JPH0562125B2 - - Google Patents
Info
- Publication number
- JPH0562125B2 JPH0562125B2 JP23883383A JP23883383A JPH0562125B2 JP H0562125 B2 JPH0562125 B2 JP H0562125B2 JP 23883383 A JP23883383 A JP 23883383A JP 23883383 A JP23883383 A JP 23883383A JP H0562125 B2 JPH0562125 B2 JP H0562125B2
- Authority
- JP
- Japan
- Prior art keywords
- macromonomer
- parts
- mercaptopropionic acid
- polymerization
- weight
- 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 - Fee Related
Links
- 239000000178 monomer Substances 0.000 claims description 19
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 238000004040 coloring Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical group CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 231100000676 disease causative agent Toxicity 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 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
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- -1 alkyl methacrylates Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明はマクロモノマーの製造方法に関するも
のである。
従来からグラフト共重合体は工業的には、ラジ
カル重合性官能基をもたない高分子量体の存在下
で、重合開始剤及び重合性単量体を乳化重合、塊
状重合又は懸濁重合することによりほとんど製造
されているが、このグラフト共重合体には多量の
グラフト化されていない重合体が含まれており、
グラフト効率が低いという欠点をもつていた。
一方、有機溶剤中で片末端カルボキシル基を有
する重合体とグリシジル基を有するラジカル重合
性単量体を反応させてなる、ラジカル重合性高分
子量単量体とラジカル重合性単量体を、ラジカル
共重合させて得られるグラフト共重合体には、グ
ラフト化されていない重合体がほとんど含まれ
ず、グラフト効率が極めて高いという特徴をもつ
ている。
しかし、このマクロモノマーを製造する際、反
応中に多量の赤褐色の着色を伴ない、商品価値が
低下するため、反応液の状態で脱色をおこなう必
要があり、工業的製造における障害となつてい
た。
通常、反応液の状態での脱色方法としては、例
えば活性炭による吸着法、及び酸化剤又は還元剤
による処理法等が知られているが、活性炭による
吸着法では充分脱色できず、一方酸化剤及び還元
剤による処理法は、マクロモノマーの変質をもた
らし好ましい方法とはいえない。さらにマクロモ
ノマーに対する貧溶媒、例えばメタノール、エタ
ノール、ｎ−ヘキサンなどに沈殿させて精製する
方法があるが、充分脱色されず、また価格がアツ
プするなどの欠点がある。このように脱色方法が
マクロモノマーの工業的製造における重要な問題
であつた。
本発明者等は、マクロモノマーを製造する際反
応中に多量の赤褐色の着色を伴うという、工業的
製造における致命的な問題点に対し、その着色の
原因について鋭意検討を行なつた。
即ち、従来の製造方法例えば特公昭43−11224
号公報にみられるように有機溶剤中でラジカル重
合性単量体をメルカプト酢酸存在下で、ラジカル
重合させて得られるプレポリマーとグリシジルメ
タクリレートをジメチルラウリルアミン触媒の存
在下で反応させて得られるマクロモノマーの反応
液は、多大の赤褐色の着色を帯びており（比較例
４；ガードナー色数 ６）この原因物質を鋭意研
究した結果、メルカプト酢酸が最大の着色原因物
質であると推定し、これについて鋭意検討を行な
つた。その結果カルボキシル基を有する連鎖移動
剤として、ラジカル重合反応で作用しているメル
カプト酢酸を３−メルカプトプロピオン酸又は２
−メルカプトプロピオン酸におきかえることによ
り、分子構造式より推定される以上に着色を大巾
に低下させることが可能となり本発明を完成する
に到つたのである。
即ち、本発明はメルカプトプロピオン酸を連鎖
移動剤として用いてエチレン性不飽和単量体をラ
ジカル重合してなる、前記メルカプトプロピオン
酸に由来するカルボキシル基を片末端に有する片
末端カルボキシル型重合体とグリシジル基を有す
るラジカル重合性単量体を触媒の存在下で反応さ
せることを特徴とするマクロモノマーの製造方法
である。
本発明におけるマクロモノマーとは、分子鎖の
片末端に重合性の官能基を有する比較的低分子量
の重合体（数平均分子量1000〜数万）を意味す
る。
次にメルカプトプロピオン酸に由来するカルボ
キシル基を片末端に有する重合体（以下プレポリ
マーという）の製造方法について述べる。
使用されるエチレン性不飽和単量体（以下モノ
マーという）としては、例えばスチレン、ビニル
トルエン、酢酸ビニル、メタクリル酸アルキル
（
The present invention relates to a method for producing macromonomers. Traditionally, graft copolymers have been produced industrially by emulsion polymerization, bulk polymerization, or suspension polymerization of a polymerization initiator and a polymerizable monomer in the presence of a polymer having no radically polymerizable functional group. However, this graft copolymer contains a large amount of ungrafted polymer;
