JPH0122282B2 - - Google Patents
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- Publication number
- JPH0122282B2 JPH0122282B2 JP12917484A JP12917484A JPH0122282B2 JP H0122282 B2 JPH0122282 B2 JP H0122282B2 JP 12917484 A JP12917484 A JP 12917484A JP 12917484 A JP12917484 A JP 12917484A JP H0122282 B2 JPH0122282 B2 JP H0122282B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- diene polymer
- liquid diene
- molecule
- trans
- 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
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- 239000007788 liquid Substances 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 21
- 150000001993 dienes Chemical class 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 125000006838 isophorone group Chemical group 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は液状ジエン系重合体およびその製造方
法に関し、詳しくは耐水性、耐薬品性にすぐれた
硬化体を与える液状ジエン系重合体およびその製
造方法に関する。
これまでにポリエーテルポリオールにジイソシ
アネートおよびメルカプトアルカノールを反応さ
せてメルカプト基を含有するオリゴウレタンを製
造する方法は知られている。しかしながら、この
オリゴウレタンを酸化して得られる硬化体は、耐
水性や耐薬品性、殊に耐アルカリ性に劣るという
欠点があり、セメント、モルタル、コンクリート
の被覆材、シール材等としては不適当なものであ
つた。
本発明はこのような従来の欠点を解消し、耐水
性、耐薬品性にすぐれた硬化性を与える新規な液
状ジエン系重合体およびその製造方法を提供する
ことを目的とするものである。
すなわち本発明は第１にブタジエン繰り返し単
位（ただし、トランス―１，４構造50％以上、ビ
ニル―１，２構造30％以下およびシス―１，４構
造残余の割合である。）４〜460個からなり、その
分子両末端に一般式
（式中、SHはメルカプト基を示し、R1はアル
キレン基を示し、R2はイソホロン基を示す。）
で表わされる基を有する液状ジエン系重合体を提
供するものである。
上記一般式〔〕で表わされる基を両末端に有
する液状ジエン系重合体を酸化して得られる硬化
体は耐水性、耐薬品性にすぐれたものである。
叙上の一般式〔〕で表わされる基を両末端に
有する液状ジエン系重合体は様々な方法により製
造することができるが、例えば以下に示す本発明
の第２により製造することができる。
すなわち、本発明は第２にブタジエン繰り返し
単位（ただし、トランス―１，４構造50％以上、
ビニル―１，２構造30％以下およびシス―１，４
構造残余の割合である。）４〜460個からなり、分
子両末端に水酸基を含有する液状ジエン系重合体
に、該液状ジエン系重合体の水酸基（OH）に対
するイソシアネート基（NCO）がNCO／OH＝
1.0〜5.0（モル比）となる量のイソホロンジイソ
シアネートおよび該ジイソシアネートのイソシア
ネート基にして0.8〜1.2倍当量のメルカプトエタ
ノールを反応させることを特徴とするブタジエン
繰り返し単位（ただし、トランス―１，４構造50
％以上、ビニル―１，２構造30％以下およびシス
―１，４構造残余の割合である。）４〜460個から
なり、その分子両末端に一般式
（式中、SHはメルカプト基を示し、R1はアル
キレン基を示し、R2はイソホロン基を示す。）
で表わされる基を有する液状ジエン系重合体の製
造方法を提供するものである。
本発明の第２において、ブタジエン繰り返し単
位（ただし、トランス―１，４構造50％以上、ビ
ニル―１，２構造30％以下およびシス―１，４構
造残余の割合である。）４〜460個からなり、分子
両末端に水酸基を含有する液状ジエン系重合体と
しては数平均分子量が300〜25000と広範囲のもの
であり、特に数平均分子量が500〜5000のものが
好ましい。
次に、上記分子両末端に水酸基を含有するジエ
ン系重合体と反応させるポリイソシアネートとし
ては、イソホロンジイソシアネートが好適であ
る。
上記分子両末端に水酸基を含有する液状ジエン
系重合体とイソホロンジイソシアネートとの反応
は通常10〜100℃の温度にて0.5〜12時間の条件に
て行なわれる。なお、イソホロンジイソシアネー
トは上記分子両末端に水酸基を有する液状ジエン
系重合体の水酸基（OH）に対するイソシアネー
ト基（NCO）がNCO／OH＝1.0〜5.0以上、好ま
しくは1.5〜5.0となるような割合で用いられる。
次に、メルカプトエタノールは通常、上記分子
両末端に水酸基を含有する液状ジエン系重合体を
イソホロンジイソシアネートとを反応させてプレ
ポリマーを形成させた後に添加してこれと反応さ
せるが、これに限定されるものではない。この反
応は通常10〜100℃の温度で0.5〜12時間加熱撹拌
することにより行なわれる。このメルカプトエタ
ノールは上記ジイソシアネートのイソシアネート
基（NCO）に対し、0.8〜1.2倍当量の割合、好ま
しくは0.95〜1.05倍当量の割合で用いられる。
このようにして上記一般式［］で表わされる
基を両末端に有する液状ジエン系重合体を製造す
ることができる。
このようにして得られる本発明の液状ジエン系
重合体は、これに二酸化マンガン、二酸化鉛、ク
ロム酸塩、有機過酸化物などの酸化剤を加え、三
本ペイントミルロールなどの混練機を用いて混練
することにより適宜形状の硬化体を形成する。な
お、硬化体を形成するにあたり、可塑剤、充填
剤、粘着付与剤、触媒等を適宜添加することもで
きる。このようにして得られる硬化体は耐水性に
すぐれるとともに、耐薬品性、特に耐アルカリ性
にすぐれたものである。
叙上の如く、本発明の液状ジエン系重合体によ
れば、耐水性、耐薬品性にすぐれていて、殊にセ
メント、モルタル、コンクリートの被覆材、シー
ル材等として有用な硬化体を得ることができる。
以下、本発明の実施例を示す。
製造例１ （前記一般式［］で表わされる基を
両末端に有する液状ゴム）
水酸基末端液状ゴム（出光石油化学(株)製、
Poly bd Ｒ―45HT、シス―１，４構造20％、ト
ランス―１，４構造60％およびビニル―１，２構
造20％水酸基当量0.82meq／ｇ）1000ｇを2l容の
セパラブルフラスコに入れ、80℃で１時間加熱真
空脱水後、常温まで冷却した。次に、イソホロン
ジイソシアネート（イソシアネート当量111）182
ｇを窒素シール下にて加え、激しく撹拌した。約
１時間常温にて撹拌後、100℃で５時間反応させ、
イソシアネート含有量2.9重量％のプレプリマー
を得た。次いで、このプレポリマーに２―メルカ
プトエタノール62.3ｇを添加し、約１時間室温で
反応させた後、100℃で１時間加熱撹拌して前記
一般式［］で表わされる基を両末満に有する液
状ゴムを得た。このものは2300ポイズ／30℃の粘
度を有しており、無色透明であつた。
また、このものの元素分析値および赤外吸収ス
ペクトルによる分析（IR分析）結果は次の通り
であつた。
元素分析値
炭素82.5重量％、水素10.5重量％、酸素3.6重量
％、
硫黄1.8重量％、窒素1.6重量％、
IR分析
ウレタン結合：1740〜1690cm-1に吸収あり
