JPH08245787A - Production of polymer having high molecular weight - Google Patents
Production of polymer having high molecular weightInfo
- Publication number
- JPH08245787A JPH08245787A JP5092795A JP5092795A JPH08245787A JP H08245787 A JPH08245787 A JP H08245787A JP 5092795 A JP5092795 A JP 5092795A JP 5092795 A JP5092795 A JP 5092795A JP H08245787 A JPH08245787 A JP H08245787A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- molecular weight
- hydroxyethyl
- high molecular
- isocyanate
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フィルム、シート、成
型物等に利用できる実用上十分な強度を持つ、高分子量
化されたポリマーの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polymer having a high molecular weight, which has practically sufficient strength and can be used in films, sheets, molded products and the like.
【０００２】[0002]
【従来の技術】結合剤に多官能イソシアネートを用い
て、水酸基を分子末端に有するポリマーを高分子量化す
る方法が知られている。それは、ポリマー末端の水酸基
とイソソアネート基が反応して、ポリマー間にウレタン
結合をつくり高分子量化するものである。2. Description of the Related Art There is known a method in which a polyfunctional isocyanate is used as a binder to increase the molecular weight of a polymer having a hydroxyl group at the molecular end. That is, a hydroxyl group at the end of the polymer and an isosonate group react with each other to form a urethane bond between the polymers to make a high molecular weight.
【０００３】また、フェノールやオキシムでブロック化
された多官能のブロック化イソシアネートを結合剤に用
いて、加熱により脱ブロック化されて生じたイソシアネ
ート基を水酸基と反応させる方法がある。（特開平５−
２８７０４２号公報等）Further, there is a method in which a polyfunctional blocked isocyanate blocked with phenol or oxime is used as a binder to react an isocyanate group generated by deblocking by heating with a hydroxyl group. (JP-A-5-
287042 publication)
【０００４】[0004]
【発明が解決しようとする課題】多官能イソシアネート
を結合剤に用いて、水酸基を末端に有するポリマーを高
分子量化する場合、理論的には、ポリマーの水酸基数に
対して、イソシアネート基数が等しくなる量のイソシア
ネートを用いる必要がある。しかし、イソシアネートは
反応性が高く、ポリマーが水分を含んでいると、ポリマ
ーの水酸基より水の方と優先的に反応し、高分子量化に
寄与しない。そこで、通常は水酸基に対して、少し過剰
のイソシアネートを用いるのが一般的である。水酸基ま
たはイソシアネート基のどちらか一方が極端に過剰であ
れば、十分に高分子量化ぜず、さらにはイソシアネート
基が多い時は、余分なイソシアネートが、ポリマーをつ
なげているウレタン結合の窒素上の活性水素と反応して
架橋体となり、系がゲル化することがある。When a polyfunctional isocyanate is used as a binder to make a polymer having a hydroxyl group at a high molecular weight, theoretically, the number of isocyanate groups is equal to the number of hydroxyl groups of the polymer. It is necessary to use an amount of isocyanate. However, isocyanate is highly reactive, and when the polymer contains water, it reacts preferentially with water rather than with the hydroxyl groups of the polymer, and does not contribute to increasing the molecular weight. Therefore, it is general to use a slight excess of isocyanate with respect to the hydroxyl group. If either the hydroxyl group or the isocyanate group is extremely excessive, the polymer will not have a sufficiently high molecular weight, and if there are too many isocyanate groups, the excess isocyanate will activate the nitrogen bond of the urethane bond connecting the polymers. It may react with hydrogen to form a cross-linked product, and the system may gel.
【０００５】またイソシアネートは一般に毒性が強く、
残存イソシアネートが問題となる分野には利用できな
い。Isocyanates are generally highly toxic,
It cannot be used in areas where residual isocyanate is a problem.
【０００６】イソシアネートをフェノールやオキシムで
ブロック化したブロック化イソシアネートもポリマーの
高分子量化に用いられている。しかし、ブロック化イソ
シアネートは、イソシアネートに比べると毒性は低いも
のの、熱等で脱ブロック化しやすく、依然毒性を有する
ことには変わりない。Blocked isocyanate obtained by blocking isocyanate with phenol or oxime is also used for increasing the polymer molecular weight. However, blocked isocyanate is less toxic than isocyanate, but is easily deblocked by heat or the like, and it still has toxicity.
