高分子量飽和ポリエステルを製造する
場合、分子量が最大値に達した後、減少に転することが
みられる。This tendency is particularly noticeable in aliphatic polyesters. For example, as shown in FIG. 1, when a high molecular weight saturated polyester is produced by the conventional deglycol reaction under reduced pressure, the molecular weight begins to decrease after reaching a maximum value.
このような場合、脂肪族で強靭なフィルムを形成させる
に足りる分子量をもったポリエステルを得ることは、従
来の脱グリコール反応に頼っていたのでは、難しい。言
いかえれば、脂肪族ポリエステルて得られる分子量では
実用性のある物性を有するフィルム３形成させることは
出来なかったといえる。In such cases, it is difficult to obtain an aliphatic polyester having a molecular weight sufficient to form a strong film by relying on conventional deglycol reactions. In other words, it can be said that it was not possible to form the film 3 having practical physical properties with the molecular weight obtained from the aliphatic polyester.
芳香族構造Ｐ有するポリエステルにしても、例７−ば粘
着７ＦＩＩヅ）ベースレシンに使用しようとする時、似
たような状況となる。この時も分子量の不十分な点はそ
のまま物性の不足として現われる。A similar situation arises when polyesters having an aromatic structure P are used in base resins. In this case, the insufficient molecular weight directly manifests itself as a lack of physical properties.
従って、本発明者らはこのような易熱分解性のポリエス
テルの分子量を極力高めるべく検討を重ねた結果、まづ
数平均分子量が５，０００以上、望ましくは１０，００
０以上で、末端基が実質的にヒドロキシル基であり、酸
成分の少なくとも１種類がコハク酸である脂肪族ポリエ
ステルに、その融点以上の熔融状態において、ヒドロキ
シル基の１／１０〜２当量相当のイソシアナート基を有
するジイソシアナートを添加することにより、意外にも
ゲル化の危険がなく円滑に高分子量ポリエステルを合成
出来ることを知り、本発明を完成することができた。Therefore, as a result of repeated studies by the present inventors to increase the molecular weight of such easily thermally decomposable polyester as much as possible, we found that the number average molecular weight is 5,000 or more, preferably 10,000.
0 or more, the terminal group is substantially a hydroxyl group, and at least one type of acid component is succinic acid. It was discovered that by adding a diisocyanate having an isocyanate group, a high molecular weight polyester can be synthesized smoothly without the risk of gelation, and the present invention was completed.
従来の一般的な常識では、高温でイソシアナートをポリ
マーに反応させることは、ゲル化が避けられないとする
ものであるが、ポリエステルの分子量を５，０００以上
とし、イソシアナートの量をヒドロキシル基の１／１０
〜２当量とすることで、ゲル化の危険性なしにポリエス
テルの分子量を高めることが可能なことを見出した点に
、本発明の意味がある。Conventional common sense holds that gelation is inevitable when isocyanates are reacted with polymers at high temperatures. 1/10 of
The meaning of the present invention lies in the discovery that by setting the amount to 2 equivalents, it is possible to increase the molecular weight of the polyester without the risk of gelation.
使用するシイ゛ノシアナートの量がイソシアナート基の
当量として、ヒドロキシル基の１／１０当量未満では
分子量増大の効果に乏しく、また２当量を超える場合は
ゲル化の危険性が大きくなる。If the amount of cyanocyanate used is less than 1/10 equivalent of hydroxyl group as equivalent of isocyanate group,
The effect of increasing the molecular weight is poor, and if the amount exceeds 2 equivalents, there is a greater risk of gelation.
本発明の主成分である飽和ポリニスデルは、酸の少くと
も一成分はコハク酸であり、グリコール成分としてはエ
チレングリコール、ブタンジオール１，４のいづれか、
または混合物である。In the saturated polynisder, which is the main component of the present invention, at least one acid component is succinic acid, and the glycol component is either ethylene glycol, butanediol 1, 4,
or a mixture.
この理由は、融点、フィルム形成性、ならびにコストか
らくるものである。The reason for this is due to melting point, film forming properties, and cost.
