【発明の詳細な説明】[Detailed description of the invention]
［産業上の利用分野］
本発明は水酸基含有液状重合体の製造方法に関し、詳し
くは過度の粘度上昇またはゲル化を伴うことなく平均官
能基（水酸基）数の高い水酸基含有液状重合体を製造す
る方法に関する。
［従来の技術及び発明が解決しようとする課題］水酸基
を含有するジエン系重合体をウレタン樹脂の原料として
用いると、耐水性、低温特性および電気特性にすぐれた
ウレタン樹脂が得られる。
通常に用いられる水酸基含有ジエン系重合体は、１分子
当りの水酸基数が２個までであるが、ウレタンフオーム
用または硬質ウレタン用の原料としては、平均水酸基数
が２．５以上のものが望まれる。
従来、平均水酸基数２．５以上のジエン系重合体を得る
方法として、平均水酸基数２程度の水酸基含有ジエン系
重合体をカチオン重合触媒の存在下で反応させる方法が
知られている（特開昭５５−１１６７０２号公報）、シ
かしながら、この方法は分子間の架橋反応によって１分
子当りの平均水酸基数の上昇を図るものであるため、生
成物の粘度上昇、が著しいうえ、平均水酸基数も最高４
．０程度であり、熱安定性にも劣るという欠点があった
。さらに、平均水酸基数４．０以上のものを得ようとす
ると、系全体がゲル化し固体状になってしまうという重
大な問題があった。
［課題を解決するための手段］
そこで、本発明本は粘度上昇またはゲル化を起すことな
く平均水酸基数の高い液状重合体を製造する方法につい
て検討したところ、液状ジエン系重合体をエポキシ化し
た後、開環処理すれば、目的を達成できることを見出し
、この知見に基づいて本発明を完成した。
すなわち、本発明は液状ジエン系重合体をエポキシ化し
たエポキシ化液状重合体を開環処理することを特徴とす
る水酸基含有液状重合体の製造方法を提供するものであ
る。
本発明で用いる液状ジエン系重合体としては、数平均分
子量が３００〜２５０００ 、好ましくは５００〜１０
０００のものであり、これらの液状ジエン系重合体とし
ては炭素数４〜１２のジエン重合体、ジエン共重合体、
さらにはこれらジエンモノマーと炭素数２〜２２のα−
オレフィン性付加重合性千ツマ−との共重合体などがあ
る。具体的にはブタジェンホモポリマー、イソプレンホ
モポリマー、クロロブレンホモポリマー、ブタジェン−
スチレンコポリマー、ブタジェン−イソプレンコポリマ
ー、ブタジェン−アクリロニトリルコポリマー、゛ブタ
ジェンー２−エチルへキシルアクリレートコポリマー、
ブタジェン−〇−オクタデシルアクリレートコポリマー
などを例示することができる。これらの中でも分子鎖内
部または分子鎖末端に水酸基を有しているものが好まし
い。
まず、本発明では上記液状ジエン系重合体をエポキシ化
剤を用いてエポキシ化し、エポキシ化液状重合体とする
。本発明で用いるエポキシ化剤としては、過ギ酸、過酢
酸、過安息香酸、過フタル酸１ｍ−クロロ過安息香酸、
ｐ−ニトロ過安息香酸、トリフルオロ過酢酸などの有機
過酸、キュメンハイドロパーオキサイド、ｔ−ブチルハ
イドロパーオキサイドなどのハイドロパーオキサイド、
その他過酸化水素などを挙げることができる。エポキシ
化の条件は液状ジエン系重合体１００重量部に対し、エ
ポキシ化剤を１〜１００重量部、好ましくは５〜６０重
量部加え、温度−１θ〜１５０℃、好ましくは０〜１０
０℃、圧力０〜３０ｋｇ／ｃ＋ａ’ Ｇ 、好ましくは
０〜ｌｏｋｇ／ｃｍ２Ｇで０．１〜２００時間、好まし
くは０．５〜５０時間反応させる。なお、エポキシ化に
際して溶媒は必ずしも必要ではないが、所望によりベン
ゼン、クロロホルム、四塩化炭素などの有機溶媒を用い
てもよい。
次に、このようにして得られたエポキシ化液状重合体を
開環処理し、水酸基含有液状重合体とする。開環処理は
、エポキシ化液状重合体１００重量部に対し、ニッケル
、パラジウム、白金、ルテニウムなどの水素添加用触媒
を０．５〜２０重量部、好ましくは１〜１５重量部加え
、温度０〜２５０℃、好ましくは２０〜１５０℃、圧力
０〜２００ ｋｇ／ｃｍ”Ｇ −１ｈ、好ましくは１〜
１００ ｋｇ／ＣＩＩ”Ｇ−Ｈｚで０．１〜２００時間
、好ましくは０．５〜１００時間反応させて行なう、な
お、開環処理に際し溶媒は必ずしも必要ではないが、所
望によりヘキサン、シクロヘキサン、イソプロピルアル
コール、２−ブタノールなどの有機溶媒を用いてもよい
。
開環処理終了後、常法に従って後処理することにより水
酸基含有液状重合体が得られる。上述の条件にて反応さ
せて得られる一水酸基含有液状重合体は、水酸基含有量
（ＯＨＶ） ０．１〜２０．Ｏｍｅｑ／ｇ 、数平均分
子量（Ｉｎ） ｓｏｏ 〜２００００ 、平均水酸基数
（７ｎ） ２．５以上（３，０〜８．０） 、粘度０．
１〜１０，０００ポイズ／３０℃のものである。なお、
平均水酸基数は次の式にて求めた。
［実施例］
次に、実施例により本発明を説明する。
製造例１（エポキシ化液状重合体の製造）攪拌機、温度
計および滴下ロートを備えた５００■オ三つロフラスコ
に無水酢酸２２５ｇを採取し、４０℃に保持しながら滴
下ロートより３０重量％通酸化水素水ｓｏｇを１時間に
わたって滴下した。
・滴下終了後、４０℃で１時間攪拌したのち室温まで冷
却して一晩放置して過酸化物を調製した。
一方、攪拌機、温度計および滴下ロートを備えた２１の
三つロフラスコに末端に水酸基を有する液状ポリブタジ
ェン（出光アーコ■製、 Ｒ−４５１１７゜数平均分子
量２８００．水酸基含有量０．７９璽ｅｑ／ｇ）２００
ｇおよびシクロヘキサン２００ｇを採取し、３０℃に保
持しながら上記過酸化物を滴下ロートよ９２時間にわた
って滴下した６滴下終了後、３０℃で１０時間攪拌を続