【０００７】本発明者らは、上記の多官能イソシアネー
トを結合剤に用いて、水酸基を分子末端に有するポリマ
ーを高分子量化する場合の問題点について検討した結
果、水酸基を分子末端に有するポリマーとヒドロキシエ
チルジカルバメートとを脱エチレングリコール反応させ
ることにより、上記の問題点を解決できることを見いだ
し、本発明を完成させた。The inventors of the present invention have studied the problems in the case of using a polyfunctional isocyanate as a binder to increase the molecular weight of a polymer having a hydroxyl group at the molecular end. It was found that the above problems can be solved by reacting hydroxyethyl dicarbamate with ethylene glycol, and the present invention was completed.
【０００８】すなわち本発明は、水酸基を分子末端に有
するポリマーから、毒性のあるイソシアネートを使用す
ることなく、またゲル化等を起こすことなく簡便に収率
よく、高分子量化されたポリマーを製造する方法を提供
することを目的とする。That is, according to the present invention, a polymer having a high molecular weight can be easily produced from a polymer having a hydroxyl group at a molecular end without using a toxic isocyanate and without causing gelation or the like in a high yield. The purpose is to provide a method.
【０００９】[0009]
【課題を解決するための手段】本発明は、水酸基を分子
末端に有するポリマー（Ｉ）と、下記一般式（１）The present invention comprises a polymer (I) having a hydroxyl group at the molecular end and a compound represented by the following general formula (1):
【００１０】[0010]
【化３】 Embedded image
【００１１】（式中、Ａは炭素数１〜１２の２価の有機
残基を表わす。）で表されるヒドロキシエチルジカルバ
メートとを、脱エチレングリコール反応させる下記一般
式（２）(Wherein A represents a divalent organic residue having 1 to 12 carbon atoms) and a hydroxyethyldicarbamate represented by the following general formula (2)
【００１２】[0012]
【化４】 [Chemical 4]
【００１３】（式中、Ａは一般式（１）と同じ、Ｂはポ
リマー（Ｉ）の反応残基、ｍは０〜５の整数、ｎは２〜
１００の整数を表わす。）で表されるポリマーを製造す
ることを特徴とする、高分子量化されたポリマーの製造
方法である。(In the formula, A is the same as in the general formula (1), B is the reaction residue of the polymer (I), m is an integer of 0 to 5, and n is 2 to
Represents an integer of 100. ) Is produced, the method for producing a polymer having a high molecular weight is characterized.
【００１４】以下に、本発明についてさらに詳細に説明
する。The present invention will be described in more detail below.
【００１５】本発明に用いるポリマー（Ｉ）としては、
水酸基を分子末端に有するポリマーであれば特に制限さ
れないが、ポリマー（Ｉ）の具体例としては、ポリエチ
レングリコ−ル、ポリプロピレングリコ−ル、ポリテト
ラエチレングリコール、ポリエピクロルヒドリン、さら
にはこれらの共重合物などのポリエーテル；ポリエチレ
ンテレフタレ−ト、ポリブチレンテレフタレ−ト等の芳
香族ポリエステル；ポリエチレンサクシネ−ト、ポリブ
チレンサクシネ−ト、ポリエチレンアジペ−ト、ポリブ
チレンアジペ−ト等の脂肪族ポリエステル；さらにはこ
れら２種以上の共重合物などのポリエステル；さらには
前記ポリエーテルと前記ポリエステルとの共重合物など
がある。特に前記ポリマー（Ｉ）としては、水酸基を分
子の両末端に有しているポリマーが、高分子量化の効果
が大きい点で好ましい。The polymer (I) used in the present invention is
The polymer (I) is not particularly limited as long as it has a hydroxyl group at its molecular terminal, but specific examples of the polymer (I) include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyepichlorohydrin, and copolymers thereof. Aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyethylene succinate, polybutylene succinate, polyethylene adipate, polybutylene adipate, etc. Examples include aliphatic polyesters; polyesters such as copolymers of two or more of these; and copolymers of the above-mentioned polyethers and polyesters. In particular, as the polymer (I), a polymer having hydroxyl groups at both ends of the molecule is preferable because the effect of increasing the molecular weight is great.