融点が８０℃以下では実用性に乏しくなるが、脂肪族ポ
リエステルで８０℃Ｕ上の融点を有するものは、コハク
酸とエチレングリコール、コハク酸とブタンジオールの
２種類に、コストも加味すれば、限定されるといっても
過言ではないからである。If the melting point is below 80°C, it will be impractical, but there are two aliphatic polyesters with a melting point above 80°C: succinic acid and ethylene glycol, and succinic acid and butanediol. It is no exaggeration to say that it is limited.
コハク酸の一部とアジピン酸、セバシン酸、或はデカメ
チレンジカルボン酸で置換することは可能であるか、そ
の割合は５０モル（％）以下が好ましい。Is it possible to replace a part of succinic acid with adipic acid, sebacic acid, or decamethylene dicarboxylic acid?The ratio is preferably 50 mol (%) or less.
同様のことはグリコール成分についても言えることであ
るが、ブタンジオール１．４の一部をヘキサシシ゛オー
ル１，６、デカメチレングリコール、で置換することは
可能である。The same thing can be said about the glycol component, but it is possible to replace a part of butanediol 1,4 with hexashidiol 1,6 or decamethylene glycol.
ポリエステル化はグリコール過剰で所望の酸価（一般に
は１０以下）迄エステル化した後、テトラアルキルチタ
ン化合物のような反応触媒の存在下で脱グリコール反応
が行われる。Polyesterification is performed by esterifying with excess glycol to a desired acid value (generally 10 or less), followed by deglycol reaction in the presence of a reaction catalyst such as a tetraalkyl titanium compound.
必要な分子量に達した段階で、ジイソシアナートの所望
量が添加される。Once the required molecular weight is reached, the desired amount of diisocyanate is added.
本発明に使用されるジイソシアナートの種顕に特に制限
はないが、市販のものがそのま才用いられる。There are no particular restrictions on the species of diisocyanate used in the present invention, but commercially available diisocyanates can be used as is.
それらの例としては、例えば２．４− トリレンジイソ
シアナート、２．４−）リレンジイソシアナートと２．
６− トリレンジイソシアナートとの混合体、ジフェニ
ルメタンジイソシアナート、Ｐ。Examples thereof include, for example, 2.4-tolylene diisocyanate, 2.4-)lylene diisocyanate and 2.4-)lylene diisocyanate.
6- Mixture with tolylene diisocyanate, diphenylmethane diisocyanate, P.
Ｐ゛−ジフェニルジイソシアナート、１，６−ナフチレ
ンジイソシアナート、キシリレンジイソシアナート、水
製化キシリレンジイソシアナート、イソホロンジイソシ
アナート、ヘキサメチレンジイソシアナートである。They are P'-diphenyl diisocyanate, 1,6-naphthylene diisocyanate, xylylene diisocyanate, aqueous xylylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
ジイソシアナート添加と同時に反応が進行し、数分後に
は反応は終了する。The reaction proceeds simultaneously with the addition of the diisocyanate and ends after a few minutes.
本発明によるジイソシアナートにより分子量を増大させ
た飽和ポリエステルは、主として、成形品、フィルム等
の用途に供することができる。The saturated polyester whose molecular weight has been increased by the diisocyanate according to the present invention can be mainly used for molded products, films, and the like.
次に本発明の理解を助けるために、以下に実施例を示す
。Next, examples will be shown below to help understand the present invention.
実ＩＬづ−
撹拌機、分溜コンデンサー、ガス導入管、温度計を付し
た１１セパラブルフラスコに、ブタンジオール】、４を
２１６＋ｙ、コハク酸を２３６ｇ加え、窒素気流中２１
０〜２２０℃でエステル化して酸価７、つ とした後、
テトラブチルチタネート１．２ｇ加え、コンデンサーを
交換、最初は３５Ｔｏ「ｒ、最終的には０．６Ｔｏｒｒ
の減圧下に約５時間脱グリコール反応Ｐ行った。ＧＰＣ
測定による数平均分子量は１６．２００であった（第２
−Ａ図参照、ポリエステルＡ）。これにヘキサメチレン
ジイソシアナート４ｙ （ＯＨ／ＮＣＯ＋、１０．８）
を温屡１９０℃で加えた。］Ｏ分闇反応後の高分子量ポ
リエステルの数平均分子量は４５，８００ ＜第２−Ｂ
図参照、ポリエステルＢ）となったが、ゲル化は生じな
かった。得られた高分子量ポリエステルは融点約１２０
℃、フィルム形成が可能で２軸延伸により強靭なフィル
ムとなった。Into a 11 separable flask equipped with a stirrer, fractionation condenser, gas inlet tube, and thermometer, add 216+y of butanediol], 4, and 236 g of succinic acid, and add 216 g of succinic acid in a nitrogen stream.
