JPS60262806A - Halogen-terminated liquid diene polymer and its production - Google Patents
Halogen-terminated liquid diene polymer and its productionInfo
- Publication number
- JPS60262806A JPS60262806A JP11817484A JP11817484A JPS60262806A JP S60262806 A JPS60262806 A JP S60262806A JP 11817484 A JP11817484 A JP 11817484A JP 11817484 A JP11817484 A JP 11817484A JP S60262806 A JPS60262806 A JP S60262806A
- Authority
- JP
- Japan
- Prior art keywords
- halogen
- diene polymer
- liquid diene
- cured product
- formula
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 150000001993 dienes Chemical class 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract 4
- 150000002367 halogens Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 6
- 239000005060 rubber Substances 0.000 abstract description 6
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920001228 polyisocyanate Polymers 0.000 abstract description 3
- 239000005056 polyisocyanate Substances 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000004636 vulcanized rubber Substances 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- -1 Hydrogen halides Chemical class 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000270298 Boidae Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 2
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- JSTCPNFNKICNNO-UHFFFAOYSA-N 4-nitrosophenol Chemical compound OC1=CC=C(N=O)C=C1 JSTCPNFNKICNNO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は末端にハロゲンを有する液状ジエン系重合体お
よびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid diene polymer having a halogen at its terminal and a method for producing the same.
液状ジエン系重合体は室温で流動性を有し、適当な化学
的処理、例えば硬化処理によって三次元網目構造を形成
し、通常の加硫ゴムと同じ物理特性を示すところの重合
体であって、これまでに分子内部にハロゲンを有する液
状ジエン系重合体は知られている。A liquid diene polymer is a polymer that has fluidity at room temperature, forms a three-dimensional network structure through appropriate chemical treatment, such as curing treatment, and exhibits the same physical properties as ordinary vulcanized rubber. Until now, liquid diene polymers having a halogen inside the molecule have been known.
しかしながら、この重合体は長鎖ジアミンや二重結合を
有するポリマーの架橋剤として有用なものであるが、三
次元架橋させた場合には末端に自由鎖が生成し、得られ
る硬化体におけるゴム弾性や動的特性が不十分であると
いう欠点があった。However, although this polymer is useful as a crosslinking agent for long-chain diamines and polymers with double bonds, when it is three-dimensionally crosslinked, free chains are generated at the ends, and the rubber elasticity of the resulting cured product is The disadvantages were that it had poor performance and dynamic properties.
本発明は従来のこのような欠点を解消し、物性のすくれ
た硬化体を得ることのできる新規な液状ジエン系重合体
とその製造方法を提供することを目的とするものである
。The object of the present invention is to provide a novel liquid diene polymer and a method for producing the same, which can overcome these conventional drawbacks and provide a cured product with poor physical properties.
すなわち本発明は第１に 一般式 ％式％（１） 〔式中、Ｘはハロゲンを示し、ｎは６〜４５０を示す。That is, the present invention firstly general formula % formula % (1) [In the formula, X represents a halogen, and n represents 6 to 450.
〕
で表わされる末端にハロゲンを有する液状ジエン系重合
体を提供するものであり、第２に一般式
％式％（）
〔式中、ｎは６〜４５０を示す。〕
で表わされる末端に水酸基を有する液状ジエン系重合体
に、ハロゲン化合物を反応させることを特徴とする一般
式
％式％（１）
〔式中、Ｘはハロゲンを示し、ｎは６〜４５０を示す。] It provides a liquid diene-based polymer having a halogen at the end represented by the general formula % () [wherein n represents 6 to 450]. ] General formula % formula % (1) characterized by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the terminal represented by [wherein, X represents a halogen, and n represents 6 to 450] show.
〕
で表わされる末端にハロゲン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。] The present invention provides a method for producing a liquid diene polymer having a halogen at the end represented by the following.
上記一般式（１）で表わされる化合物において、Ｘは一
ヒ述の如くハロゲン（フッ素、塩素５臭素。In the compound represented by the above general formula (1), X is a halogen (fluorine, chlorine and pentabromine) as described above.
ヨウ素）を示している。また、ｎは６〜４５０を示して
いる。iodine). Moreover, n has shown 6-450.
本発明の第１はこのように分子両末端にハロゲンを有す
る新規な液状ジエン系重合体であり、硬化処理によって
ゴム弾性や動的特性にすぐれた硬化体を得ることができ
る。The first aspect of the present invention is thus a novel liquid diene polymer having halogens at both ends of the molecule, and a cured product having excellent rubber elasticity and dynamic properties can be obtained by curing treatment.