【００１６】本発明で用いるヒドロキシエチルジカルバ
メートは、前記一般式（１）で表されるものであれば特
に限定されず、一般式（１）中のＡは、炭素数１〜１２
の２価の有機残基を表わし、酸素、窒素、硫黄、ハロゲ
ン元素を含んでいてもよい。The hydroxyethyl dicarbamate used in the present invention is not particularly limited as long as it is represented by the general formula (1), and A in the general formula (1) has 1 to 12 carbon atoms.
Represents a divalent organic residue, and may contain oxygen, nitrogen, sulfur and halogen elements.
【００１７】本発明で用いるヒドロキシエチルジカルバ
メートは、エチレンカ−ボネ−トとアルキルジアミンと
から容易に合成できる。アルキルジアミンとしては特に
制限はなく、例として挙げれば、エチレンジアミン、テ
トラメチレンジアミン、ヘキサメチレンジアミン、ジア
ミノシクロヘキサン、ジアミノジエチルエーテル等の脂
肪族ジアミンやフェニレンジアミン、キシリレンジアミ
ン、ジアミノジフェニルエーテル等の芳香族ジアミンが
ある。The hydroxyethyldicarbamate used in the present invention can be easily synthesized from ethylene carbonate and alkyldiamine. The alkyldiamine is not particularly limited, and examples thereof include aliphatic diamines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, diaminocyclohexane, diaminodiethylether and phenylenediamine, xylylenediamine, aromatic diamines such as diaminodiphenylether. There is.
【００１８】本発明に用いるヒドロキシエチルジカルバ
メートの添加量としては、イソシアネートを用いる時に
比べて自由度があるので、水酸基を分子末端に有するポ
リマーの水酸基当量に応じて適宜決めれば良い。The addition amount of hydroxyethyl dicarbamate used in the present invention has a degree of freedom compared to the case of using isocyanate, and therefore may be appropriately determined according to the hydroxyl equivalent of a polymer having a hydroxyl group at the molecular end.
【００１９】本発明の製造方法においては、水酸基を分
子末端に有するポリマーに、ヒドロキシエチルジカルバ
メートを所定量添加し、減圧条件下で加熱攪拌して、生
成するエチレングリコ−ルを除くことにより行うことが
できる。また、水酸基を分子末端に有するポリマーに、
ヒドロキシエチルジカルバメートの原料である、エチレ
ンカ−ボネ−トとジアミンを添加して、反応系内でヒド
ロキシエチルジカルバメートを生成させてそれを反応に
用いてもよい。In the production method of the present invention, a predetermined amount of hydroxyethyldicarbamate is added to a polymer having a hydroxyl group at the molecular end, and the mixture is heated and stirred under reduced pressure to remove the ethylene glycol produced. be able to. In addition, the polymer having a hydroxyl group at the molecular end,
It is also possible to add ethylene carbonate and a diamine, which are raw materials of hydroxyethyl dicarbamate, to generate hydroxyethyl dicarbamate in the reaction system and use it for the reaction.
【００２０】本発明における、水酸基を分子末端に有す
るポリマーと、ヒドロキシエチルジカルバメートとの反
応において、触媒として有機金属、金属錯体、金属塩等
の金属系触媒を用いてもよい。具体的には、ジブチル錫
ジラウリレート、オクチル酸錫、オクチル酸鉛等が挙げ
られる。In the reaction of the polymer having a hydroxyl group at the molecular end thereof with hydroxyethyldicarbamate in the present invention, a metal-based catalyst such as an organic metal, a metal complex or a metal salt may be used as a catalyst. Specific examples include dibutyltin dilaurate, tin octylate, and lead octylate.
【００２１】反応温度としては、反応を速くするために
は高い方が有利であるが、高すぎると着色等のポリマ−
の劣化があるので、１００から３００℃の範囲、好まし
くは、１５０から２５０℃の範囲である。It is advantageous that the reaction temperature is high in order to accelerate the reaction, but if it is too high, the polymer such as coloring is polymerized.
Therefore, the temperature is in the range of 100 to 300 ° C., preferably 150 to 250 ° C.
【００２２】反応の際の減圧度としては、生成するエチ
レングリコ−ルを効率良く除くために、５ｍｍＨｇ以
下、好ましくは、１ｍｍＨｇ以下である。The degree of pressure reduction during the reaction is 5 mmHg or less, preferably 1 mmHg or less in order to efficiently remove the ethylene glycol produced.