After being esterified at 0 to 220°C to give an acid value of 7.
Added 1.2g of tetrabutyl titanate, replaced the condenser, initially 35Torr, finally 0.6Torr
The deglycol reaction P was carried out for about 5 hours under reduced pressure. GPC
The number average molecular weight measured was 16.200 (second
- See figure A, polyester A). To this, hexamethylene diisocyanate 4y (OH/NCO+, 10.8)
was added at a temperature of 190°C. ] The number average molecular weight of the high molecular weight polyester after the O darkening reaction is 45,800 <Second-B
As shown in the figure, polyester B) was obtained, but gelation did not occur. The resulting high molecular weight polyester has a melting point of approximately 120
℃, film formation was possible and a strong film was obtained by biaxial stretching.
火ＩＬｕ
撹拌機、分溜コンデンサー、ガス導入管、温度計を付し
た１１セパラブルフラスコに、コハク酸２０２ｇ、ブタ
ンジオール１．４を２１６ｙ、アジピン酸２９ｇを仕込
み、２００〜２１０℃でエステル化して酸価９．１とし
た後、コンデンサーを交換し、テトライソプロピルチタ
ネート１ｇを加ノー、２１０〜２２０℃、最終的には０
．７Ｔｏｒｒ迄減圧し、数平均分子量１０．２００のポ
リエステル（Ｃ）を合成した。202 g of succinic acid, 216 y of butanediol, and 29 g of adipic acid were placed in a 11 separable flask equipped with a stirrer, fractionation condenser, gas inlet tube, and thermometer, and esterified at 200 to 210°C. After setting the acid value to 9.1, the condenser was replaced and 1 g of tetraisopropyl titanate was added at 210-220°C, finally at 0.
．． The pressure was reduced to 7 Torr, and polyester (C) having a number average molecular weight of 10.200 was synthesized.
引続いて温度を１９０℃に下げ、ヘキサメチレンジイソ
シアナート５ｇを加え、１５分反応させた。ＯＨ、／
Ｎ ＣＯ比は約１／１であった。ゲル化は生じなかった
。Subsequently, the temperature was lowered to 190° C., 5 g of hexamethylene diisocyanate was added, and the mixture was reacted for 15 minutes. OH, /
The NCO ratio was approximately 1/1. No gelation occurred.
得られたポリエステル（Ｄ）は数平均分子量４８．９０
０、微黄白色ワックス状て、フィルム形成性が認められ
た。The obtained polyester (D) had a number average molecular weight of 48.90
0. Slightly yellowish white wax-like appearance, film-forming properties were observed.
４創１Ｊ
撹拌機、分溜コンデンサー、温度計、ガス導入管を付し
た１１セパラブルフラスコに、エチレングリコール１５
０ｇ−コハク酸２３６ ｇを仕込み、１９５〜２１０°
Ｃで窒素ガス気流中エステル化して酸価７．つとした後
、コンデンサーを交換し、テトラブチルチタネート１ｇ
加え温度２１０〜２２０℃で最終的には０ 、７ Ｔｏ
ｒｒの減圧とし、数平均分子量１１．８００のポリエス
テル（Ｅ）を合成した後、温度を１９０℃に下げ、ジフ
ェニルメタンジイソシアナート’５．５ｇ（○Ｈ／ＮＣ
Ｏ埃１１０．８５＞を加え、１０分間反応させた所、数
平均分子量は約４０，０００となりゲル化は生じなかっ
た。4 wounds 1J Into a 11 separable flask equipped with a stirrer, fractionation condenser, thermometer, and gas inlet tube, add ethylene glycol 15
0g - 236g of succinic acid was charged and heated to 195-210°
Esterified with C in a nitrogen gas stream to give an acid value of 7. After cooling, replace the condenser and add 1g of tetrabutyl titanate.
Addition temperature is 210-220℃ and finally 0,7 To
After synthesizing polyester (E) with a number average molecular weight of 11.800 under reduced pressure of
When O dust 110.85> was added and reacted for 10 minutes, the number average molecular weight was approximately 40,000 and no gelation occurred.
