JPS6286012A - Production of liquid diene copolymer - Google Patents
Production of liquid diene copolymerInfo
- Publication number
- JPS6286012A JPS6286012A JP22477685A JP22477685A JPS6286012A JP S6286012 A JPS6286012 A JP S6286012A JP 22477685 A JP22477685 A JP 22477685A JP 22477685 A JP22477685 A JP 22477685A JP S6286012 A JPS6286012 A JP S6286012A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- diene
- copolymer
- liquid diene
- epoxy group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 19
- 239000007788 liquid Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000178 monomer Substances 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001993 dienes Chemical class 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 239000000565 sealant Substances 0.000 abstract description 2
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical class C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 abstract 1
- 238000013019 agitation Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 azo compound Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920006311 Urethane elastomer Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- LEKIODFWYFCUER-UHFFFAOYSA-N 2-methylidenebut-3-enenitrile Chemical compound C=CC(=C)C#N LEKIODFWYFCUER-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004672 reactive softener Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ウレタンエラストマーの製造、樹脂、ゴムの
改質材、接着剤、電子線レジスト材等に用いられる液状
ジエン系共重合体の製造方法に関する。さらに詳しくは
分子内に水酸基とエポキシ基を有し、その水酸基含量が
比較的高い液状ジエン系共重合体の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to the production of urethane elastomers, the production of liquid diene copolymers used in resins, rubber modifiers, adhesives, electron beam resist materials, etc. Regarding the method. More specifically, the present invention relates to a method for producing a liquid diene copolymer that has a hydroxyl group and an epoxy group in its molecule and has a relatively high hydroxyl group content.
従来、ブタジェンのようなジエン系モノマーと、アクリ
ル酸グリシジルのようなモノマーとを、δ。Conventionally, diene monomers such as butadiene and monomers such as glycidyl acrylate have been used for δ.
δ′−アゾビス（δ−シアノ）−ｎ−ペンタノールのよ
うな水酸基を有するアブ化合物の存在下、または２．２
′−アゾビスイソブチロニトリルのようなアゾ化合物と
メルカプトエタノールのようなメルカプトアルカノール
の存在下、共重合せしめて、分子内に水酸基とエポキシ
基を有する液状ジエン系共重合体を製造することが知ら
れている。in the presence of an Ab compound having a hydroxyl group such as δ′-azobis(δ-cyano)-n-pentanol, or 2.2
It is possible to copolymerize an azo compound such as '-azobisisobutyronitrile and a mercaptoalkanol such as mercaptoethanol to produce a liquid diene copolymer having a hydroxyl group and an epoxy group in the molecule. Are known.
しかしながら、アゾ化合物を用いる方法においては、共
重合反応を行うにあたりジメチルホルムアミドなどの特
別な溶剤を用いる必要があり、しかも残渣の除去に再沈
など煩雑な処理工程を必要とした。またアゾ化合物とメ
ルカプトアルカノールを用いる方法においては、得られ
る共重合体の水酸基含量が０．３〜０．４ （ｍｅｑ／
ｇ）と低いものであり、例えばイソシアネート化合物と
反応させてウレタンエラストマーを製造するにあたって
も反応性の小さいものであった。However, in the method using an azo compound, it is necessary to use a special solvent such as dimethylformamide to carry out the copolymerization reaction, and furthermore, the removal of the residue requires complicated processing steps such as reprecipitation. In addition, in the method using an azo compound and a mercaptoalkanol, the hydroxyl group content of the resulting copolymer is 0.3 to 0.4 (meq/
g), and the reactivity was low even when reacting with an isocyanate compound to produce a urethane elastomer, for example.
本発明はこのような欠点を解消した液状ジエン系共重合
体の製造方法を提供することを目的とする。An object of the present invention is to provide a method for producing a liquid diene copolymer that eliminates these drawbacks.
本発明の液状ジエン系共重合体の製造方法は、ジエン系
モノマーとエポキシ基含有モノマーとを、過酸化水素の
存在下、共重合せしめることを特徴とする。The method for producing a liquid diene copolymer of the present invention is characterized by copolymerizing a diene monomer and an epoxy group-containing monomer in the presence of hydrogen peroxide.