【００２３】[0023]
【実施例】以下に本発明の実施例を示すが、本発明はこ
れに限定されない。また、実施例中の部は重量部を示
す。ポリマーの数平均分子量は、ＧＰＣにより求めた標
準ポリスチレン換算の分子量である。EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. Moreover, the part in an Example shows a weight part. The number average molecular weight of the polymer is the molecular weight in terms of standard polystyrene determined by GPC.
【００２４】参考例１ 撹拌装置を付けた５００ｍｌフラスコに、エチレンカー
ボネート８８．０ｇを仕込んで加熱溶融させた後、ヘキ
サメチレンジアミン（８５％水溶液）５４．６ｇを内温
を５０℃に保ちながら滴下し反応させることにより、ビ
ス（２−ヒドロキシエチル）ヘキサメチレンジカルバメ
−ト６５．２ｇ（収率４８．５％）を得た。Reference Example 1 A 500 ml flask equipped with a stirrer was charged with 88.0 g of ethylene carbonate and heated and melted. Then, 54.6 g of hexamethylenediamine (85% aqueous solution) was added dropwise while keeping the internal temperature at 50 ° C. The reaction was carried out to obtain 65.2 g (yield 48.5%) of bis (2-hydroxyethyl) hexamethylene dicarbamate.
【００２５】実施例１ 反応容器にポリエチレングリコ−ル（三洋化成（株）
製、ＰＥＧ−４０００Ｎ、平均分子量３０００）１００
部、参考例１で合成した、ビス（２−ヒドロキシエチ
ル）ヘキサメチレンジカルバメ−ト１０部およびジブチ
ル錫ジラウリレ−ト０．５部を仕込み、１５０℃、１ｍ
ｍＨｇ以下で５時間反応させた。その結果、カルバミン
酸エステル結合によって高分子量化された数平均分子量
２９０００のポリエチレングリコ−ルを製造した。Example 1 Polyethylene glycol (Sanyo Kasei Co., Ltd.) was placed in a reaction vessel.
Manufactured by PEG-4000N, average molecular weight 3000) 100
Part, 10 parts of bis (2-hydroxyethyl) hexamethylene dicarbamate synthesized in Reference Example 1 and 0.5 part of dibutyltin dilaurate were charged, and the temperature was 150 ° C. and 1 m.
The reaction was carried out at mHg or less for 5 hours. As a result, a polyethylene glycol having a number average molecular weight of 29000 and having a high molecular weight through a carbamate bond was produced.
【００２６】実施例２ ビス（２−ヒドロキシエチル）ヘキサメチレンジカルバ
メ−ト２０部用いる以外は、実施例１と同様の条件で反
応を行った。その結果、カルバミン酸エステル結合によ
って高分子量化された数平均分子量１０００００のポリ
エチレングリコ−ルを製造した。Example 2 The reaction was carried out under the same conditions as in Example 1 except that 20 parts of bis (2-hydroxyethyl) hexamethylene dicarbamate was used. As a result, a polyethylene glycol having a number average molecular weight of 100,000 and having a high molecular weight by a carbamate bond was produced.
【００２７】実施例３ ビス（２−ヒドロキシエチル）ヘキサメチレンジカルバ
メ−ト４０部用いる以外は、実施例１と同様の条件で反
応を行った。その結果、カルバミン酸エステル結合によ
って高分子量化された数平均分子量５４０００のポリエ
チレングリコ−ルを製造した。Example 3 The reaction was carried out under the same conditions as in Example 1 except that 40 parts of bis (2-hydroxyethyl) hexamethylenedicarbamate was used. As a result, a polyethylene glycol having a number average molecular weight of 54,000, which had a high molecular weight by a carbamic acid ester bond, was produced.
【００２８】実施例４ 反応容器にポリエチレングリコ−ル（三洋化成（株）
製、ＰＥＧ−２００００、数平均分子量３００００）１
００部、ビス（２−ヒドロキシエチル）ヘキサメチレン
ジカルバメ−ト２部およびジブチル錫ジラウリレ−ト
０．５部を仕込み、１５０℃、１ｍｍＨｇ以下で５時間
反応させた。その結果、カルバミン酸エステル結合によ
って高分子量化された数平均分子量１２２０００のポリ
エチレングリコ−ルを製造した。Example 4 Polyethylene glycol (Sanyo Kasei Co., Ltd.) was placed in a reaction vessel.