It had the disadvantage of low grafting efficiency. On the other hand, a radically polymerizable high molecular weight monomer and a radically polymerizable monomer, which are obtained by reacting a polymer having a carboxyl group at one end with a radically polymerizable monomer having a glycidyl group in an organic solvent, are combined into a radically polymerizable monomer. The graft copolymer obtained by polymerization contains almost no non-grafted polymer and has an extremely high grafting efficiency. However, when producing this macromonomer, a large amount of reddish-brown coloring occurs during the reaction, reducing the commercial value, so it is necessary to decolorize the reaction solution, which has been an obstacle in industrial production. . Generally, methods for decolorizing the reaction solution include adsorption using activated carbon and treatment using an oxidizing agent or reducing agent.However, the adsorption method using activated carbon cannot achieve sufficient decolorization; The treatment method using a reducing agent is not a preferable method because it causes deterioration of the macromonomer. Furthermore, there is a method of purifying the macromonomer by precipitation in a poor solvent such as methanol, ethanol, n-hexane, etc., but this method has drawbacks such as insufficient decolorization and increased cost. As described above, the decolorization method has been an important problem in the industrial production of macromonomers. The inventors of the present invention have conducted extensive research into the cause of the coloring, which is a fatal problem in industrial production, in which a large amount of reddish-brown coloring occurs during the reaction when producing a macromonomer. That is, conventional manufacturing methods such as Japanese Patent Publication No. 43-11224
As seen in the publication, a macro is obtained by reacting a prepolymer obtained by radical polymerization of a radically polymerizable monomer in an organic solvent in the presence of mercaptoacetic acid with glycidyl methacrylate in the presence of a dimethyl lauryl amine catalyst. The monomer reaction solution had a large amount of reddish-brown coloring (Comparative Example 4; Gardner color number 6).As a result of intensive research into the causative agent, we estimated that mercaptoacetic acid was the most causative agent of the coloring, and we We conducted a thorough study. As a result, as a chain transfer agent having a carboxyl group, mercaptoacetic acid acting in a radical polymerization reaction can be replaced with 3-mercaptopropionic acid or 2-mercaptopropionic acid.
- By replacing it with mercaptopropionic acid, it became possible to reduce the coloration to a greater extent than estimated from the molecular structure formula, which led to the completion of the present invention. That is, the present invention relates to a single-end carboxyl type polymer having a carboxyl group derived from mercaptopropionic acid at one end, which is obtained by radical polymerizing an ethylenically unsaturated monomer using mercaptopropionic acid as a chain transfer agent. This is a method for producing a macromonomer, which is characterized by reacting a radically