JPS6345724B2 - - Google Patents
Info
- Publication number
- JPS6345724B2 JPS6345724B2 JP59158897A JP15889784A JPS6345724B2 JP S6345724 B2 JPS6345724 B2 JP S6345724B2 JP 59158897 A JP59158897 A JP 59158897A JP 15889784 A JP15889784 A JP 15889784A JP S6345724 B2 JPS6345724 B2 JP S6345724B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- halogen
- formula
- liquid diene
- repeating units
- 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
Links
- 229920001577 copolymer Polymers 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 150000002366 halogen compounds Chemical class 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 10
- -1 isocyanate compound Chemical class 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000021736 acetylation Effects 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000012948 isocyanate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 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
- 239000000543 intermediate Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920005604 random copolymer Polymers 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 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
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 239000004970 Chain extender Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 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
- 125000003277 amino group Chemical group 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
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 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
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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、末端にハロゲンを有する液状ジエン
系共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 copolymer having a terminal halogen and a method for producing the same.
従来より、末端に水酸基を有する液状ブタジエ
ン―スチレン共重合体あるいは末端に水酸基を有
する液状ブタジエン―アクリロニトリル共重合体
等が知られており、硬化体原料,種々の中間体等
として有効に用いられている。 Liquid butadiene-styrene copolymers having a hydroxyl group at the end or liquid butadiene-acrylonitrile copolymers having a hydroxyl group at the end have been known for some time, and are effectively used as raw materials for cured products and various intermediates. There is.
しかしながら、これらの共重合体は硬化処理等
において鎖延長剤としてジカルボン酸等を用いる
と、エステル結合が形成され、得られる硬化体は
耐水性,耐薬品性などに劣つたものとなる欠点が
あつた。また、硬化処理にイソシアネート化合物
を用いると、空気中の水分とイソシアネート化合
物が反応し、二酸化炭素が発生して得られる硬化
体が発泡する。そのため、硬化処理雰囲気下の水
分に留意しなければならなかつた。 However, these copolymers have the disadvantage that when dicarboxylic acids or the like are used as chain extenders during curing treatment, ester bonds are formed, resulting in the resulting cured product having poor water resistance, chemical resistance, etc. Ta. Further, when an isocyanate compound is used in the curing treatment, the moisture in the air and the isocyanate compound react, carbon dioxide is generated, and the resulting cured product foams. Therefore, it was necessary to pay attention to moisture in the curing atmosphere.
本発明は上記の問題点を解消した新規共重合体
およびその製造方法を提供することを目的として
いる。 An object of the present invention is to provide a new copolymer that solves the above problems and a method for producing the same.
すなわち本発明は、ブタジエン繰り返し単位
(但し、シス―1,4構造0.15〜0.25、トランス
―1,4構造0.55〜0.65、ビニル―1,2構造
0.15〜0.25の割合である。)4〜460個
および式
(式中、Yはフエニル基あるいはシアノ基を示
す。)で表わされる繰り返し単位2〜230個からな
る共重合体であつて、分子末端にハロゲンを有す
る液状ジエン系共重合体(以下、第1発明とい
う。)およびブタジエン繰り返し単位(但し、シ
ス―1,4構造0.15〜0.25、トランス―1,4構
造0.55〜0.65、ビニル―1,2構造0.15〜0.25の
割合である。)4〜460個
および
(式中、Yはフエニル基あるいはシアノ基を示
す。)で表わされる繰り返し単位2〜230個からな
る共重合体であつて、分子末端に水酸基を有する
液状ジエン系共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ブタジエン繰り返し単位
(但し、シス―1,4構造0.15〜0.25、トランス
―1,4構造0.55〜0.65、ビニル―1,2構造
0.15〜0.25の割合である。)4〜460個
および式
からなる(式中、Yは前記と同じである。)で表
わされる繰り返し単位2〜230個共重合体であつ
て、分子末端にハロゲンを有する液状ジエン系共
重合体の製造方法(以下、第2発明という。)を
提供するものである。 That is, the present invention has a butadiene repeating unit (however, 0.15 to 0.25 of cis-1,4 structure, 0.55 to 0.65 of trans-1,4 structure, 0.55 to 0.65 of vinyl-1,2 structure)
The ratio is between 0.15 and 0.25. ) 4 to 460 pieces and formula (In the formula, Y represents a phenyl group or a cyano group.) A liquid diene-based copolymer (hereinafter referred to as the first ) and butadiene repeating units (however, the ratio is 0.15 to 0.25 for cis-1,4 structure, 0.55 to 0.65 for trans-1,4 structure, and 0.15 to 0.25 for vinyl-1,2 structure) 4 to 460 units. and (In the formula, Y represents a phenyl group or a cyano group.) A copolymer consisting of 2 to 230 repeating units and having a hydroxyl group at the end of the molecule, a liquid diene copolymer is reacted with a halogen compound. Butadiene repeating unit characterized by having a structure of
The ratio is between 0.15 and 0.25. ) 4 to 460 pieces and formula A method for producing a liquid diene copolymer having halogen at the molecular end, which is a copolymer with 2 to 230 repeating units represented by (wherein Y is the same as above) (hereinafter referred to as No. 2 invention).