メルカプト基：2600〜2550cm-1に吸収あり
水酸基：3200〜3600cm-1に吸収なし
製造例２ （メルカプト末端ポリオキシプロピレ
ングリコールの製造）
ポリオキシプロピレングリコール（トリオー
ル、エチレンオキサイド含量9.0重量％、水酸基
当量0.55meq／ｇ）1000ｇを２容のセパラブル
フラスコに入れ、80℃で１時間加熱脱水後、常温
まで冷却した。次に、イソホロンジイソシアネー
ト（イソシアネート当量111）122ｇを窒素シール
下にて加え、激しく撹拌した。約１時間常温にて
撹拌後、100℃で５時間反応させ、イソシアネー
ト含有量2.1重量％のプレポリマーを得た。次い
で、このプレポリマーに２−メルカプトエタノー
ル41.7ｇを添加し、約１時間室温で反応させた
後、100℃で１時間加熱撹拌してメルカプト末端
ポリオキシプロピレングリコールを得た。このも
のは1200ボイズ／23℃の粘度を有しており、無色
透明であつた。
また、このものの元素分析値および赤外吸収ス
ペクトルによる分析（IR分析）結果は次の通り
であつた。
元素分析値
炭素60.3重量％、水素9.9重量％、窒素1.0重
量％、硫黄1.1重量％、酸素27.6重量％
IR分析
ウレタン結合：1740〜1690cm-1に吸収あり
メルカプト基：2600〜2550cm-1に吸収あり
水酸基：3200〜3600cm-1に吸収なし
実施例 １
上記製造例１で得られた前記一般式［］で表
わされる基を両末端に有する液状ゴム100ｇと二
酸化鉛（和光純薬(株)製、一級、乳鉢で粉砕して使
用）10ｇを三本ペイントミルロールを用いて混練
後、泡を巻き込まないように型枠（厚さ１cm×縦
５cm×横５cm）へ流し込み硬化体を得た。得られ
た硬化体の物性の測定結果を第１表に示す。
実施例 ２
実施例１において、二酸化鉛の代わりに二酸化
マンガン（和光純薬(株)製，特級，乳鉢で粉砕して
使用）12ｇを用いたこと以外は実施例１と同様に
して硬化体を得、その物性を測定した。結果を第
１表に示す。
比較例 １
実施例１において、製造例１で得られた前記一
般式［］で表わされる基を両末端に有する液状
ゴムの代わりに製造例２で得られた前記一般式
［］で表わされる基を両末端に有するポリオキ
シプロピレングリコールを用いたこと以外は実施
例１と同様にして硬化体を得、その物性を測定し
た。結果を第１表に示す。
比較例 ２
比較例１において、二酸化鉛の代わりに二酸化
マンガン12ｇを用いたこと以外は比較例１と同様
にして硬化体を得、その物性を測定した。結果を
第１表に示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid diene polymer and a method for producing the same, and more particularly to a liquid diene polymer that provides a cured product with excellent water resistance and chemical resistance, and a method for producing the same. A method for producing an oligourethane containing a mercapto group by reacting a polyether polyol with a diisocyanate and a mercapto alkanol is known. However, the cured product obtained by oxidizing this oligourethane has the disadvantage of poor water resistance, chemical resistance, and especially alkali resistance, and is therefore unsuitable for use as coating materials for cement, mortar, concrete, sealing materials, etc. It was hot. The object of the present invention is to eliminate such conventional drawbacks and provide a novel liquid diene polymer that exhibits excellent water resistance, chemical resistance, and curability, and a method for producing the same. That is, the present invention firstly provides 4 to 460 butadiene repeating units (however, the proportion is 50% or more of trans-1,4 structure, 30% or less of vinyl-1,2 structure, and the remainder of cis-1,4 structure). It consists of a general formula at both ends of the molecule. (In the formula, SH represents a mercapto group, R 1 represents an alkylene group, and R 2 represents an isophorone group.) A liquid diene polymer having a group represented by the following is provided. A cured product obtained by oxidizing a liquid diene polymer having groups represented by the above general formula [] at both ends has excellent water resistance and chemical resistance. The liquid diene polymer having groups represented by the above general formula [] at both ends can be produced by various methods, and for example, it can be produced by the second method of the present invention shown below. That is, the second aspect of the present invention is a butadiene repeating unit (however, trans-1,4 structure of 50% or more,
Vinyl-1,2 structure less than 30% and cis-1,4
It is the proportion of structural residuals. ) isocyanate group (NCO) for the hydroxyl group (OH) of the liquid diene polymer is NCO/OH=
A butadiene repeating unit characterized by reacting isophorone diisocyanate in an amount of 1.0 to 5.0 (molar ratio) and mercaptoethanol in an amount of 0.8 to 1.2 times equivalent to the isocyanate group of the diisocyanate (however, trans-1,4 structure 50