本発明に用いられるジエン系モノマーとしては、特に制
限されないが、４通常は炭素数４〜１２のジオレフィン
系不飽和の非置換−２２−置換−１もしくは２，３−置
換−１，３−ジエンが用いられる。ここで置換基として
はアルキル基、了り−ル基、ハロゲン、シアノ基、ニト
ロ基などがある。The diene monomer used in the present invention is not particularly limited, but is usually a diolefinically unsaturated unsubstituted-22-substituted-1 or 2,3-substituted-1,3- having 4 to 12 carbon atoms. A diene is used. Examples of the substituent include an alkyl group, an aryl group, a halogen, a cyano group, and a nitro group.
具体的なモノマーとしては、１，３−ブタジェン、イソ
プレン、１，３−ペンタジェン、クロロブレン、２．３
−ジクロロブタジェン、２−シアノ−１，３−ブタジェ
ン、２，３−ジメチル−１，３−ブタジェンなどがある
。Specific monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, chlorobrene, 2.3
-dichlorobutadiene, 2-cyano-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and the like.
本発明に用いられるエポキシ基含有モノマーとしては、
とくに制限されないが、不飽和グリシジルエステル、例
えばアクリル酸グリシジル、メタクリル酸グリシジルや
アリルグリシジルエーテル等が用いられる。The epoxy group-containing monomer used in the present invention includes:
Although not particularly limited, unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether can be used.
本発明は上記ジエン系モノマーとエポキシ基含有モノマ
ーとを過酸化水素の存在下、共重合せしめるものである
が、両者の配合割合は、特に制限されないが通常はジエ
ン系モノマー５０〜９８ｗｔ％に対し、エポキシ基含荀
モノマーを５０〜２ｗｔ％で使用する。In the present invention, the diene monomer and the epoxy group-containing monomer are copolymerized in the presence of hydrogen peroxide, and the blending ratio of both is not particularly limited, but is usually 50 to 98 wt% of the diene monomer. , the epoxy group-containing monomer is used in an amount of 50 to 2 wt%.
本発明においては、基本的にはジエン系モノマーとエポ
キシ基含有モノマーを共重合させるものであるが、必要
に応じジエン系モノマーの一部をエチレン性不飽和モノ
マーで置き換えることができ、炭素数２〜２２個のα−
オレフィン付加重合性モノマーが用いられる。具体的に
は、スチレン、α−メチルスチレン、ビニルトルエン、
メタクリル酸メチル、アクリル酸、塩化ビニル、塩化ビ
ニリデン、アクリロニトリル、アクリルアミド、２−エ
チルへキシルアクリレート、ｎ−オクタデシルアクリレ
ート、無水マレイン酸、ブテン、２−ヒドロキシエチル
メタクリレートなどである。In the present invention, basically a diene monomer and an epoxy group-containing monomer are copolymerized, but if necessary, a part of the diene monomer can be replaced with an ethylenically unsaturated monomer. ~22 α−
An olefin addition polymerizable monomer is used. Specifically, styrene, α-methylstyrene, vinyltoluene,
These include methyl methacrylate, acrylic acid, vinyl chloride, vinylidene chloride, acrylonitrile, acrylamide, 2-ethylhexyl acrylate, n-octadecyl acrylate, maleic anhydride, butene, and 2-hydroxyethyl methacrylate.