第1発明の共重合体はブタジエン繰り返し単位
および
(式中、Yはフエニル基あるいはシアノ基を示
す。)で表わされる繰り返し単位すなわち、スチ
レンあるいはアクリロニトリル繰り返し単位から
なり、分子両末端にハロゲンを有する液状ジエン
系共重合体である。ブタジエン繰り返し単位は通
常4〜460個程度含まれ、スチレンあるいはアク
リロニトリル繰り返し単位は2〜230個程度含ま
れるものである。これらの繰り返し単位の配列は
特に制限はなく、ランダム共重合体,ブロツク共
重合体等いずれのものであつても良い。また、ハ
ロゲンとしては塩素,臭素,フツ素およびヨウ素
が挙げられるが、特に塩素および臭素が好まし
い。 The copolymer of the first invention has butadiene repeating units and (In the formula, Y represents a phenyl group or a cyano group.) It is a liquid diene copolymer consisting of repeating units represented by styrene or acrylonitrile repeating units, and having halogens at both molecular ends. It usually contains about 4 to 460 butadiene repeating units, and about 2 to 230 styrene or acrylonitrile repeating units. The arrangement of these repeating units is not particularly limited, and may be any one such as a random copolymer or a block copolymer. Examples of halogen include chlorine, bromine, fluorine and iodine, with chlorine and bromine being particularly preferred.
第1発明は、このような分子両末端にハロゲン
を有する新規な液状ジエン系共重合体である。こ
のものは硬化処理において、イソシアネート化合
物の代りにジアミン化合物を使用することがで
き、発泡が生じることもなく、また耐薬品性,耐
水性等も良好である。 The first invention is a novel liquid diene copolymer having halogens at both ends of the molecule. This product can use a diamine compound instead of an isocyanate compound in the curing treatment, does not cause foaming, and has good chemical resistance, water resistance, etc.
上記の第1発明の新規な液状ジエン系共重合体
は様々な方法により製造することができるが、例
えば以下に述べる第2発明の方法により好適に製
造することができる。 Although the novel liquid diene copolymer of the first invention described above can be produced by various methods, for example, it can be suitably produced by the method of the second invention described below.
すなわち、上記ブタジエン繰り返し単位および
スチレンあるいはアクリロニトリル繰り返し単位
からなる共重合体であつて、分子両末端に水酸基
を有する液状ジエン系共重合体にハロゲン化合物
を反応させることにより第1発明の共重合体を製
造することができる。原料である分子両末端に水
酸基を有する液状ジエン系共重合体は通常、ブタ
ジエン繰り返し単位(但し、シス―1,4構造
0.15〜0.25、トランス―1,4構造0.55〜0.65、
ビニル―1,2構造0.15〜0.25の割合のものを用
いる。)4〜460個、スチレンあるいはアクリロニ
トリル繰り返し単位2〜230個程度を含有するも
のである。共重合体はランダム共重合体,ブロツ
ク共重合体等いずれのものであつても良い。 That is, the copolymer of the first invention is produced by reacting a halogen compound with a liquid diene copolymer consisting of the above-mentioned butadiene repeating unit and styrene or acrylonitrile repeating unit and having hydroxyl groups at both molecular ends. can be manufactured. The raw material liquid diene copolymer having hydroxyl groups at both ends of the molecule usually has butadiene repeating units (however, cis-1,4 structure
0.15~0.25, trans-1,4 structure 0.55~0.65,
A vinyl-1,2 structure having a ratio of 0.15 to 0.25 is used. ) 4 to 460 repeating units, and 2 to 230 styrene or acrylonitrile repeating units. The copolymer may be a random copolymer, a block copolymer, or the like.