% or more, 30% or less of vinyl-1,2 structure, and the remaining proportion of cis-1,4 structure. ) consists of 4 to 460 molecules, with the general formula at both ends of the molecule. (In the formula, SH represents a mercapto group, R 1 represents an alkylene group, and R 2 represents an isophorone group.) A method for producing a liquid diene polymer having a group represented by the following is provided. In the second aspect of the present invention, 4 to 460 butadiene repeating units (however, the proportion is 50% or more of trans-1,4 structure, 30% or less of vinyl-1,2 structure, and the remainder of cis-1,4 structure). Liquid diene polymers containing hydroxyl groups at both ends of the molecule have a wide range of number average molecular weights, ranging from 300 to 25,000, with those having a number average molecular weight of 500 to 5,000 being particularly preferred. Next, as the polyisocyanate to be reacted with the diene polymer containing hydroxyl groups at both ends of the molecule, isophorone diisocyanate is suitable. The reaction between the liquid diene polymer containing hydroxyl groups at both ends of the molecule and isophorone diisocyanate is usually carried out at a temperature of 10 to 100°C for 0.5 to 12 hours. In addition, isophorone diisocyanate is used in a ratio such that the isocyanate group (NCO) to the hydroxyl group (OH) of the liquid diene polymer having hydroxyl groups at both ends of the molecule is NCO/OH = 1.0 to 5.0 or more, preferably 1.5 to 5.0. used. Next, mercaptoethanol is usually added after reacting the liquid diene polymer containing hydroxyl groups at both ends of the molecule with isophorone diisocyanate to form a prepolymer, but is not limited to this. It's not something you can do. This reaction is usually carried out by heating and stirring at a temperature of 10 to 100°C for 0.5 to 12 hours. This mercaptoethanol is used in an amount of 0.8 to 1.2 times equivalent, preferably 0.95 to 1.05 times equivalent, to the isocyanate group (NCO) of the diisocyanate. In this way, a liquid diene polymer having groups represented by the above general formula [] at both ends can be produced. The liquid diene polymer of the present invention thus obtained is prepared by adding an oxidizing agent such as manganese dioxide, lead dioxide, chromate, or organic peroxide, and using a kneading machine such as a three-roll paint mill roll. By kneading the mixture, a cured product having an appropriate shape is formed. In addition, in forming a cured body, a plasticizer, a filler, a tackifier, a catalyst, etc. can also be added as appropriate. The cured product thus obtained has excellent water resistance and chemical resistance, particularly alkali resistance. As mentioned above, according to the liquid diene polymer of the present invention, it is possible to obtain a cured product which has excellent water resistance and chemical resistance and is particularly useful as a coating material, a sealing material, etc. for cement, mortar, and concrete. Can be done. Examples of the present invention will be shown below. Production Example 1 (Liquid rubber having groups represented by the above general formula [] at both ends) Hydroxyl group-terminated liquid rubber (manufactured by Idemitsu Petrochemical Co., Ltd.,
Put 1000 g of Poly bd R-45HT (20% cis-1,4 structure, 60% trans-1,4 structure and 20% vinyl-1,2 structure, hydroxyl equivalent 0.82 meq/g) into a 2 L separable flask, After heating and vacuum dehydration at 80°C for 1 hour, the mixture was cooled to room temperature. Next, isophorone diisocyanate (isocyanate equivalent weight 111) 182