行した０反応終了後、３１の分液ロートに反応混合物を
入れ、１．５ Ｉｌの水を添加して振とうし、分！ｌ処
理した。上相を大過剰のへキサンに沈殿させ、次いでト
ルエンに溶解させるという操作を繰り返し、最後に軽沸
点分を留去して無色透明のエポキシ化液状重合体を得た
。得られたエポキシ化液状重合体の性状は、エポキシ当
量４２０．水酸基含有量０．７４ｍｅｑ／ｇ 、数平均
分子量２９９０、粘度５１０ポイズ／３０℃であった。
製造例２（エポキシ化液状重合体の製造）製造例１にお
いて無水酢酸の使用量を４５ｇ１３０重量％過酸化水素
水の使用量を１０ｇとしたこと以外は、製造例１と同様
の操作を行ないエポキシ化液状重合体を得た。得られた
エポキシ化液状重合体の性状は、エポキシ当量１１８０
．水酸基含有量ｏ、ｙ７ｍｅｑ／ｇ 、数平均分子量２
８６０．粘度１６５ボイズ／３０℃であった。
製造例３（エポキシ化液状重合体の製造）製造例２にお
いて、末端に水酸基を有する液状ポリブタジェンＲ−４
５ＨＴの代わりに末端に水酸基を有するポリブタジェン
Ｒ−１５ＨＴ （出光アーコ■製。
数平均分子量１２２０．水酸基含有量１．ａａｍｅｑ／
ｇ）を用いたこと以外は製造例２と同様の操作を行ない
、エポキシ化液状重合体を得た。得られたエポキシ化液
状重合体の性状は、エポキシ当量１１２０．水酸基含量
ｔ、ａ２ｍｅｑ／ｇ 、数平均分子量１２６０．粘度５
２ボイズ／３０℃であった。
製造例４（エポキシ化液状重合体の製造）ｔｎのステン
レス製耐圧反応容器にイソプレン２００ ｇ、 ５０重
量％通酸化水素水ｌａｇおよび溶媒としてｎ−ブチルア
ルコール１００ｇを仕込み、温度１２０℃、圧力Ｍａｘ
８ ｋｇ／ｃｍ’、Ｇで２時間反応させた０反応終了
後、反応容器から反応物を抜き出し、水６００ ｇと共
に分液ロートに入れ振とうした後、３時間静置して油相
を分離した。得られた油相を１００℃、２ ｍｍＨｇで
２時間熱発させて溶媒、千ツマー０低沸点成分を留去し
、分子鎖末端に水酸基を有する液状ポリイソプレンを６
８重量％の収率で得た。得られた液状ポリイソプレンの
性状は、数平均分子量２１５０．水酸基含有量０．９６
鳳ｅＱ／ｇであった。
次に、上記の耐圧反応容器に得られた分子鎖末端に水酸
基を有する液状ポリイソプレン５０ｇおよびクロロホル
ム１００ｍＮを採取し、ここにメタクロロ過安息香酸１
２．５ｇをクロロホルム３０ｈｊに溶解した溶液を攪拌
下に２時間にわたって滴下した。
滴下終了後、２５℃で３時間リフラックスした後、室温
に降下して２４時間放置した。続いて、反応容器を冷却
し、析出したメタクロロ安息香酸の結晶を炉別した後、
炉液を分液ロートにて２０重量％亜硫酸水素ナトリウム
水溶液５０１ｊで１回、１０重量％炭酸水素ナトリウム
水溶液１００閤１で３回、飽和食塩水１００■！で１回
、純水２００ｓｊで２回洗浄した。
さらに、洗浄した炉液を１００℃、１ ａｍ）Ｉｇで２
時間熱発させて低沸点留分を留去し、エポキシ化液状重
合体を得た。得られたエポキシ化液状重合体の性状は、
エポキシ当量６２９．水酸基含有量ｏ、ｓｓｍｅｑ／ｇ
、数平均分子量２２２０．粘度２１４ポイズ／３０℃
であった。
実施例１〜４
１１のステンレス製耐圧反応容器を用いて、製造例１〜
４で得られたエポキシ化液状重合体１００重量部に対し
、第１表に示した触媒および溶媒を加え、第１表に示し
た温度０時間、圧力で開環処理を行なった。開環処理後
、１μ■メンブランフィルタ−で触媒を除去し、続いて
１００℃、１ ｍ８８ｇで２時間熱発させて溶媒および
低沸点成分を留去して水酸基含有液状重合体を得た。得
られた水酸基含有液状重合体の性質を第１表に示す。
比較例１
温度計と攪拌機をとりつけた容量３００ｍＮの３つロフ
ラスコにジエンポリマーＰｏ１ｙ ｂｄ Ｒ−４５ＨＴ
（出光アーコ■製、平均分子量約２８００．水酸基含
有量０．７９■ｅｑ／ｇ 、 １分子当りの水酸基数２
３） ５０ｇ 、塩化エチレン１００ ｇおよび三フッ
化ホウ素−ジメチルエーテル錯体０．１ｇを仕込み窒素
気流下ガラス製５００■１３つロフラスコ中で０℃で３
時間反応させた０次いで、その反応物を２００■！のメ
タノール中に攪拌しながら徐々に注入し、静置後、生成
物を分取した０分取した生成物を減圧下に４０℃で乾燥
し、無色透明な水酸基含有液状重合体４１１ｇを得た。
得られた水酸基含有液状重合体の性質を第２表に示す。
比較例２
比較例１において、三フッ化ホウ素−ジメチルエーテル
錯体の代わりに塩化アルミニウムｏ、ｏｓｇを用い、反
応温度を５℃としたこと以外は比較例１と同様の操作を
行ない、水酸基含有液状重合体４７ｇを得た。得られた
水酸基含有液状重合体の性質を第２表に示す。
第 １ 表
＄１ 日本エンゲル八ルド■製
＄１ 重合体１００ｇを２００＠ｊ ビーカーに入れ、
８０℃のオーブン中で１週間放置した後、表面に“皮張
り”を生じたものを×、生じなかったものを０とした。