ここで用いられるハロゲン化合物としては通
常、用いられているものであれば良く、例えば臭
化水素(HBr),塩化水素(HCl),フツ化水素
(HF),ヨウ化水素(HI)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。ここで三ハロゲン
化リンとしては具体的にはPBr3,PCl3などがあ
り、また五ハロゲン化リンとしてはPBr5,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クロルベンゼン,
プロムベンゼン,クロルトルエン,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,チオニルプロ
マイドなどのハロゲン化チオニル;アセチルクロ
ライド,アセチルプ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,チオニルプロマイドな
どのハロゲン化チオニルが好適に用いられる。 The halogen compound used here may be one that is normally used, such as hydrogen bromide (HB r ), hydrogen chloride (HCl), hydrogen fluoride (HF), hydrogen iodide (HI), etc. Hydrogen halide: Examples include phosphorus halides such as phosphorus trihalide and phosphorus pentahalide. Here, specific examples of phosphorus trihalides include PB r3 and PCl 3 , and examples of phosphorus pentahalides include PB r5 and PCl 5 .
and so on. Further, as the phosphorus halide, a compound of phosphorus and bromine can also be used.
In addition, halogen compounds include chlorobenzene,
Aryl halides such as prombenzene, chlorotoluene, and bromotoluene; Alkyl halides such as methyl chloride, methyl bromide, carbon tetrachloride, and carbon tetrabromide; Thionyl halides such as thionyl chloride and thionyl bromide; acetyl chloride, acetyl Examples include acid halides such as bromide. Among these, thionyl halides such as thionyl chloride and thionyl bromide are particularly preferably used.
上記2種の繰り返し単位と末端に水酸基を有す
る共重合体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1〜10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 above two types of repeating units and a copolymer having a hydroxyl group at the terminal 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 100°C.
0.1 to 24 hours at 20 atmospheres, preferably 1 to 10 atmospheres,
Preferably it is carried out 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
溶媒としてはベンゼン,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p―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,ジニトロフエノール,ニトロ
ソフエ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. Solvents used in this case include benzene, chloroform, dimethylformamide, acetonitrile, etc.
It is also possible to use a combination of two or more of the above solvents. Other stabilizers such as p-quinone, hydroquinone, hydroquinone monomethyl ether, BHT, dinitrophenol, nitrosophenol, etc. may be added if necessary.
このようにして第1発明の末端にハロゲンを有
する新規な液状ジエン系共重合体を製造すること
ができる。 In this way, the novel liquid diene copolymer having a halogen at the end according to the first invention can be produced.
このように、本発明の方法により得られる液状
ジエン系共重合体はジアミン化合物を用いて容易
に硬化させることができ、また得られた硬化体は
耐薬品性,耐水性などが極めて優れたものであ
る。 As described above, the liquid diene copolymer obtained by the method of the present invention can be easily cured using a diamine compound, and the obtained cured product has extremely excellent chemical resistance, water resistance, etc. It is.
それ故、本発明の液状ジエン系共重合体は硬化
処理により性質の改善された硬化体を容易に製造
することができる。 Therefore, by curing the liquid diene copolymer of the present invention, a cured product with improved properties can be easily produced.
したがつて、本発明の液状ジエン系共重合体は
硬化体原料あるいは種々の中間体として有用なも
のである。 Therefore, the liquid diene copolymer of the present invention is useful as a raw material for a cured product or as a variety of intermediates.
なお、本発明の末端にハロゲンを有する液状ジ
エン系共重合体に、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
する液状ジエン系共重合体を製造することができ
る。 Note that a liquid diene copolymer having an amino group at the terminal can be produced by further reacting the liquid diene copolymer having a halogen at the terminal with ammonia or an amine.
