JPH0356251B2 - - Google Patents
Info
- Publication number
- JPH0356251B2 JPH0356251B2 JP63304471A JP30447188A JPH0356251B2 JP H0356251 B2 JPH0356251 B2 JP H0356251B2 JP 63304471 A JP63304471 A JP 63304471A JP 30447188 A JP30447188 A JP 30447188A JP H0356251 B2 JPH0356251 B2 JP H0356251B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- average molecular
- polymer
- caprolactone
- producing
- 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
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- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
本発明は、ラクトン重合体、詳しくは分子量分
布の狭いラクトン重合体およびその製造法に関す
る。
分子量が500〜5000のラクトン重合体はポリウ
レタン、塗料等の原料として非常に有用なもので
ある。
しかし、従来の分子量が500〜5000のラクトン
重合体は、分子量分布が広く重量平均分子量／数
平均分子量が2.5〜3.5もあり、実用上種々の問題
があつた。
本発明者は、ゲルパーミエーシヨンクロマトグ
ラフイー（以下GPCと称す）により、従来のラ
クトン重合体の分子量分布を研究し、その分子量
分布を滴正に調整するならば、実用上非常にすぐ
れた特性を与えるラクトン重合体が得られること
を見い出し、本発明を完成するに至つた。
すなわち、本発明は重量平均分子量／数平均分
子量が2.0以下であり、分子量が500〜5000である
分子量分布の狭いラクトン重合体およびその製造
法に関する。
本発明でいうラクトン重合体は、ε−カプロラ
クトンを活性水素を有する開始剤の存在下に開環
重合したものである。特に本発明は、塩素、ブロ
ム、ヨウ素等のハロゲン化第１スズからなる触媒
0.1〜50ppm及び多価アルコール又は多価アミン
からなる活性水素を有する開始剤の存在下にε−
カプロラクトンを開環重合して、重量平均分子
量／数平均分子量が1.1〜2.0であり、分子量が
500〜5000であるε−カプロラクトン重合体を製
造することを特徴とするラクトン重合体の製造法
に関するものである。開始剤としては、ジオー
ル、トリオールなどの多価アルコールや多価アミ
ンが利用できる。ジオールとしては、エチレング
リコール、ジエチレングリコール、１，４−ブチ
レングリコール、１，６−ヘキサンジオール、ネ
オペンチルグリコールなどが開示され、トリオー
ルとしては、トリメチロールプロパンなどが例示
できる。その他の多価アルコールとして、アクリ
ルポリオール、スチレンアリルアルコール共重合
体、ポリエステルポリオール等の水酸基を有する
高分子量樹脂も利用できる。多価アミンとしては
エチレンジアミン、ジエチレントリアミン、エタ
ノールアミン、さらには芳香族ポリアミン等も利
用できる。
本発明でいう分子量とは、ラクトン重合体の水
酸基価を測定し、次式により求めた値である。
分子量＝56.1×Ｎ×1000／水酸基価
水酸基価はJIS Ｋ−1557の6.4に準じて測定す
る。
Ｎは開始剤の官能基数である。
本発明のラクトン重合体の分子量は500〜5000
である。
以上述べたことから理解できるように、所定の
分子量を得るための重合開始剤の使用量は上記計
算式によつて定義できる。
又、分子量分布を示す重量平均分子量と数平均
分子量の比（W／N）は、GPCにより求める。
装 置 島津製作所のLC−3A
溶 媒 テトラヒドロフラン １ml／min
温 度 室 温
カラム 島津製作所の HSG−PRE １本
HSG−20 １本
HSG−15 ３本
HSG−10 １本
検出器 昭和電工のShodex RI SE−11
本発明のラクトン重合体の重量平均分子量／数
平均分子量は1.1以上2.0以下である。
次に本発明の重合体の製造法について説明す
る。
本発明の製造法においては、塩素、ブロム、ヨ
ウ素等のハロゲン化第１スズを触媒として用い
る。触媒量としては、ε−カプロラクトンの総重
量に対して0.1〜50ppmである。0.1ppm未満で
は、重合は進行せず、50ppmより多くでは、分子
量分布の狭い重合体を得ることは困難となる。反
応温度は、一般には100〜230℃、好ましくは120
〜190℃である。
これに対して、従来公知の触媒TBT（テトラブ
チルチタネート）は、開環付加重合はもちろんの
こと、エステル交換反応にも奇与するため、分子
量分布の広いものができてしまう。
本発明からなるラクトン重合体は、従来品に比
べ、分子量分布が狭く、かつ粘度も低く、融点も
若干低いという特徴をもつものである。
即ち実施例にも示す如く、重合体の粘度は75℃
におけるＢ型粘度計で300cps未満であり、融点は
常温から100℃までで、ワツクス状のものである。
本発明からなるラクトン重合体は、分子量分布
が狭いため、ウレタンエラストマー、ウレタン接
着剤、ウレタン塗料等、ポリウレタンの原料とし
て非常に有用なものである。
例えば、スパンデツクスの分野に用いれば、弾
性回復改良がすぐれたものを提供することができ
る。また、二液型ウレタン塗料のポリオール成分
としてハイソリツド塗料を提供することができ
る。
実施例１〜４及び比較例１〜３
＜分子量2000の場合＞
１の三ツ口セパラブルフラスコにε−カプロ
ラクトン969ｇ（8.5モル）、エチレングリコール
31ｇ（0.5モル）及び触媒を所定量を加え、温度
計、コンデンサー、窒素ガス吹込み配管を取付
け、窒素ガス雰囲気で所定温度で反応した。反応
終了はガスクロマトグラフイーでε−カプロラク
トンを測定し0.5％以下になつた時点で冷却し、
取り出し製品とした。
実施例５及び比較例４
＜分子量1250の場合＞
上記に準ずる。但しε−カプロラクトン594ｇ
（5.2モル）エチレングリコール31ｇ（0.5モル）
を仕込んだ。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lactone polymer, particularly a lactone polymer with a narrow molecular weight distribution, and a method for producing the same. Lactone polymers with a molecular weight of 500 to 5,000 are very useful as raw materials for polyurethane, paints, etc. However, conventional lactone polymers with a molecular weight of 500 to 5,000 have a wide molecular weight distribution and a weight average molecular weight/number average molecular weight of 2.5 to 3.5, and have had various practical problems. The present inventor studied the molecular weight distribution of conventional lactone polymers using gel permeation