第 ２ 表[Industrial Application Field] The present invention relates to a method for producing a hydroxyl group-containing liquid polymer, and more specifically, a method for producing a hydroxyl group-containing liquid polymer with a high average number of functional groups (hydroxyl groups) without excessive increase in viscosity or gelation. Regarding the method. [Prior Art and Problems to be Solved by the Invention] When a diene polymer containing a hydroxyl group is used as a raw material for a urethane resin, a urethane resin having excellent water resistance, low-temperature properties, and electrical properties can be obtained. Generally used hydroxyl group-containing diene polymers have a maximum of 2 hydroxyl groups per molecule, but as raw materials for urethane foam or rigid urethane, those with an average number of hydroxyl groups of 2.5 or more are desirable. It will be done. Conventionally, as a method for obtaining a diene polymer having an average number of hydroxyl groups of 2.5 or more, a method is known in which a hydroxyl group-containing diene polymer having an average number of hydroxyl groups of about 2 is reacted in the presence of a cationic polymerization catalyst (JP-A No. However, since this method aims to increase the average number of hydroxyl groups per molecule through an intermolecular crosslinking reaction, the viscosity of the product increases significantly, and the average number of hydroxyl groups increases. The maximum number is 4
．． It had a drawback of being inferior in thermal stability. Furthermore, when attempting to obtain a product with an average number of hydroxyl groups of 4.0 or more, there was a serious problem in that the entire system gelled and became solid. [Means for Solving the Problems] Therefore, the present invention investigated a method for producing a liquid polymer with a high average number of hydroxyl groups without causing viscosity increase or gelation, and found that a liquid diene polymer was epoxidized. It was subsequently discovered that the object could be achieved by ring-opening treatment, and the present invention was completed based on this knowledge. That is, the present invention provides a method for producing a hydroxyl group-containing liquid polymer, which comprises ring-opening an epoxidized liquid polymer obtained by epoxidizing a liquid diene polymer. The liquid diene polymer used in the present invention has a number average molecular weight of 300 to 25,000, preferably 500 to 10.
000, and these liquid diene polymers include diene polymers having 4 to 12 carbon atoms, diene copolymers,
Furthermore, these diene monomers and α-
Examples include copolymers with olefinic addition-polymerizable polymers. Specifically, butadiene homopolymer, isoprene homopolymer, chloroprene homopolymer, butadiene-