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
冷却管つき1の容三ツ口フラスコに水酸基末
端液状ポリブタジエン―スチレン共重合体(数平
均分子量2800,水酸基含有量0.65meq/g,出光
石油化学(株)製,商品名「Polybd CS―15」(シス
―1,4構造20%,トランス―1,4構造60%,
ビニル―1,2構造20%,ブタジエン単位75%,
スチレン単位25%)50.0g,クロロホルム600ml、
およびピリジン4gを加え、5℃に冷却した。次
いで、この溶液に10ml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(株)製、特級)5.3
gを30分かけて滴下した。その後、温度を5℃に
保つたまま2時間反応を行ない、さらにクロロホ
ルム還流下、6時間反応を行なつた。反応終了
後、100mlの蒸留水を加えて撹拌し、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2の分液ロートに移し、約600mlの蒸留水
を加えて洗浄を2回行なつた。分液後、溶剤を除
去して反応物39.3gを得た。Example 1 A hydroxyl-terminated liquid polybutadiene-styrene copolymer (number average molecular weight 2800, hydroxyl group content 0.65meq/g, manufactured by Idemitsu Petrochemical Co., Ltd., product name "Polybd CS-15") was placed in a three-neck flask with a capacity of 1 and equipped with a cooling tube. (20% cis-1,4 structure, 60% trans-1,4 structure,
Vinyl-1,2 structure 20%, butadiene unit 75%,
Styrene unit 25%) 50.0g, chloroform 600ml,
and 4 g of pyridine were added, and the mixture was cooled to 5°C. Next, thionyl chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade) 5.3 diluted with 10 ml of chloroform was added to this solution.
g was added dropwise over 30 minutes. Thereafter, the reaction was carried out for 2 hours while maintaining the temperature at 5° C., and the reaction was further carried out for 6 hours under refluxing of chloroform. After the reaction was completed, 100 ml of distilled water was added and stirred to remove unreacted thionyl chloride. Next, this reaction solution was transferred to No. 2 separating funnel, and washed twice by adding about 600 ml of distilled water. After separation, the solvent was removed to obtain 39.3 g of a reaction product.
この反応生成物の分析結果を以下に示す。 The analysis results of this reaction product are shown below.
水酸基当量 0.06meq/g
(アセチル化法による)
粘 度 165ポイズ/30℃
元素分析値(重量%)
炭素:87.6, 水素:10.0,
酸素: 0.0, 塩素: 2.3
また、この反応生成物の赤外吸収スペクトルに
よる分析(IR分析)の結果、3200〜3600cm-1に
おける水酸基の吸収が消失していることが認めら
れた。Hydroxyl group equivalent: 0.06 meq/g (by acetylation method) Viscosity: 165 poise/30°C Elemental analysis values (wt%) Carbon: 87.6, Hydrogen: 10.0, Oxygen: 0.0, Chlorine: 2.3 In addition, infrared radiation of this reaction product As a result of absorption spectrum analysis (IR analysis), it was found that the absorption of hydroxyl groups at 3200 to 3600 cm -1 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りに
チオニルブロマイド10.0gを用いたこと以外は実
施例1と同様にして反応生成物を得た。Example 2 A reaction product was obtained in the same manner as in Example 1 except that 10.0 g of thionyl bromide was used instead of thionyl chloride.
この反応生成物の分析結果を次に示す。 The analysis results of this reaction product are shown below.
水酸基当量 0.02meq/g
(アセチル化法による)
粘 度 180ポイズ/30℃
元素分析値(重量%)
炭素:85.0, 水素:9.8,
酸素: 0.0, 塩素:5.2
また、反応生成物のIR分析の結果、3200〜
3600cm-1における水酸基の吸収が消失しているこ
とが認められた。Hydroxyl group equivalent: 0.02 meq/g (by acetylation method) Viscosity: 180 poise/30°C Elemental analysis values (wt%) Carbon: 85.0, Hydrogen: 9.8, Oxygen: 0.0, Chlorine: 5.2 In addition, IR analysis of the reaction product Result, 3200~
It was observed that the absorption of hydroxyl groups at 3600 cm -1 disappeared.
実施例 3
実施例1において原料として水酸基末端液状ポ
リブタジエン―スチレン共重合体の代りに水酸基
末端液状ポリブタジエン―アクリロニトリル共重
合体(数平均分子量2800,水酸基含有量
0.60meq/g,出光石油化学(株)製、商品名
「PolybdCN―15」(シス―1,4構造20%,トラ
ンス―1,4構造60%,ビニル―1,2構造20
%,ブタジエン単位85%,ニトリル単位15%)
50.0gを用いたこと以外は実施例1と同様にして
反応生成物を40.3g得た。Example 3 In Example 1, a hydroxyl group-terminated liquid polybutadiene-acrylonitrile copolymer (number average molecular weight 2800, hydroxyl group content
0.60meq/g, manufactured by Idemitsu Petrochemical Co., Ltd., product name "PolybdCN-15" (20% cis-1,4 structure, 60% trans-1,4 structure, 20% vinyl-1,2 structure)
%, butadiene units 85%, nitrile units 15%)
40.3 g of a reaction product was obtained in the same manner as in Example 1 except that 50.0 g was used.