polymerizable monomer having a glycidyl group in the presence of a catalyst. The macromonomer in the present invention means a relatively low molecular weight polymer (number average molecular weight of 1,000 to several tens of thousands) having a polymerizable functional group at one end of the molecular chain. Next, a method for producing a polymer having a carboxyl group derived from mercaptopropionic acid at one end (hereinafter referred to as prepolymer) will be described. Examples of the ethylenically unsaturated monomers (hereinafter referred to as monomers) used include styrene, vinyltoluene, vinyl acetate, and alkyl methacrylates (
【式】Ｒは炭素数１〜18のアル
キル基）、アクリル酸アルキル（CH2＝CH−
COOR、Ｒは炭素数１〜18のアルキル基）、Ｎ−
ビニルピロリドン、等の単独又は２種以上の混合
物が使用されるが、カルボキシル基等のグリシジ
ル基と反応性の基を有するモノマーは好ましくな
い。
また、使用しうる有機溶剤としては、ラジカル
重合させて得られたプレポリマーを溶解するもの
で、かつ反応中において不活性なものであればよ
く、例えばベンゼン、トルエン、キシレン、トリ
フロロトルエン、クロルベンゼン、酢酸エチル、
酢酸プロピル、酢酸ブチル、酢酸メトキシエチ
ル、酢酸エトキシエチル、ジオキサン、メチルイ
ソブチルケトン、シクロヘキサノン、Ｎ，Ｎ−ジ
メチルホルムアミド、などの単独又は２種以上の
混合物が使用される。
プレポリマーの分子量としては、製造されたマ
クロモノマーがラジカル重合性を損うことがない
範囲であればよく、好ましい分子量としては数平
均分子量1000〜数万である。連鎖移動剤として
は、メルカプトプロピオン酸即ち２−メルカプト
プロピオン酸又は３−メルカプトプロピオン酸を
用いるが、その使用量はモノマー100重量部に対
し、0.2〜12重量部が好ましく、0.5〜12重量部が
特に好ましい。0.2重量部未満では高分子量の重
合体となりやすく、また重合性が悪くなる傾向が
あり、一方12重量部を越えると分子量が1000未満
となりやすく不適当である。
重合開始剤としては、ベンゾイルパーオキシ
ド、ラウロイルパーオキシド等のパーオキシド系
及びアゾビスイソブチロニトリル（以下AIBNと
称する）、アゾビスジメチルバレロニトリル等の
アゾビス系が使用しうるが、好ましくはアゾビス
系の重合開始剤が使用される。
本発明におけるプレポリマーの製造方法は、連
鎖移動剤としてメルカプトプロピオン酸を用い、
有機溶剤中でモノマーを常法によりラジカル重合
させる方法である。
本発明におけるマクロモノマーの製造に用いら
れるグリシジル基を有するラジカル重合性単量体
としてはグリシジルメタクリレート、グリシジル
アクリレート等があげられ、又触媒としては三級
アミン、四級アンモニウム塩及び四級ホスホニウ
ム塩が好ましく、四級アンモニウム塩及び四級ホ
スホニウム塩がさらに好ましい。具体的にはトリ
エチルアミン、トリプロピルアミン、テトラメチ
ルエチレンジアミン、ジメチルラウリルアミン、
トリエチルベンジルアンモニウムクロライド、ト
リメチルセチルアンモニウムブロマイド、テトラ
ブチルアンモニウムブロマイド、トリメチルベン
ジルアンモニウムクロライド、トリフエニルブチ
ルホスホニウムブロマイド、テトラブチルホスホ
ニウムブロマイドなどが好適に使用される。
本発明におけるマクロモノマーの製造方法とし
ては、メルカプトプロピオン酸存在下でラジカル
重合させて得られたプレポリマーの反応液のまま
の状態で、又は場合によつては沈澱精製した後、
再度有機溶剤にとかした状態にして、プレポリマ
ー濃度30〜60重量％、触媒濃度0.1〜５重量％及
びグリシジル基を有するラジカル重合性単量体プ
レポリマーのカルボキシル基当量の１〜３倍当量
使用し、反応温度70〜150℃で加熱反応させるこ
とにより、マクロモノマーを含む反応液を得る。
さらに又、好ましくはグリシジル基を有するラジ
カル重合性単量体の重合を防止するために重合防
止剤、例えばハイドロキノン、ハイドロキノンモ
ノメチルエーテル等を50〜500ppmに添加すると
よい。
本発明によれば、脱色剤を使用することなく、
脱色剤を使用した場合に比べて着色が極めて少な
いマクロモノマーが工業的に用意に製造可能とな
り、さらにはこのマクロモノマーを使用したグラ
フト効率の高いグラフト共重合体も着色が極めて
少なくなり、その工業的価値は極めて大きいもの
である。
以下に実施例及び比較例をあげて本発明をさら
に具体的に説明する。
なお各例における部は重量部を、％は重量％を
意味し、またハーゼン色数及びガードナー色数は
JIS Ｋ−6901に従つて測定した。
実施例 １
撹拌機、還流冷却器、滴下ロート、温度計、及
びN2ガス吹込口を備えたガラスフラスコに溶剤
として酢酸ブチル105.5部を仕込み、N2ガス導入
下80〜85℃にてメチルメタクリレート（以下
MMAと略記する）100部、３−メルカプトプロ
ピオン酸3.5部及びAIBN2部の混合溶液を４時間
かかつて連続的に滴下して重合を行なつた。その
後、同温度で２時間加熱した後95℃で１時間加熱
して重合を終了した。
得られたプレポリマーの反応液の酸価を測定し
たところ0.147mg当量／ｇであつた。又、130℃１
時間加熱減量によるプレポリマー濃度は50％であ
つた。
ついで、この反応液200部に対してグリシジル
メタクリレート5.4部（1.3倍当量／COOH）、触
媒としてテトラブチルアンモニウムブロマイド１
部（0.49％）及び重合防止剤としてハイドロキノ
ンモノメチルエーテル0.04部（200ppm）を加え、
反応温度95℃にて８時間反応させた。
得られた末端メタクリレート型メチルメタクリ
レートマクロモノマーの反応液の酸価測定したと
ころ、0.001mg当量／ｇ以下であり、酸価の減少
にもとづく反応率は99％以上であつた。又、反応
液の着色はハーゼン色数50であつた。
GPCによるマクロモノマーのポリスチレン換
算数平均分子量は2820であり、重量平均分子量は
4620であつた。
さらに得られたマクロモノマーの反応液60部、
MMA60部、アクリル酸10部、AIBN3部及びメ
チルエチルケトン267部を仕込み70℃にてラジカ
ル重合したところ、重量平均分子量26000のグラ
フトポリマーが得られ、未反応のマクロモノマー