Styrene copolymer, butadiene-isoprene copolymer, butadiene-acrylonitrile copolymer, butadiene-2-ethylhexyl acrylate copolymer,
Examples include butadiene-〇-octadecyl acrylate copolymer. Among these, those having a hydroxyl group inside the molecular chain or at the end of the molecular chain are preferred. First, in the present invention, the liquid diene polymer is epoxidized using an epoxidizing agent to obtain an epoxidized liquid polymer. Epoxidizing agents used in the present invention include performic acid, peracetic acid, perbenzoic acid, perphthalic acid, 1m-chloroperbenzoic acid,
organic peracids such as p-nitrobenzoic acid and trifluoroperacetic acid; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide;
Other examples include hydrogen peroxide. The epoxidation conditions are as follows: 1 to 100 parts by weight, preferably 5 to 60 parts by weight, of an epoxidizing agent are added to 100 parts by weight of the liquid diene polymer, and the temperature is -1θ to 150°C, preferably 0 to 10°C.
The reaction is carried out at 0°C and a pressure of 0 to 30 kg/c+a'G, preferably 0 to 10 kg/cm2G, for 0.1 to 200 hours, preferably 0.5 to 50 hours. Although a solvent is not necessarily required for epoxidation, an organic solvent such as benzene, chloroform, or carbon tetrachloride may be used if desired. Next, the epoxidized liquid polymer thus obtained is subjected to ring-opening treatment to obtain a hydroxyl group-containing liquid polymer. In the ring-opening treatment, 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight of a hydrogenation catalyst such as nickel, palladium, platinum, or ruthenium is added to 100 parts by weight of the epoxidized liquid polymer at a temperature of 0 to 100 parts by weight. 250°C, preferably 20 to 150°C, pressure 0 to 200 kg/cm”G −1h, preferably 1 to
The reaction is carried out at 100 kg/CII''G-Hz for 0.1 to 200 hours, preferably 0.5 to 100 hours. Note that a solvent is not necessarily required for the ring opening treatment, but if desired, hexane, cyclohexane, isopropyl An organic solvent such as alcohol or 2-butanol may be used. After completion of the ring-opening treatment, a hydroxyl group-containing liquid polymer can be obtained by post-treatment according to a conventional method. Monohydroxyl group-containing liquid polymer obtained by reaction under the above-mentioned conditions The liquid polymer contained has a hydroxyl group content (OHV) of 0.1-20. ), viscosity 0.