この反応生成物の分析結果を以下に示す。 The analysis results of this reaction product are shown below.
水酸基当量 0.03meq/g
(アセチル化法による)
粘 度 760ポイズ/30℃
元素分析値(重量%)
炭素:83.7, 水素:10.0,
酸素: 0.1, 窒素: 3.8,
塩素: 2.5
また、IR分析の結果、3200〜3600cm-1におけ
る水酸基の吸収が消失していることが認められ
た。Hydroxyl group equivalent: 0.03meq/g (by acetylation method) Viscosity: 760 poise/30℃ Elemental analysis values (wt%) Carbon: 83.7, Hydrogen: 10.0, Oxygen: 0.1, Nitrogen: 3.8, Chlorine: 2.5 In addition, IR analysis As a result, it was observed that the absorption of hydroxyl groups at 3200 to 3600 cm -1 disappeared.
実施例 4
実施例3においてチオニルクロライドの代りに
チオニルブロマイド10.0gを用いたこと以外は実
施例3と同様にして反応生成物を得た。Example 4 A reaction product was obtained in the same manner as in Example 3 except that 10.0 g of thionyl bromide was used instead of thionyl chloride.
この反応生成物の分析結果を以下に示す。 The analysis results of this reaction product are shown below.
水酸基当量 0.01meq/g
(アセチル化法による)
粘 度 920ポイズ/30℃
元素分析値(重量%)
炭素:81.2, 水素:9.7,
酸素: 0.0, 窒素:3.7,
臭素: 5.4
また、IR分析の結果、3200〜3600cm-1におけ
る水酸基の吸収が消失していることが認められ
た。Hydroxyl group equivalent: 0.01meq/g (by acetylation method) Viscosity: 920 poise/30℃ Elemental analysis values (wt%) Carbon: 81.2, Hydrogen: 9.7, Oxygen: 0.0, Nitrogen: 3.7, Bromine: 5.4 In addition, IR analysis As a result, it was observed that the absorption of hydroxyl groups at 3200 to 3600 cm -1 disappeared.
応用例
上記実施例2および4で得られた臭素末端液状
ポリブタジエン共重合体100gにメチル化テトラ
エチルテトラミン9.0gを加えて混合撹拌し、脱
泡させて硬化物を製造した。Application Example 9.0 g of methylated tetraethyltetramine was added to 100 g of the bromine-terminated liquid polybutadiene copolymer obtained in Examples 2 and 4 above, mixed and stirred, and defoamed to produce a cured product.
これらの硬化物を70℃の熱水中に168時間浸漬
処理したときの重量変化率は0.1重量%以下であ
つた。 When these cured products were immersed in hot water at 70°C for 168 hours, the weight change rate was 0.1% by weight or less.