chromatography (hereinafter referred to as GPC), and found that if the molecular weight distribution could be adjusted to a positive droplet, it would be extremely effective in practical use. The inventors have discovered that a lactone polymer that provides these properties can be obtained, and have completed the present invention. That is, the present invention relates to a lactone polymer with a narrow molecular weight distribution having a weight average molecular weight/number average molecular weight of 2.0 or less and a molecular weight of 500 to 5000, and a method for producing the same. The lactone polymer referred to in the present invention is obtained by ring-opening polymerization of ε-caprolactone in the presence of an initiator having active hydrogen. In particular, the present invention provides catalysts comprising stannous halides such as chlorine, bromine, iodine, etc.
ε-
Ring-opening polymerization of caprolactone results in a weight average molecular weight/number average molecular weight of 1.1 to 2.0, and a molecular weight of
The present invention relates to a method for producing a lactone polymer, characterized by producing an ε-caprolactone polymer having a molecular weight of 500 to 5,000. As the initiator, polyhydric alcohols and polyhydric amines such as diols and triols can be used. Examples of diols include ethylene glycol, diethylene glycol, 1,4-butylene glycol, 1,6-hexanediol, and neopentyl glycol, and examples of triols include trimethylolpropane. As other polyhydric alcohols, high molecular weight resins having hydroxyl groups such as acrylic polyols, styrene allyl alcohol copolymers, and polyester polyols can also be used. As the polyvalent amine, ethylenediamine, diethylenetriamine, ethanolamine, aromatic polyamine, etc. can also be used. The molecular weight in the present invention is a value obtained by measuring the hydroxyl value of a lactone polymer and using the following formula. Molecular weight = 56.1 x N x 1000/hydroxyl value The hydroxyl value is measured according to 6.4 of JIS K-1557. N is the number of functional groups in the initiator. The molecular weight of the lactone polymer of the present invention is 500 to 5000
It is. As can be understood from the above description, the amount of polymerization initiator used to obtain a predetermined molecular weight can be defined by the above calculation formula. Further, the ratio ( W / N ) between the weight average molecular weight and the number average molecular weight, which indicates the molecular weight distribution, is determined by GPC. Equipment Shimadzu LC-3A Solvent Tetrahydrofuran 1 ml/min Temperature Room Temperature Column Shimadzu HSG-PRE 1 HSG-20 1 HSG-15 3 HSG-10 1 Detector Showa Denko Shodex RI SE -11 The weight average molecular weight/number average molecular weight of the lactone polymer of the present invention is 1.1 or more and 2.0 or less. Next, a method for producing the polymer of the present invention will be explained. In the production method of the present invention, stannous halides such as chlorine, bromine, and iodine are used as catalysts. The amount of catalyst is 0.1 to 50 ppm based on the total weight of ε-caprolactone. If it is less than 0.1 ppm, polymerization will not proceed, and if it is more than 50 ppm, it will be difficult to obtain a polymer with a narrow molecular weight distribution. The reaction temperature is generally 100 to 230°C, preferably 120°C.