Manufactured by PEG-20000, number average molecular weight 30,000) 1
00 parts, bis (2-hydroxyethyl) hexamethylene dicarbamate 2 parts and dibutyltin dilaurate 0.5 part were charged and reacted at 150 ° C. and 1 mmHg or less for 5 hours. As a result, a polyethylene glycol having a number average molecular weight of 122000, which had a high molecular weight through a carbamate bond, was produced.
【００２９】実施例５ セルフクリーニング型２軸混合機（（株）栗本鉄工所製
ＫＲＣ−Ｓ１リアクター）に、ポリエチレングリコ−ル
（三洋化成（株）製、ＰＥＧ−２００００、平均分子量
３００００）１００部、ビス（２−ヒドロキシエチル）
ヘキサメチレンジカルバメ−ト２部およびジブチル錫ジ
ラウリレ−ト０．０５部仕込み、１５０℃、１ｍｍＨｇ
以下で２時間反応させることにより、数平均分子量４９
０００のカルバミン酸エステル結合によって高分子量化
されたポリエチエレングリコ−ルを製造した。Example 5 100 parts of polyethylene glycol (manufactured by Sanyo Kasei Co., Ltd., PEG-20000, average molecular weight 30000) was added to a self-cleaning twin-screw mixer (KRC-S1 reactor manufactured by Kurimoto Iron Works Co., Ltd.). , Bis (2-hydroxyethyl)
Charged with 2 parts of hexamethylene dicarbamate and 0.05 parts of dibutyltin dilaurate, 150 ° C., 1 mmHg
By reacting for 2 hours below, a number average molecular weight of 49
Polyethylene glycol having a high molecular weight of 000 carbamate bonds was prepared.
【００３０】参考例２ オートクレーブに無水コハク酸５００．９部、テトラ−
ｎ−ブトキシジルコニウム４．９３部を加え窒素置換を
行った。次いで、撹拌下１３０℃まで昇温して無水コハ
ク酸を溶融し、同温度でオートクレーブ内の圧力を４．
０〜８．４ｋｇｆ／ｃｍ２に維持しながら、酸化エチレ
ン２６７．０部を１時間あたり４７部の添加速度で５．
７時間にわたって連続的に導入した。酸化エチレン導入
後１３０℃で３．０時間熟成反応を行うことにより数平
均分子量１２０００のポリエステルを得た。Reference Example 2 500.9 parts of succinic anhydride in an autoclave, tetra-
Nitrogen substitution was carried out by adding 4.93 parts of n-butoxyzirconium. Then, the temperature was raised to 130 ° C. with stirring to melt the succinic anhydride, and the pressure in the autoclave was set to 4. at the same temperature.
While maintaining 0 to 8.4 kgf / cm2, 267.0 parts of ethylene oxide was added at an addition rate of 47 parts per hour.
It was introduced continuously for 7 hours. After introducing ethylene oxide, a maturing reaction was performed at 130 ° C. for 3.0 hours to obtain a polyester having a number average molecular weight of 12,000.
【００３１】実施例６ 参考例２で得たポリエステル１００部、ビス（２−ヒド
ロキシエチル）ヘキサメチレンジカルバメ−ト５部、ジ
ブチル錫ジラウリレ−ト０．５部を反応容器に仕込み、
１９０℃、１ｍｍＨｇ以下で５時間反応させた。その結
果、カルバミン酸エステル結合によって高分子量化され
た数平均分子量３５０００のポリエステルを製造した。Example 6 100 parts of the polyester obtained in Reference Example 2, 5 parts of bis (2-hydroxyethyl) hexamethylene dicarbamate and 0.5 part of dibutyltin dilaurate were placed in a reaction vessel.
The reaction was carried out at 190 ° C. and 1 mmHg or less for 5 hours. As a result, a polyester having a number average molecular weight of 35,000, which had a high molecular weight through a carbamate bond, was produced.
【００３２】比較例１ 反応容器にポリエチレングリコ−ル（三洋化成（株）
製、ＰＥＧ−４０００Ｎ、平均分子量３０００）１００
部、ヘキサメチレンジイソシアネート１０部およびジブ
チル錫ジラウリレ−ト０．５部を仕込み、１５０℃で反
応させたところ、すぐに反応物の粘度が増大しゲル化が
起こった。Comparative Example 1 Polyethylene glycol (Sanyo Kasei Co., Ltd.) was placed in a reaction vessel.