1 to 10,000 poise/30°C. In addition,
The average number of hydroxyl groups was determined using the following formula. [Example] Next, the present invention will be explained with reference to an example. Production Example 1 (Production of epoxidized liquid polymer) 225 g of acetic anhydride was collected in a 500-inch three-hole flask equipped with a stirrer, a thermometer, and a dropping funnel, and oxidized to 30% by weight through the dropping funnel while maintaining the temperature at 40°C. Hydrogen water sog was added dropwise over 1 hour. - After completion of the dropwise addition, the mixture was stirred at 40°C for 1 hour, then cooled to room temperature and left overnight to prepare peroxide. On the other hand, liquid polybutadiene having a hydroxyl group at the end (manufactured by Idemitsu Arco ■, R-45117, number average molecular weight 2800, hydroxyl group content 0.79 eq/g) was placed in 21 three-necked flasks equipped with a stirrer, a thermometer, and a dropping funnel. )200
g and 200 g of cyclohexane were collected, and the above peroxide was added dropwise through the dropping funnel over 92 hours while maintaining the temperature at 30°C. After the completion of the dropwise addition, stirring was continued for 10 hours at 30°C. Pour the reaction mixture into a funnel, add 1.5 Il of water, shake, and leave for 1 minute! l treated. The operation of precipitating the upper phase in a large excess of hexane and then dissolving it in toluene was repeated, and finally the light boiling point components were distilled off to obtain a colorless and transparent epoxidized liquid polymer. The properties of the obtained epoxidized liquid polymer were as follows: epoxy equivalent: 420. The hydroxyl group content was 0.74 meq/g, the number average molecular weight was 2990, and the viscosity was 510 poise/30°C. Production Example 2 (Production of Epoxidized Liquid Polymer) The same procedure as in Production Example 1 was carried out to produce epoxy A liquefied polymer was obtained. The properties of the obtained epoxidized liquid polymer were as follows: epoxy equivalent: 1180
．． Hydroxyl group content o, y7 meq/g, number average molecular weight 2
860. The viscosity was 165 voids/30°C. Production Example 3 (Production of Epoxidized Liquid Polymer) In Production Example 2, liquid polybutadiene R-4 having a hydroxyl group at the terminal
Polybutadiene R-15HT having a hydroxyl group at the end instead of 5HT (manufactured by Idemitsu Arco ■. Number average molecular weight 1220. Hydroxyl group content 1.aameq/
An epoxidized liquid polymer was obtained by carrying out the same operation as in Production Example 2 except that g) was used. The properties of the obtained epoxidized liquid polymer were as follows: epoxy equivalent: 1120. Hydroxyl group content t, a2meq/g, number average molecular weight 1260. Viscosity 5
It was 2 voices/30°C. Production Example 4 (Production of epoxidized liquid polymer) 200 g of isoprene, 50% by weight hydrogen peroxide solution lag, and 100 g of n-butyl alcohol as a solvent were placed in a TN stainless steel pressure-resistant reaction vessel, and the temperature was 120°C and the pressure was max.
After the reaction was completed for 2 hours at 8 kg/cm' and G, the reactant was extracted from the reaction vessel, placed in a separatory funnel with 600 g of water, shaken, and left to stand for 3 hours to separate the oil phase. did. The obtained oil phase was heated at 100°C and 2 mmHg for 2 hours to distill off the solvent and low-boiling point components, and the liquid polyisoprene having a hydroxyl group at the end of the molecular chain was purified.