~190℃. On the other hand, the conventionally known catalyst TBT (tetrabutyl titanate) not only participates in ring-opening addition polymerization but also participates in transesterification reactions, resulting in products with a wide molecular weight distribution. The lactone polymer of the present invention is characterized by a narrower molecular weight distribution, lower viscosity, and slightly lower melting point than conventional products. That is, as shown in the examples, the viscosity of the polymer was 75°C.
It is less than 300 cps on a B-type viscometer, the melting point is from room temperature to 100°C, and it is wax-like. Since the lactone polymer of the present invention has a narrow molecular weight distribution, it is very useful as a raw material for polyurethanes such as urethane elastomers, urethane adhesives, and urethane paints. For example, when used in the field of spandex, it can provide improved elastic recovery. Furthermore, a high solids paint can be provided as a polyol component of a two-component urethane paint. Examples 1 to 4 and Comparative Examples 1 to 3 <For molecular weight 2000> 969 g (8.5 mol) of ε-caprolactone and ethylene glycol were placed in the three-necked separable flask of 1.
31 g (0.5 mol) and a predetermined amount of catalyst were added, a thermometer, a condenser, and a nitrogen gas blowing pipe were attached, and the reaction was carried out at a predetermined temperature in a nitrogen gas atmosphere. To complete the reaction, measure ε-caprolactone using gas chromatography, and when it reaches 0.5% or less, cool it.
It was taken out and made into a product. Example 5 and Comparative Example 4 <For molecular weight 1250> Same as above. However, ε-caprolactone 594g
(5.2 mol) Ethylene glycol 31g (0.5 mol)
I prepared it. 【table】
Claims (1)
ズからなる触媒0.1〜50ppm及び多価アルコール
又は多価アミンからなる活性水素を有する開始剤
の存在下に100〜230℃の温度でε−カプロラクト
ンを開環重合して、重量平均分子量／数平均分子
量が1.1〜2.0であり、分子量が500〜5000で75℃
におけるＢ型粘度計による粘度は300cps未満であ
り、融点が常温から100℃であるε−カプロラク
トン重合体を製造することを特徴とする分子量分
布の狭いラクトン重合体の製造法。1. ε-caprolactone at a temperature of 100 to 230°C in the presence of 0.1 to 50 ppm of a catalyst consisting of a stannous halide such as chlorine, bromine, or iodine, and an initiator having active hydrogen consisting of a polyhydric alcohol or a polyhydric amine. Ring-opening polymerization with a weight average molecular weight/number average molecular weight of 1.1 to 2.0 and a molecular weight of 500 to 5000 at 75℃
A method for producing a lactone polymer with a narrow molecular weight distribution, characterized by producing an ε-caprolactone polymer having a viscosity measured by a B-type viscometer of less than 300 cps and a melting point ranging from room temperature to 100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63304471A JPH02628A (en) | 1988-12-01 | 1988-12-01 | Lactone polymer of narrow molecular weight distribution and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63304471A JPH02628A (en) | 1988-12-01 | 1988-12-01 | Lactone polymer of narrow molecular weight distribution and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02628A JPH02628A (en) | 1990-01-05 |
| JPH0356251B2 true JPH0356251B2 (en) | 1991-08-27 |
Family
ID=17933419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63304471A Granted JPH02628A (en) | 1988-12-01 | 1988-12-01 | Lactone polymer of narrow molecular weight distribution and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02628A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0783009A2 (en) | 1995-12-01 | 1997-07-09 | Hokushin Corporation | Method for producing millable polyurethanes and polyurethane elastomers |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0592668B1 (en) * | 1991-07-03 | 1999-03-10 | Kanebo, Ltd. | Method and device for the manufacture of a thermoplastic polyurethane elastomer |
| US6008312A (en) * | 1995-12-01 | 1999-12-28 | Hokushin Corp | Method for producing millable polyurethanes and polyurethane elastomers |
| EP0776921A3 (en) * | 1995-12-01 | 1997-08-13 | Hokushin Corp | Method for the preparation of amorphous polymer chains of elastomers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA782039B (en) * | 1977-05-23 | 1979-09-26 | American Cyanamid Co | Surgical articles |
-
1988
- 1988-12-01 JP JP63304471A patent/JPH02628A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0783009A2 (en) | 1995-12-01 | 1997-07-09 | Hokushin Corporation | Method for producing millable polyurethanes and polyurethane elastomers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02628A (en) | 1990-01-05 |
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