上記本発明の第１の新規な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、例えば以下に述べ
る本発明の第２の方法により製造することができる。The first novel liquid diene polymer of the present invention can be produced by various methods, and for example, can be produced by the second method of the present invention described below.
すなわち、上記一般式（ｎ）で表わされる末端に水酸基
を有する液状ジエン系重合体に、ハロゲン化合物を反応
させることにより製造することができる。上記一般式Ｃ
Ｉ＋）で表わされる化合物において、ｎは６〜４５０を
示している。That is, it can be produced by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the terminal represented by the above general formula (n). General formula C above
In the compound represented by I+), n is 6 to 450.
また、ハロゲン化合物は通常用いられているものでよく
様々なものが挙げられる。例えば臭化水素（ＨＢｒ）、
塩化水素（ＨＣＩ）、フン化水素（ＨＦ）、 ヨウ化水
素（Ｈｌ）などのハロゲン化水素；三ハロゲン化リン、
五ハロゲン化リンなどのハロゲン化リンが挙げられる。Further, the halogen compound may include a variety of commonly used halogen compounds. For example, hydrogen bromide (HBr),
Hydrogen halides such as hydrogen chloride (HCI), hydrogen fluoride (HF), and hydrogen iodide (Hl); phosphorus trihalide,
Examples include phosphorus halides such as phosphorus pentahalide.
ここで三ハロゲン化リンとしては具体的にはＰＢ、、、
ＰＣｌ３などがあり、また五ハロゲン化リンとしてはＰ
Ｂ、Ｓ。Specifically, the phosphorus trihalide is PB,...
PCl3, etc., and P as a phosphorus pentahalide.
B.S.
ＰＣｌ５などがある。さらに、ハロゲン化リンとしては
リンと臭素との化合物などを用いることもできる。また
、ハロゲン化合物としてはさらにクロルベンゼン、ブロ
ムベンゼン、クロルトルエン。Examples include PCl5. Further, as the phosphorus halide, a compound of phosphorus and bromine can also be used. Furthermore, halogen compounds include chlorobenzene, bromobenzene, and chlorotoluene.
ブロムトルエンなどのハロゲン化アリール；塩化メチル
、臭化メチル、四塩化炭素、四臭化炭素などのハロゲン
化アルキル；チオニルクロライド。Aryl halides such as bromotoluene; alkyl halides such as methyl chloride, methyl bromide, carbon tetrachloride, carbon tetrabromide; thionyl chloride.
チオニルブロマイドなどのハロゲン化チオニル；アセチ
ルクロライド５アセチルブロマイドなどの酸ハロゲン化
物等を挙げることができる。これらの中でもとりわけチ
オニルクロライド、チオニルブロマイドなどのハロゲン
化チオニルが好適に用いられる。Examples include thionyl halides such as thionyl bromide; acid halides such as acetyl chloride and acetyl bromide. Among these, thionyl halides such as thionyl chloride and thionyl bromide are particularly preferably used.
上記一般式（ＩＩ）で表わされる化合物とハロゲン化合
物との反応は通常、温度−１０〜２００℃、好ましくは
０〜１００℃、圧力１〜２０気圧、好ましくは１〜ｌＯ
気圧にて０．１〜２４時間、好ましくは１〜１２時間行
なわれる。The reaction between the compound represented by the above general formula (II) and a halogen compound is usually carried out at a temperature of -10 to 200°C, preferably 0 to 100°C, and a pressure of 1 to 20 atm, preferably 1 to 10
It is carried out at atmospheric pressure for 0.1 to 24 hours, preferably for 1 to 12 hours.
また、この反応は無溶媒下でも進行するが、溶媒を用い
ることが好ましい。その場合に使用する溶媒としてはヘ
ンゼソ、クロロホルム、ジメチルホルムアミド、アセト
ニトリルなどが挙げられ、上記溶媒を２種類以上組合せ
て使用することもできる。その他必要により安定剤、例
えばφ−キノン、ハイドロキノン、ハイドロキノンモノ
メチルエーテル、ＢＨＴ、 ジニトロフェノール、ニト
ロソフェノール等を添加することができる。Further, although this reaction proceeds even in the absence of a solvent, it is preferable to use a solvent. Examples of the solvent used in this case include chlorine, chloroform, dimethylformamide, acetonitrile, and the like, and two or more of the above solvents can also be used in combination. Other stabilizers such as φ-quinone, hydroquinone, hydroquinone monomethyl ether, BHT, dinitrophenol, nitrosophenol, etc. may be added if necessary.