本発明の重合反応は特に溶媒を必要とはしないが、通常
、アルコール、アルコールと水の混合物、エーテル、ケ
トン、脂肪族炭化水素、芳香族炭化水素、ハロゲン化炭
化水素等の溶媒中で行うことが好ましい。このような溶
媒として、メタノール、エタノール、ｎ−プロパツール
、イソプロパツール、ブタノール、プロピルエーテル、
テトラヒドロフラン、酢酸エチル、セロソルブ、セロソ
ルブアセテート、エチルセルソルブ、アセトンなどやこ
れらの混合物がある。溶媒の使用量は全仕込み量（モノ
マー、溶媒、過酸化水素等）の５〜５０Ｑｗｔ％、好ま
しくは３０〜３００ｗｔ％である。Although the polymerization reaction of the present invention does not particularly require a solvent, it is usually carried out in a solvent such as alcohol, a mixture of alcohol and water, ether, ketone, aliphatic hydrocarbon, aromatic hydrocarbon, or halogenated hydrocarbon. is preferred. Such solvents include methanol, ethanol, n-propanol, isopropanol, butanol, propyl ether,
Examples include tetrahydrofuran, ethyl acetate, cellosolve, cellosolve acetate, ethyl cellosolve, acetone, and mixtures thereof. The amount of the solvent used is 5 to 50 Qwt%, preferably 30 to 300 Qwt% of the total amount charged (monomer, solvent, hydrogen peroxide, etc.).
過酸化水素は全モノマー１００重量部に対し、０．１〜
５０重量部、好ましくは０．３〜３０重量部が用いられ
る。過酸化水素は通常、３０〜８０％水溶液、好ましく
は約５０％水溶液として使用される。Hydrogen peroxide is 0.1 to 100 parts by weight of all monomers.
50 parts by weight are used, preferably 0.3 to 30 parts by weight. Hydrogen peroxide is typically used as a 30-80% aqueous solution, preferably about 50% aqueous solution.
本発明の重合反応条件は、使用するジエン系モノマー等
の種類、使用量などにより異なり、一義的に特定できな
いが、通常は攪拌下、反応温度５０〜２００℃、好まし
くは８０〜１５０°Ｃ１反応圧力０〜２００ ｋｇ／ｃ
ｄＧ、好ましくは１〜１００ｋｇ／ａｄＧで０．１〜２
４時間、好ましくは０．２〜２０時間反応させることに
より液状ジエン系共重合体を製造することができる。The polymerization reaction conditions of the present invention vary depending on the type of diene monomer used, the amount used, etc., and cannot be unambiguously specified, but are usually performed under stirring at a reaction temperature of 50 to 200°C, preferably 80 to 150°C. Pressure 0~200 kg/c
dG, preferably 0.1-2 at 1-100 kg/adG
A liquid diene copolymer can be produced by reacting for 4 hours, preferably 0.2 to 20 hours.
このようにして得られた液状ジエン系共重合体は分子内
の水酸基含量が高く、イソシアネート化合物と反応させ
てウレタンエラストマーを製造するにあたっても反応性
が高く、ウレタンエラストマー原料として好適なもので
ある。The liquid diene copolymer thus obtained has a high content of hydroxyl groups in the molecule and has high reactivity when reacting with an isocyanate compound to produce a urethane elastomer, making it suitable as a raw material for a urethane elastomer.
本発明の共重合体により改質が可能な樹脂類としては、
液状または固形のエポキシ樹脂、フェノール樹脂、ポリ
テルペン樹脂、クマロン・インデン樹脂、キシレン樹脂
、芳香族石油樹脂、ウレタン樹脂、ロジン系樹脂、塩化
ビニルペースト、塩化ゴム、塩素化ポリエチレン、ポリ
エステル樹脂およびアスファルト等があるがこれらに限
定されるものではない。Resins that can be modified with the copolymer of the present invention include:
Liquid or solid epoxy resins, phenolic resins, polyterpene resins, coumaron/indene resins, xylene resins, aromatic petroleum resins, urethane resins, rosin resins, vinyl chloride paste, chlorinated rubber, chlorinated polyethylene, polyester resins, asphalt, etc. Yes, but not limited to these.
またこの共重合体の反応性と接着性などを利用して、−
Ｗｔ性または二液性組成物として、弾性シーラント、接
着剤、ライニング材、コーテイング材、塗料、粘着材、
ゴムの反応性軟化剤等として利用することができる。In addition, by utilizing the reactivity and adhesive properties of this copolymer, -
Wt-based or two-component compositions include elastic sealants, adhesives, lining materials, coating materials, paints, adhesive materials,
It can be used as a reactive softener for rubber.