g was added under a nitrogen blanket and stirred vigorously. After stirring at room temperature for about 1 hour, react at 100℃ for 5 hours,
A preprimer with an isocyanate content of 2.9% by weight was obtained. Next, 62.3 g of 2-mercaptoethanol was added to this prepolymer and reacted at room temperature for about 1 hour, and then heated and stirred at 100°C for 1 hour to obtain a polymer having groups represented by the general formula [] at both ends. A liquid rubber was obtained. This product had a viscosity of 2300 poise/30°C and was colorless and transparent. Further, the elemental analysis values and the results of infrared absorption spectrum analysis (IR analysis) of this product were as follows. Elemental analysis values Carbon 82.5% by weight, Hydrogen 10.5% by weight, Oxygen 3.6% by weight, Sulfur 1.8% by weight, Nitrogen 1.6% by weight, IR analysis Urethane bond: Absorption occurs between 1740 and 1690 cm -1 Mercapto group: between 2600 and 2550 cm -1 Absorption Hydroxyl group: No absorption between 3200 and 3600 cm -1 Production example 2 (Production of mercapto-terminated polyoxypropylene glycol) 2 volumes of 1000 g of polyoxypropylene glycol (triol, ethylene oxide content 9.0% by weight, hydroxyl group equivalent 0.55 meq/g) The mixture was placed in a separable flask and dehydrated by heating at 80°C for 1 hour, then cooled to room temperature. Next, 122 g of isophorone diisocyanate (isocyanate equivalent: 111) was added under a nitrogen blanket and stirred vigorously. After stirring at room temperature for about 1 hour, the mixture was reacted at 100° C. for 5 hours to obtain a prepolymer with an isocyanate content of 2.1% by weight. Next, 41.7 g of 2-mercaptoethanol was added to this prepolymer and reacted at room temperature for about 1 hour, followed by heating and stirring at 100° C. for 1 hour to obtain mercapto-terminated polyoxypropylene glycol. This product had a viscosity of 1200 voids/23°C and was colorless and transparent. Further, the elemental analysis values and the results of infrared absorption spectrum analysis (IR analysis) of this product were as follows. Elemental analysis Carbon 60.3% by weight, Hydrogen 9.9% by weight, Nitrogen 1.0% by weight, Sulfur 1.1% by weight, Oxygen 27.6% by weight IR analysis Urethane bond: Absorbed between 1740 and 1690 cm -1 Mercapto group: Absorbed between 2600 and 2550 cm -1 Hydroxyl group: No absorption at 3200 to 3600 cm -1 Example 1 100 g of the liquid rubber obtained in Production Example 1 and having groups represented by the general formula [] at both ends and lead dioxide (manufactured by Wako Pure Chemical Industries, Ltd.) , first grade, crushed in a mortar and used) was kneaded using three paint mill rolls, and poured into a mold (1 cm thick x 5 cm long x 5 cm wide) to obtain a cured product, taking care not to involve bubbles. Table 1 shows the measurement results of the physical properties of the obtained cured product. Example 2 A cured product was produced in the same manner as in Example 1, except that 12 g of manganese dioxide (manufactured by Wako Pure Chemical Industries, Ltd., special grade, used by crushing in a mortar) was used instead of lead dioxide. and its physical properties were measured. The results are shown in Table 1. Comparative Example 1 In Example 1, instead of the liquid rubber having the groups represented by the general formula [] obtained in Production Example 1 at both ends, the group represented by the general formula [] obtained in Production Example 2 was used. A cured product was obtained in the same manner as in Example 1 except that polyoxypropylene glycol having at both ends was used, and its physical properties were measured. The results are shown in Table 1. Comparative Example 2 A cured product was obtained in the same manner as in Comparative Example 1, except that 12 g of manganese dioxide was used instead of lead dioxide, and its physical properties were measured. The results are shown in Table 1. 【table】