Obtained with a yield of 8% by weight. The obtained liquid polyisoprene had a number average molecular weight of 2150. Hydroxyl group content 0.96
It was Otori eQ/g. Next, 50 g of the obtained liquid polyisoprene having a hydroxyl group at the end of the molecular chain and 100 mN of chloroform were collected in the above-mentioned pressure-resistant reaction vessel, and 1 mL of metachloroperbenzoic acid was added.
A solution of 2.5 g dissolved in 30 hj of chloroform was added dropwise over 2 hours with stirring. After completion of the dropwise addition, the mixture was refluxed at 25° C. for 3 hours, then cooled to room temperature and left for 24 hours. Next, the reaction vessel was cooled, and the precipitated crystals of metachlorobenzoic acid were separated by furnace.
The furnace liquid was mixed in a separatory funnel once with 20% by weight sodium bisulfite aqueous solution 501j, 3 times with 100% 100ml of 10% by weight aqueous sodium hydrogencarbonate solution, and 100ml of saturated brine! It was washed once with water and twice with 200 sj of pure water. Furthermore, the washed furnace solution was heated at 100°C with 1 am) Ig for 2 hours.
The low boiling point fraction was distilled off by emitting heat for a period of time to obtain an epoxidized liquid polymer. The properties of the obtained epoxidized liquid polymer are as follows:
Epoxy equivalent: 629. Hydroxyl group content o, ssmeq/g
, number average molecular weight 2220. Viscosity 214 poise/30℃
Met. Examples 1 to 4 Production examples 1 to 4 were carried out using 11 stainless steel pressure-resistant reaction vessels.
The catalyst and solvent shown in Table 1 were added to 100 parts by weight of the epoxidized liquid polymer obtained in Step 4, and ring-opening treatment was performed at the temperature and pressure shown in Table 1 for 0 hours. After the ring-opening treatment, the catalyst was removed using a 1 μι membrane filter, followed by heat generation at 100° C. and 1 m 88 g for 2 hours to distill off the solvent and low-boiling components to obtain a hydroxyl group-containing liquid polymer. Table 1 shows the properties of the obtained hydroxyl group-containing liquid polymer. Comparative Example 1 Diene polymer Po1y bd R-45HT was placed in a three-bottle flask with a capacity of 300 mN equipped with a thermometer and a stirrer.
(manufactured by Idemitsu Arco ■, average molecular weight approximately 2800, hydroxyl group content 0.79 ■eq/g, number of hydroxyl groups per molecule 2)
3) Prepare 50 g of ethylene chloride, 100 g of ethylene chloride, and 0.1 g of boron trifluoride-dimethyl ether complex at 0°C in a 500 mm glass flask under a nitrogen stream.
The reactant was reacted for 0 hours, then the reactant was reacted for 200 hours! The product was gradually poured into methanol with stirring, and after standing still, the product was collected. The collected product was dried at 40°C under reduced pressure to obtain 411 g of a colorless and transparent hydroxyl group-containing liquid polymer. . The properties of the obtained hydroxyl group-containing liquid polymer are shown in Table 2. Comparative Example 2 The same operation as in Comparative Example 1 was performed except that aluminum chloride o, osg was used instead of the boron trifluoride-dimethyl ether complex and the reaction temperature was 5°C. A total of 47 g was obtained. The properties of the obtained hydroxyl group-containing liquid polymer are shown in Table 2. Table 1 $1 Manufactured by Nippon Engel Hult ■ Put 100g of polymer into a 200@j beaker.
After being left in an oven at 80° C. for one week, those that developed “skinning” on the surface were rated “×” and those that did not were rated “0”. Table 2
【発明の効果】 □
本発明ビよれば、過度の粘度上昇またはゲル化を起こす
ことなく平均水酸基数の高い液状重合体を得ることがで
きる。しかも、得られた水酸基含有液状重合体は熱安定
性がよいため、ウレタンフオームや硬質ウレタン用の原
料として有用である。 、
特許出願人 出光石油化学株式会社[Effects of the Invention] □ According to the present invention B, a liquid polymer having a high average number of hydroxyl groups can be obtained without excessive increase in viscosity or gelation. Furthermore, the obtained hydroxyl group-containing liquid polymer has good thermal stability and is therefore useful as a raw material for urethane foams and rigid urethanes. , Patent applicant Idemitsu Petrochemical Co., Ltd.