以下実施例により本発明を説明するが、本発明の範囲は
これらの実施例に限定されるものではない。The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited to these Examples.
第１表に本発明の実施例および比較例の共重合体製造条
件、共重合体の諸性質について測定した結果を示す。Table 1 shows the conditions for producing copolymers of Examples and Comparative Examples of the present invention, and the results of measuring various properties of the copolymers.
実施例１〜５
攪拌機を備えたステンレス製耐圧容器に表示の割合で表
示の成分を仕込み、６０分間で昇温した後、表示の条件
で重合を行った。Examples 1 to 5 The indicated components were charged in the indicated ratios into a stainless steel pressure-resistant container equipped with a stirrer, the temperature was raised for 60 minutes, and then polymerization was carried out under the indicated conditions.
その後、容器外表面に空気を吹付けて降温し、表示の後
処理を行い共重合体を得た。Thereafter, air was blown onto the outer surface of the container to lower the temperature, and the indicated post-treatments were performed to obtain a copolymer.
比較例１〜３
３０分間で昇温したこと、０．０５重量部の４−ｔ−ブ
チルカテコールを含む１重量部のトルエンを添加して重
合を停止したこと以外は実施例と同様に表示のとおり反
応を行い、共重合体を得た。Comparative Examples 1 to 3 The same procedures as in Examples were carried out except that the temperature was raised for 30 minutes and the polymerization was stopped by adding 1 part by weight of toluene containing 0.05 part by weight of 4-t-butylcatechol. The reaction was carried out as described above to obtain a copolymer.
なお、表中の数値は別に記載のない限り重量部を意味す
る。In addition, the numerical values in the table mean parts by weight unless otherwise stated.
本発明により得られた液状ジエン系共重合体は水酸基含
量が高く、また本発明の製造方法は、特別な溶媒を使用
しなくても重合反応を行うことができ、さらに重合物の
後処理も簡便であり、本発明の工業的価値は極めて大で
ある。The liquid diene copolymer obtained by the present invention has a high hydroxyl group content, and the production method of the present invention allows the polymerization reaction to be carried out without using a special solvent, and furthermore, the post-treatment of the polymer can be carried out. It is simple and the industrial value of the present invention is extremely large.
Claims (1)
過酸化水素の存在下、共重合せしめることを特徴とする
液状ジエン系共重合体の製造方法。1. A diene monomer and an epoxy group-containing monomer,
A method for producing a liquid diene copolymer, which comprises copolymerizing in the presence of hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22477685A JPS6286012A (en) | 1985-10-11 | 1985-10-11 | Production of liquid diene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22477685A JPS6286012A (en) | 1985-10-11 | 1985-10-11 | Production of liquid diene copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6286012A true JPS6286012A (en) | 1987-04-20 |
Family
ID=16819030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22477685A Pending JPS6286012A (en) | 1985-10-11 | 1985-10-11 | Production of liquid diene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6286012A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5018583A (en) * | 1973-06-01 | 1975-02-27 | ||
| JPS5470393A (en) * | 1977-11-16 | 1979-06-06 | Denki Kagaku Kogyo Kk | Chloroprene liquid polymer and its production |
| JPS60112808A (en) * | 1983-11-25 | 1985-06-19 | Idemitsu Petrochem Co Ltd | Preparation of hydroxyl group-containing diene polymer |
-
1985
- 1985-10-11 JP JP22477685A patent/JPS6286012A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5018583A (en) * | 1973-06-01 | 1975-02-27 | ||
| JPS5470393A (en) * | 1977-11-16 | 1979-06-06 | Denki Kagaku Kogyo Kk | Chloroprene liquid polymer and its production |
| JPS60112808A (en) * | 1983-11-25 | 1985-06-19 | Idemitsu Petrochem Co Ltd | Preparation of hydroxyl group-containing diene polymer |
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