得られたポリエステル（Ｆ）はやや黄褐色を帯びたワ／
クス状で、融点約１〕０°Ｃ、フィルム形成性が認めら
れた。The obtained polyester (F) has a slightly yellowish brown color.
It was in the shape of a locust, had a melting point of about 1]0°C, and had film-forming properties.
〔発明の効果］
本発明は上記のように構成したので、比較的低融点の脂
肪族ポリエステルの分子量を増大させ、成形体、フィル
ム等の用途に有用なポリエステル材料を提供することが
できる。[Effects of the Invention] Since the present invention is configured as described above, it is possible to increase the molecular weight of an aliphatic polyester having a relatively low melting point, thereby providing a polyester material useful for applications such as molded bodies and films.
第１図は、従来の減圧反応による高分子量飽和ポリエス
テルの製造における、時間と分子量分布の関係を示す図
である。
第２−Ａ図は、実施例１におけるポリエステルＡのＧＰ
Ｃ測定結果を示す図である。
第２−、 Ｂ図は、実施例】におけるポリエステルＢの
ＧＰＣ測定結果を示す図である。
特許出願人 昭和高分子株式会社
鼾工勺好量（Ｍｎ）
反応ｇ度−・−・・−２２０’Ｃ
（減圧反応時間）
第２−Ａ図
ポリエステルＡ
ＭＮ’＝１６，２００FIG. 1 is a diagram showing the relationship between time and molecular weight distribution in the production of high molecular weight saturated polyester by conventional reduced pressure reaction. Figure 2-A shows the GP of polyester A in Example 1.
It is a figure showing a C measurement result. Figure 2-B is a diagram showing the GPC measurement results of polyester B in Example. Patent applicant Showa Kobunshi Co., Ltd. Amount (Mn) Reaction degree - - 220'C (Decompression reaction time) Figure 2-A Polyester A MN' = 16,200
Claims (3)
的にヒドロキシル基であり、酸成分の少くとも一種類が
コハク酸である脂肪族ポリエステルに、その融点以上の
熔融状態において、ヒドロキシル基の１／１０〜２当量
相当のイソシアナート基を有するジイソシアナートを添
加することよりなる、高分子量化された脂肪族ポリエス
テルの製造方法。(1) An aliphatic polyester having a number average molecular weight of 5,000 or more, whose end groups are essentially hydroxyl groups, and at least one type of acid component is succinic acid, is added to A method for producing a high-molecular-weight aliphatic polyester, which comprises adding a diisocyanate having an isocyanate group equivalent to 1/10 to 2 equivalents of the group.
チレングリコールであることを特徴とする、請求項第１
項記載の方法。(2) Claim 1, characterized in that the polyhydric alcohol component in the aliphatic polyester is ethylene glycol.
The method described in section.
タンジオール１，４であることを特徴とする、請求項第
１項記載の方法。(3) The method according to claim 1, wherein the polyhydric alcohol component in the aliphatic polyester is 1,4 butanediol.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31784990A JP2825969B2 (en) | 1990-11-26 | 1990-11-26 | Method for producing aliphatic polyester |
| US07/797,033 US5306787A (en) | 1990-11-26 | 1991-11-25 | Method for producing saturated polyester |
| DE69127676T DE69127676T2 (en) | 1990-11-26 | 1991-11-25 | A method of making saturated polyester |
| EP91310812A EP0488617B1 (en) | 1990-11-26 | 1991-11-25 | A method for producing saturated polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31784990A JP2825969B2 (en) | 1990-11-26 | 1990-11-26 | Method for producing aliphatic polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04189822A true JPH04189822A (en) | 1992-07-08 |
| JP2825969B2 JP2825969B2 (en) | 1998-11-18 |
Family
ID=18092743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31784990A Expired - Lifetime JP2825969B2 (en) | 1990-11-26 | 1990-11-26 | Method for producing aliphatic polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2825969B2 (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5445778A (en) * | 1993-11-03 | 1995-08-29 | Cheil Synthetics Inc. | Method for the production of aliphatic copolyester film |
| EP0694874A2 (en) | 1994-07-25 | 1996-01-31 | Toppan Printing Co., Ltd. | Biodegradable cards |
| US5496923A (en) * | 1993-09-20 | 1996-03-05 | Mitsui Toatsu Chemicals, Inc. | Purification process of aliphatic polyester |