Manufactured by PEG-4000N, average molecular weight 3000) 100
Parts, 10 parts of hexamethylene diisocyanate and 0.5 parts of dibutyltin dilaurate were charged and reacted at 150 ° C., the viscosity of the reaction product immediately increased and gelation occurred.
【００３３】[0033]
【発明の効果】本発明において用いるヒドロキシエチル
ジカルバメートは、イソシアネートと比較すると毒性は
低く安全性が高い。またイソシアネートは、水やアルコ
ール等の活性水素を持った化合物があると反応して失活
するが、ヒドロキシエチルジカルバメートはそれらの物
質に対して安定なので、高分子量化させるポリマーの乾
燥等の前処理は不要である。そして、ヒドロキシエチル
ジカルバメートは、それ単独でも脱エチレングリコール
反応してカルバミン酸エステル結合をつくるので、イソ
シアネートを用いる時に要求される、添加量の厳密なコ
ントロールは必要ない。The hydroxyethyldicarbamate used in the present invention has low toxicity and high safety as compared with isocyanate. In addition, isocyanate reacts with and deactivates when there is a compound having active hydrogen such as water or alcohol, but since hydroxyethyldicarbamate is stable to these substances, it is necessary to dry it before drying the polymer to make it high molecular weight. No processing is necessary. Since hydroxyethyldicarbamate alone undergoes a deethylene glycol reaction to form a carbamic acid ester bond, strict control of the addition amount required when using an isocyanate is not necessary.
【００３４】したがって本発明によれば、毒性のあるイ
ソシアネートを使用することなく、また乾燥等の前処理
も不要で、添加量のふれによりゲル化等を起こすことも
なく、安全で簡便に収率よく安定的に、水酸基を分子末
端に有するポリマーから高分子量化されたポリマーを製
造できる。該ポリマーは、実用上十分な強度を持ち、フ
ィルム、シート、成型物等に有用である。Therefore, according to the present invention, a toxic isocyanate is not used, pretreatment such as drying is not necessary, gelation does not occur due to fluctuation of the addition amount, and the yield is safe and simple. A polymer having a high molecular weight can be produced in a stable manner from a polymer having a hydroxyl group at the molecular end. The polymer has practically sufficient strength and is useful for films, sheets, molded products and the like.
Claims (2)
（Ｉ）と、下記一般式（１） 【化１】 （式中、Ａは炭素数１〜１２の２価の有機残基を表わ
す。）で表されるヒドロキシエチルジカルバメートと
を、脱エチレングリコール反応させ下記一般式（２） 【化２】 （式中、Ａは一般式（１）と同じ、Ｂはポリマー（Ｉ）
の反応残基、ｍは０〜５の整数、ｎは２〜１００の整数
を表わす。）で表されるポリマーを製造することを特徴
とする、高分子量化されたポリマーの製造方法。1. A polymer (I) having a hydroxyl group at the molecular end, and a compound represented by the following general formula (1): (In the formula, A represents a divalent organic residue having 1 to 12 carbon atoms.) A hydroxyethyldicarbamate represented by the following general formula (2) (In the formula, A is the same as in the general formula (1), and B is the polymer (I).
Is a reaction residue, m is an integer of 0 to 5, and n is an integer of 2 to 100. The manufacturing method of the high molecular weight polymer characterized by manufacturing the polymer represented by these.
リオールまたはポリエステルポリオールである請求項１
に記載の製造方法。2. The polymer (I) is a polyether polyol or a polyester polyol.