Claims (1)
―１，４構造50％以上、ビニル―１，２構造30％
以下およびシス―１，４構造残余の割合である。）
４〜460個からなり、その分子両末端に一般式 （式中、SHはメルカプト基を示し、R1はアル
キレン基を示し、R2はイソホロン基を示す。） で表わされる基を有する液状ジエン系重合体。 ２ ブタジエン繰り返し単位（ただし、トランス
―１，４構造50％以上、ビニル―１，２構造30％
以下およびシス―１，４構造残余の割合である。）
４〜460個からなり、分子両末端に水酸基を含有
する液状ジエン系重合体に、該液状ジエン系重合
体の水酸基（OH）に対するイソシアネート基
（NCO）がNCO／OH＝1.0〜5.0（モル比）となる
量のイソホロンジイソシアネートおよび該ジイソ
シアネートのイソシアネート基に対して0.8〜1.2
倍当量のメルカプトエタノールを反応させること
を特徴とするブタジエン繰り返し単位（ただし、
トランス―１，４構造50％以上、ビニル―１，２
構造30％以下およびシス―１，４構造残余の割合
である。）４〜460個からなり、その分子両末端に
一般式 （式中、SHはメルカプト基を示し、R1はアル
キレン基を示し、R2はイソホロン基を示す。） で表わされる基を有する液状ジエン系重合体の製
造方法。[Claims] 1 Butadiene repeating unit (50% or more of trans-1,4 structure, 30% of vinyl-1,2 structure)
The following is the proportion of residual cis-1,4 structure. )
Consists of 4 to 460 molecules, with a general formula at both ends of the molecule. (In the formula, SH represents a mercapto group, R 1 represents an alkylene group, and R 2 represents an isophorone group.) A liquid diene polymer having a group represented by the following. 2 Butadiene repeating units (50% or more of trans-1,4 structure, 30% of vinyl-1,2 structure)
The following is the proportion of residual cis-1,4 structure. )
A liquid diene polymer containing 4 to 460 hydroxyl groups at both ends of the molecule has an isocyanate group (NCO) relative to the hydroxyl group (OH) of the liquid diene polymer at a ratio of NCO/OH=1.0 to 5.0 (molar ratio ) of isophorone diisocyanate and the isocyanate group of the diisocyanate from 0.8 to 1.2
Butadiene repeating unit characterized by reacting double equivalents of mercaptoethanol (however,
Trans-1,4 structure 50% or more, vinyl-1,2
This is the proportion of 30% or less structure and the remaining cis-1,4 structure. ) consists of 4 to 460 molecules, with the general formula at both ends of the molecule. (In the formula, SH represents a mercapto group, R 1 represents an alkylene group, and R 2 represents an isophorone group.) A method for producing a liquid diene polymer having a group represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12917484A JPS619411A (en) | 1984-06-25 | 1984-06-25 | Liquid diene polymer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12917484A JPS619411A (en) | 1984-06-25 | 1984-06-25 | Liquid diene polymer and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS619411A JPS619411A (en) | 1986-01-17 |
| JPH0122282B2 true JPH0122282B2 (en) | 1989-04-26 |
Family
ID=15002975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12917484A Granted JPS619411A (en) | 1984-06-25 | 1984-06-25 | Liquid diene polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS619411A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08508518A (en) * | 1993-01-06 | 1996-09-10 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Oligomer polyamine cross-linking agent having steric hindrance and coating containing the cross-linking agent |
-
1984
- 1984-06-25 JP JP12917484A patent/JPS619411A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS619411A (en) | 1986-01-17 |
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