このようにして上記一般式（１）で表わされる末端にハ
ロゲンを有する新規な液状ジエン系重合体を製造するこ
とができる。In this way, a novel liquid diene polymer having a halogen at the terminal represented by the above general formula (1) can be produced.
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
エポキシ樹脂、有機ポリイソシアネート化合物等と反応
させることによってゴム弾性、動的特性にすぐれた硬化
体を製造することができる。The liquid diene polymer of the present invention thus obtained can be reacted with an epoxy resin, an organic polyisocyanate compound, etc. to produce a cured product with excellent rubber elasticity and dynamic properties.
したがって、本発明の液状ジエン系重合体は、樹脂改質
剤あるいは硬化体原料等として有効に利用することがで
きる。Therefore, the liquid diene polymer of the present invention can be effectively used as a resin modifier or a raw material for a cured product.
なお、畝上の如く一般式（Ｉｔ）で表わされる末端に水
酸基を有する液状ジエン系重合体にハロゲン化合物を反
応させて得られる、一般式（１）で表わされる末端にハ
ロゲンを有する液状ジエン系重合体に、さらにアンモニ
アあるいはアミンを反応させることにより末端にアミノ
基を有する液状ジエン系重合体を製造することができる
。この末端にアミノ基を有する液状ジエン系重合体をエ
ポキシ樹脂や有機ポリイソシアネート化合物等と反応さ
せることにより得られる硬化体は耐水性、耐薬品性等に
一層すぐれたものとなる。In addition, a liquid diene polymer having a halogen at the end represented by the general formula (1) obtained by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the end represented by the general formula (It) as shown in Ujigami. A liquid diene polymer having an amino group at the end can be produced by reacting the polymer with ammonia or an amine. A cured product obtained by reacting this liquid diene polymer having an amino group at its terminal with an epoxy resin, an organic polyisocyanate compound, etc. has better water resistance, chemical resistance, etc.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
実施例１
冷却管付き１１容の三ツロフラスコに、水酸基末端液状
ポリブタジェン（数平均分子量２８００゜水酸基含量０
．７９ ＋ｗｅｑ／ ｇ 、出光石油化学■製。Example 1 A hydroxyl-terminated liquid polybutadiene (number average molecular weight 2800°, hydroxyl group content 0
．． 79 +weq/g, manufactured by Idemitsu Petrochemical ■.
Ｐｏ１ｙ ｂｄ Ｒ−４５ＨＴ） ５３．４ｇ、反応溶
媒としてクロロホルム６００ｍｊ！、反応助剤としてピ
リジン４ｇを加え５℃に冷却した。次いで、この溶液に
ｌ Ｏｍｊ！のクロロホルムで希釈したチオニルクロラ
イド（和光純薬■製、特級） ５．７ ｇを３０分かけ
て滴下した。その後、温度を５℃に保ったまま２時間反
応を行ない、さらにクロロホルム還流下、６時間反応を
行なった。反応終了後、１００ｍ７！の蒸留水を加えて
攪拌し、未反応のチオニルクロライドを除去した。次い
で、この反応液を２１の分液ロートに移し、約６００ｍ
ｌの蒸留水を加えて洗浄を２回行なった。分液後、溶剤
を除去し、反応物４０．３ｇを得た。Poly bd R-45HT) 53.4g, 600mj of chloroform as a reaction solvent! 4 g of pyridine was added as a reaction aid, and the mixture was cooled to 5°C. Then add l Omj! to this solution. 5.7 g of thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade) diluted with chloroform was added dropwise over 30 minutes. Thereafter, the reaction was carried out for 2 hours while the temperature was maintained at 5°C, and the reaction was further carried out for 6 hours under refluxing of chloroform. After the reaction, 100m7! of distilled water was added and stirred to remove unreacted thionyl chloride. Next, this reaction solution was transferred to a 21 separatory funnel, about 600 m
Washing was carried out twice by adding 1 liter of distilled water. After separation, the solvent was removed to obtain 40.3 g of a reaction product.
この反応物の物性の分析結果を以下に示す。The analysis results of the physical properties of this reactant are shown below.