は検出されなかつた。
実施例２〜10及び比較列１〜４
実施例１と同様の方法により実施した結果を表
−１に示した。[Formula] R is an alkyl group having 1 to 18 carbon atoms), alkyl acrylate (CH 2 = CH-
COOR, R is an alkyl group having 1 to 18 carbon atoms), N-
Vinylpyrrolidone or the like may be used alone or in a mixture of two or more, but monomers having a group reactive with a glycidyl group such as a carboxyl group are not preferred. In addition, the organic solvent that can be used is one that dissolves the prepolymer obtained by radical polymerization and is inert during the reaction, such as benzene, toluene, xylene, trifluorotoluene, chloride, etc. benzene, ethyl acetate,
Propyl acetate, butyl acetate, methoxyethyl acetate, ethoxyethyl acetate, dioxane, methyl isobutyl ketone, cyclohexanone, N,N-dimethylformamide, and the like may be used alone or in a mixture of two or more. The molecular weight of the prepolymer may be within a range that does not impair the radical polymerizability of the produced macromonomer, and the preferred molecular weight is a number average molecular weight of 1,000 to several tens of thousands. As the chain transfer agent, mercaptopropionic acid, that is, 2-mercaptopropionic acid or 3-mercaptopropionic acid, is used, and the amount used is preferably 0.2 to 12 parts by weight, and 0.5 to 12 parts by weight, based on 100 parts by weight of the monomer. Particularly preferred. If it is less than 0.2 parts by weight, the polymer tends to have a high molecular weight and the polymerizability tends to be poor, while if it exceeds 12 parts by weight, the molecular weight tends to be less than 1000, which is unsuitable. As the polymerization initiator, peroxide type such as benzoyl peroxide and lauroyl peroxide, and azobis type such as azobisisobutyronitrile (hereinafter referred to as AIBN) and azobisdimethylvaleronitrile can be used, but azobis type is preferable. A polymerization initiator is used. The method for producing a prepolymer in the present invention uses mercaptopropionic acid as a chain transfer agent,
This is a method in which monomers are radically polymerized in an organic solvent using a conventional method. Examples of the radically polymerizable monomer having a glycidyl group used in the production of the macromonomer in the present invention include glycidyl methacrylate and glycidyl acrylate, and examples of the catalyst include tertiary amines, quaternary ammonium salts, and quaternary phosphonium salts. Preferably, quaternary ammonium salts and quaternary phosphonium salts are more preferable. Specifically, triethylamine, tripropylamine, tetramethylethylenediamine, dimethyllaurylamine,
Triethylbenzylammonium chloride, trimethylcetylammonium bromide, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triphenylbutylphosphonium bromide, tetrabutylphosphonium bromide, and the like are preferably used. The method for producing the macromonomer in the present invention includes using the reaction solution of a prepolymer obtained by radical polymerization in the presence of mercaptopropionic acid as it is, or after purification by precipitation in some cases.