The manufacturing method described in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5092795A JPH08245787A (en) | 1995-03-10 | 1995-03-10 | Production of polymer having high molecular weight |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5092795A JPH08245787A (en) | 1995-03-10 | 1995-03-10 | Production of polymer having high molecular weight |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08245787A true JPH08245787A (en) | 1996-09-24 |
Family
ID=12872454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5092795A Pending JPH08245787A (en) | 1995-03-10 | 1995-03-10 | Production of polymer having high molecular weight |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08245787A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011162237A1 (en) * | 2010-06-24 | 2011-12-29 | 大日精化工業株式会社 | Self-crosslinkable polyhydroxy polyurethane resin, resinaceous material that contains the resin, process for production of the resin, and imitation leather, surfacing material and weatherstrip material, using the resin |
| CN105001400A (en) * | 2015-05-08 | 2015-10-28 | 北京化工大学 | Method for preparing biodegradable aliphatic thermoplastic poly (ester urethane) and elastomer thereof through non-isocyanate method |
| CN105273185A (en) * | 2014-07-21 | 2016-01-27 | 北京化工大学 | Method for preparing aliphatic-aromatic mixed block thermoplastic polyurethane through nonisocyanate method |
| US9359719B2 (en) | 2011-04-04 | 2016-06-07 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinkable polysiloxane-modified polyhydroxy polyurethane resin, process for producing said resin, resin material comprising said resin, and artificial leather produced utilizing said resin |
| US9394462B2 (en) | 2009-11-25 | 2016-07-19 | Dainichiseika Color & Chemicals Mfg. Co., Ltd | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
| CN106317406A (en) * | 2015-06-16 | 2017-01-11 | 北京化工大学 | Method for preparing biodegradable thermoplastic polyurethane with benzene ring structure through nonisocyanate method |
| CN106700068A (en) * | 2016-11-15 | 2017-05-24 | 北京化工大学 | Non-isocyanate preparation method of fatty-group biodegradable polyurethane thermoplastic elastomer |
| CN107141471A (en) * | 2016-03-01 | 2017-09-08 | 北京化工大学 | The method that non-isocyanate method prepares aliphatic biodegradable thermoplastic polyurethane and elastomer |
| US10000609B2 (en) | 2010-08-26 | 2018-06-19 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, resin material containing same, method for producing same, artificial leather comprising same, and thermoplastic polyolefin skin material comprising same |
-
1995
- 1995-03-10 JP JP5092795A patent/JPH08245787A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9394462B2 (en) | 2009-11-25 | 2016-07-19 | Dainichiseika Color & Chemicals Mfg. Co., Ltd | Polysiloxane-modified polyhydroxy polyurethane resin, method for producing same, heat-sensitive recording material using the resin, imitation leather, thermoplastic polyolefin resin skin material, material for weather strip, and weather strip |
| WO2011162237A1 (en) * | 2010-06-24 | 2011-12-29 | 大日精化工業株式会社 | Self-crosslinkable polyhydroxy polyurethane resin, resinaceous material that contains the resin, process for production of the resin, and imitation leather, surfacing material and weatherstrip material, using the resin |
| US10066048B2 (en) | 2010-06-24 | 2018-09-04 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinkable polyhydroxy polyurethane resin, resinaceous material that contains the resin, process for production of the resin, and imitation leather, surfacing material and weatherstrip material, using the resin |
| US10000609B2 (en) | 2010-08-26 | 2018-06-19 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinking polysiloxane-modified polyhydroxy polyurethane resin, resin material containing same, method for producing same, artificial leather comprising same, and thermoplastic polyolefin skin material comprising same |
| US9359719B2 (en) | 2011-04-04 | 2016-06-07 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Self-crosslinkable polysiloxane-modified polyhydroxy polyurethane resin, process for producing said resin, resin material comprising said resin, and artificial leather produced utilizing said resin |
| CN105273185A (en) * | 2014-07-21 | 2016-01-27 | 北京化工大学 | Method for preparing aliphatic-aromatic mixed block thermoplastic polyurethane through nonisocyanate method |
| CN105001400A (en) * | 2015-05-08 | 2015-10-28 | 北京化工大学 | Method for preparing biodegradable aliphatic thermoplastic poly (ester urethane) and elastomer thereof through non-isocyanate method |
| CN106317406A (en) * | 2015-06-16 | 2017-01-11 | 北京化工大学 | Method for preparing biodegradable thermoplastic polyurethane with benzene ring structure through nonisocyanate method |
| CN107141471A (en) * | 2016-03-01 | 2017-09-08 | 北京化工大学 | The method that non-isocyanate method prepares aliphatic biodegradable thermoplastic polyurethane and elastomer |
| CN106700068A (en) * | 2016-11-15 | 2017-05-24 | 北京化工大学 | Non-isocyanate preparation method of fatty-group biodegradable polyurethane thermoplastic elastomer |
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