水酸基当量 Ｑ、 ０８ ＠ｅｑ／ ｇ（アセチル化法
による）
塩素含有量 １．８７重景気
粘 度 １２５ボイズ／１５°Ｃ
元素分析値
炭素 ８７．０％、 水素 １０．９％。Hydroxyl group equivalent Q, 08 @eq/g (by acetylation method) Chlorine content 1.87 Heavy-duty viscosity 125 boids/15°C Elemental analysis carbon 87.0%, hydrogen 10.9%.
酸素 ０．３％、 塩素 １．８７％
また、赤外吸収スペクトルによる分析（ＩＲ分析）の結
果、３２００〜３６００ｃｍ−’における水酸基による
吸収が消失していることが認められた。Oxygen: 0.3%, Chlorine: 1.87% Furthermore, as a result of infrared absorption spectrum analysis (IR analysis), it was recognized that absorption by hydroxyl groups at 3200 to 3600 cm-' had disappeared.
実施例２
実施例１において、チオニルクロライドの代わりにチオ
ニルクロライド１０．０ｇを用いたこと以外は実施例１
と同様にして反応物を得た。Example 2 Example 1 except that 10.0 g of thionyl chloride was used instead of thionyl chloride in Example 1.
A reaction product was obtained in the same manner as above.
この反応物の物性の分析結果を以下に示す。The analysis results of the physical properties of this reactant are shown below.
水酸基当量 Ｑ、 ０３ ｎ＋ｅｑ／ ｇ（アセチル化
法による）
臭素含有量 ４．１２重量％
粘 度 ２３０ボイズ／１５℃
元素分析値
炭素 ８５．０％５ 水素 １０．６％。Hydroxyl group equivalent Q, 03 n+eq/g (by acetylation method) Bromine content 4.12% by weight Viscosity 230 boids/15°C Elemental analysis Carbon 85.0%5 Hydrogen 10.6%.
酸素 ０．３％、 臭素 ４．１％
また、ＩＲ分析の結果、３２００〜３６００ｃ＋ａ−’
における水酸基による吸収が消失していることが認めら
れた。Oxygen 0.3%, Bromine 4.1% Also, as a result of IR analysis, 3200~3600c+a-'
It was observed that the absorption by hydroxyl groups in .
応用例
上記実施例２で得られた臭素末端液状ポリブタジェン１
００ｇにメチル化テトラエチルテトラミン９ｇを加え、
混合攪拌して脱泡させ硬化物を得た。この硬化物は良好
な弾性を示した。Application example Bromine-terminated liquid polybutadiene 1 obtained in Example 2 above
Add 9g of methylated tetraethyltetramine to 00g,
A cured product was obtained by mixing and stirring to defoam. This cured product showed good elasticity.
Claims (2)
体。(1) General formula % formula % [In the formula, X represents a halogen, and n represents 6 to 450. ] A liquid diene polymer having a halogen at the end represented by:
に、ハロゲン化合物を反応させることを特徴とする一般
式 ％式％ 〔式中、Ｘはハロゲンを示し、ｎは６〜４５０を示す。 〕 で表わされる末端にハロゲン終を有する液状ジエン系重
合体の製造方法。(2) General formula % formula % [wherein n represents 6 to 450]. ] General formula % formula % characterized by reacting a halogen compound with a liquid diene polymer having a hydroxyl group at the terminal represented by [Formula, X represents a halogen and n represents 6 to 450]. ] A method for producing a liquid diene polymer having a halogen terminus represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11817484A JPS60262806A (en) | 1984-06-11 | 1984-06-11 | Halogen-terminated liquid diene polymer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11817484A JPS60262806A (en) | 1984-06-11 | 1984-06-11 | Halogen-terminated liquid diene polymer and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60262806A true JPS60262806A (en) | 1985-12-26 |
| JPS6345723B2 JPS6345723B2 (en) | 1988-09-12 |
Family
ID=14729954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11817484A Granted JPS60262806A (en) | 1984-06-11 | 1984-06-11 | Halogen-terminated liquid diene polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60262806A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3506742A (en) * | 1965-08-09 | 1970-04-14 | Polymer Corp | Terminally active liquid diolefin polymers,preparation and vulcanizates thereof |
-
1984
- 1984-06-11 JP JP11817484A patent/JPS60262806A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3506742A (en) * | 1965-08-09 | 1970-04-14 | Polymer Corp | Terminally active liquid diolefin polymers,preparation and vulcanizates thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6345723B2 (en) | 1988-09-12 |
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