| EP0703260A1 (en) | 1994-09-21 | 1996-03-27 | Tonen Corporation | Aliphatic polyester and a process for the preparation thereof |
| WO1996019521A1 (en) * | 1994-12-21 | 1996-06-27 | Showa Denko Kabushiki Kaisha | Aliphatic polyester resin and process for producing the same |
| US5714230A (en) * | 1993-11-18 | 1998-02-03 | Mitsui Toatsu Chemicals, Inc. | Degradable aliphatic polyester formed products |
| WO2001019887A1 (en) * | 1999-09-10 | 2001-03-22 | Mitsui Chemicals, Inc. | Polyurethane resin with degradability |
| WO2002062572A1 (en) | 2001-02-05 | 2002-08-15 | Ishida Co., Ltd. | Biodegradable bags for packing foods available in high-speed production |
| JP2006213825A (en) * | 2005-02-03 | 2006-08-17 | Chiba Univ | Method for producing barrier material excellent in heat stability |
| WO2008126896A1 (en) | 2007-04-10 | 2008-10-23 | Ajinomoto Co., Inc. | Method for production of organic acid |
| WO2008133161A1 (en) | 2007-04-17 | 2008-11-06 | Ajinomoto Co., Inc. | Method for production of acidic substance having carboxyl group |
| WO2008133131A1 (en) | 2007-04-16 | 2008-11-06 | Ajinomoto Co., Inc. | Method for production of organic acid |
| WO2009072562A1 (en) | 2007-12-06 | 2009-06-11 | Ajinomoto Co., Inc. | Process for production of organic acid |
| WO2009075303A1 (en) | 2007-12-12 | 2009-06-18 | Mitsubishi Chemical Corporation | Aliphatic polyester resin and method for producing the same |
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1990
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|---|---|---|---|---|
| US5496923A (en) * | 1993-09-20 | 1996-03-05 | Mitsui Toatsu Chemicals, Inc. | Purification process of aliphatic polyester |
| US5679767A (en) * | 1993-09-20 | 1997-10-21 | Mitsui Toatsu Chemicals, Inc. | Purification process of aliphatic polyester |
| US5445778A (en) * | 1993-11-03 | 1995-08-29 | Cheil Synthetics Inc. | Method for the production of aliphatic copolyester film |
| US5714230A (en) * | 1993-11-18 | 1998-02-03 | Mitsui Toatsu Chemicals, Inc. | Degradable aliphatic polyester formed products |
| US5763098A (en) * | 1993-11-18 | 1998-06-09 | Mitsui Chemicals, Inc. | Degradable aliphatic polyester formed products |
| EP0694874A2 (en) | 1994-07-25 | 1996-01-31 | Toppan Printing Co., Ltd. | Biodegradable cards |
| EP0703260A1 (en) | 1994-09-21 | 1996-03-27 | Tonen Corporation | Aliphatic polyester and a process for the preparation thereof |
| WO1996019521A1 (en) * | 1994-12-21 | 1996-06-27 | Showa Denko Kabushiki Kaisha | Aliphatic polyester resin and process for producing the same |
| US5714569A (en) * | 1994-12-21 | 1998-02-03 | Showa Denko K.K. | Aliphatic polyester resin and method for producing same |
| WO2001019887A1 (en) * | 1999-09-10 | 2001-03-22 | Mitsui Chemicals, Inc. | Polyurethane resin with degradability |
| US6555645B1 (en) | 1999-09-10 | 2003-04-29 | Mitsui Chemicals, Inc. | Degradable polyurethane resin |
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| JP2006213825A (en) * | 2005-02-03 | 2006-08-17 | Chiba Univ | Method for producing barrier material excellent in heat stability |
| JP4605524B2 (en) * | 2005-02-03 | 2011-01-05 | 国立大学法人 千葉大学 | Method for producing barrier material with excellent thermal stability |
| WO2008126896A1 (en) | 2007-04-10 | 2008-10-23 | Ajinomoto Co., Inc. | Method for production of organic acid |
| WO2008133131A1 (en) | 2007-04-16 | 2008-11-06 | Ajinomoto Co., Inc. | Method for production of organic acid |
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