Claims (1)
ス―1,4構造0.55〜0.75、ビニル―1,2構造
0.15〜0.25の割合である。)4〜460個および式 (式中、Yはフエニル基あるいはシアノ基を示
す。)で表わされる繰り返し単位2〜230個からな
る共重合体であつて、分子末端にハロゲンを有す
る液状ジエン系共重合体。 2 ハロゲンが臭素あるいは塩素である特許請求
の範囲第1項記載の共重合体。 3 ブタジエン繰り返し単位(但し、シス―1,
4構造0.15〜0.25、トランス―1,4構造0.55〜
0.75、ビニル―1,2構造0.15〜0.25の割合であ
る。)4〜460個および 式 (式中、Yはフエニル基あるいはシアノ基を示
す。)で表わされる繰り返し単位2〜230個からな
る共重合体であつて、分子末端に水酸基を有する
液状ジエン系共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ブタジエン繰り返し単位
(但し、シス―1,4構造0.15〜0.25、トランス
―1,4構造0.55〜0.75、ビニル―1,2構造
0.15〜0.25の割合である。)4〜460個および 式 (式中、Yは前記と同じである。) で表わされる繰り返し単位2〜230個からなる共
重合体であつて、分子末端にハロゲンを有する液
状ジエン系共重合体の製造方法。 4 ハロゲンが臭素あるいは塩素である特許請求
の範囲第3項記載の製造方法。[Claims] 1 Butadiene repeating unit (However, cis-1,4 structure 0.15 to 0.25, trans-1,4 structure 0.55 to 0.75, vinyl-1,2 structure
The ratio is between 0.15 and 0.25. ) 4 to 460 pieces and formula (In the formula, Y represents a phenyl group or a cyano group.) A liquid diene copolymer consisting of 2 to 230 repeating units and having a halogen at the molecular end. 2. The copolymer according to claim 1, wherein the halogen is bromine or chlorine. 3 Butadiene repeating unit (however, cis-1,
4 structure 0.15~0.25, trans-1,4 structure 0.55~
0.75, vinyl-1,2 structure 0.15-0.25. ) 4 to 460 pieces and formula (In the formula, Y represents a phenyl group or a cyano group.) A copolymer consisting of 2 to 230 repeating units and having a hydroxyl group at the end of the molecule, a liquid diene copolymer is reacted with a halogen compound. Butadiene repeating unit characterized by having a structure of
The ratio is between 0.15 and 0.25. ) 4 to 460 pieces and formula (In the formula, Y is the same as above.) A method for producing a liquid diene copolymer having 2 to 230 repeating units and having a halogen at the molecular end. 4. The manufacturing method according to claim 3, wherein the halogen is bromine or chlorine.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15889784A JPS6137804A (en) | 1984-07-31 | 1984-07-31 | Liquid, halogen-terminated diene copolymer and its production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15889784A JPS6137804A (en) | 1984-07-31 | 1984-07-31 | Liquid, halogen-terminated diene copolymer and its production |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6137804A JPS6137804A (en) | 1986-02-22 |
JPS6345724B2 true JPS6345724B2 (en) | 1988-09-12 |
Family
ID=15681758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15889784A Granted JPS6137804A (en) | 1984-07-31 | 1984-07-31 | Liquid, halogen-terminated diene copolymer and its production |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6137804A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2749579B1 (en) | 2011-09-12 | 2017-11-15 | Zeon Corporation | Conjugated diene polymer and method for producing same |
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
- 1984-07-31 JP JP15889784A patent/JPS6137804A/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 |
---|---|
JPS6137804A (en) | 1986-02-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2001213820A (en) | Method of producing 1,1,1,3,3-pentachloro-propane | |
HUT75954A (en) | Process for the manufacture of 1,1,1,3,3-pentafluoropropane | |
JPS6117815B2 (en) | ||
JP3498272B2 (en) | Triorgano substituted tin lithium initiator | |
JPS6345724B2 (en) | ||
JP4776996B2 (en) | Method for synthesizing tetrafluoroparaxylene | |
JPH0329798B2 (en) | ||
JPS63283756A (en) | Activity sustaining improved catalyst system for double-decomposing olefin | |
US5955638A (en) | Process for preparation of 2-chloro-1-propene | |
JP2000086545A (en) | Production of 1,1,1,3,3-pentachloropropane | |
JP2008031337A5 (en) | ||
JPH0360326B2 (en) | ||
EP0429967B1 (en) | Process for the liquid phase chlorination of 1,3-butadiene | |
JPH0149368B2 (en) | ||
JP3459892B2 (en) | Fluorinated surfactant compound and method for producing the same | |
JPS642601B2 (en) | ||
JPS6345723B2 (en) | ||
US5072062A (en) | Bromination method | |
US5348923A (en) | Silica-based substrates modified by grafting of polyalkylguanidinium groups, their process of manufacture and their use as catalysts | |
JPS6072836A (en) | Manufacture of 3,4-dichlorobenzotrihalogenide | |
Rosin et al. | Tetrachlorinated rubber: The addition of carbon tetrachloride to 1, 4‐polybutadiene | |
JP2003313016A (en) | Method for producing cof2 | |
US3835177A (en) | Process for the preparation of benzonitrile | |
US4129699A (en) | Process for the hydrohalogenation of buta-diene-containing polymers | |
JPS6176538A (en) | Rubber composition |