The prepolymer concentration is 30 to 60% by weight, the catalyst concentration is 0.1 to 5% by weight, and an equivalent of 1 to 3 times the carboxyl group equivalent of the radically polymerizable monomer prepolymer having a glycidyl group is used after it is dissolved in an organic solvent again. Then, a reaction solution containing a macromonomer is obtained by carrying out a heating reaction at a reaction temperature of 70 to 150°C.
Furthermore, it is preferable to add a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, etc. in an amount of 50 to 500 ppm in order to prevent polymerization of the radically polymerizable monomer having a glycidyl group. According to the present invention, without using a bleaching agent,
It is now possible to easily produce a macromonomer industrially that has very little coloration compared to when a decolorizing agent is used, and graft copolymers that use this macromonomer and have high grafting efficiency also have very little coloration, making it possible to manufacture them industrially. Its value is extremely large. EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples. In each example, parts mean parts by weight, % means weight %, and the Hazen color number and Gardner color number are
Measured according to JIS K-6901. Example 1 A glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and an N2 gas inlet was charged with 105.5 parts of butyl acetate as a solvent, and methyl methacrylate was added at 80 to 85°C while introducing N2 gas. (below
Polymerization was carried out by continuously dropping a mixed solution of 100 parts of MMA), 3.5 parts of 3-mercaptopropionic acid, and 2 parts of AIBN over a period of 4 hours. Thereafter, the mixture was heated at the same temperature for 2 hours and then heated at 95°C for 1 hour to complete the polymerization. The acid value of the resulting prepolymer reaction solution was measured and found to be 0.147 mg equivalent/g. Also, 130℃1
The prepolymer concentration due to time heating loss was 50%. Next, 5.4 parts of glycidyl methacrylate (1.3 times equivalent/COOH) and 1 part of tetrabutylammonium bromide as a catalyst were added to 200 parts of this reaction solution.
(0.49%) and 0.04 parts (200 ppm) of hydroquinone monomethyl ether as a polymerization inhibitor,
The reaction was carried out at a reaction temperature of 95°C for 8 hours. When the acid value of the resulting reaction solution of the terminal methacrylate type methyl methacrylate macromonomer was measured, it was 0.001 mg equivalent/g or less, and the reaction rate based on the decrease in the acid value was 99% or more. The reaction solution was colored with a Hazen color number of 50. The polystyrene equivalent number average molecular weight of the macromonomer by GPC is 2820, and the weight average molecular weight is
It was 4620. Furthermore, 60 parts of the obtained macromonomer reaction solution,
When 60 parts of MMA, 10 parts of acrylic acid, 3 parts of AIBN, and 267 parts of methyl ethyl ketone were charged and radical polymerized at 70°C, a graft polymer with a weight average molecular weight of 26,000 was obtained, and no unreacted macromonomer was detected. Examples 2 to 10 and Comparative Rows 1 to 4 Table 1 shows the results obtained using the same method as in Example 1.
【表】【table】
Claims (1)
用いてエチレン性不飽和単量体をラジカル重合し
てなる、前記メルカプトプロピオン酸に由来する
カルボキシル基を片末端に有する片末端カルボキ
シル型重合体とグリシジル基を有するラジカル重
合性単量体を触媒の存在下で反応させることを特
徴とするマクロモノマーの製造方法。1 A carboxyl-type polymer at one end, which is obtained by radical polymerizing an ethylenically unsaturated monomer using mercaptopropionic acid as a chain transfer agent, and which has a carboxyl group derived from the mercaptopropionic acid at one end, and a glycidyl group. A method for producing a macromonomer, which comprises reacting a radically polymerizable monomer in the presence of a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23883383A JPS60133007A (en) | 1983-12-20 | 1983-12-20 | Preparation of macromonomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23883383A JPS60133007A (en) | 1983-12-20 | 1983-12-20 | Preparation of macromonomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60133007A JPS60133007A (en) | 1985-07-16 |
| JPH0562125B2 true JPH0562125B2 (en) | 1993-09-07 |
Family
ID=17035947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23883383A Granted JPS60133007A (en) | 1983-12-20 | 1983-12-20 | Preparation of macromonomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60133007A (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62212415A (en) * | 1986-03-13 | 1987-09-18 | Toagosei Chem Ind Co Ltd | Production of oligomer |
| JPH01178512A (en) * | 1987-12-29 | 1989-07-14 | Nitto Denko Corp | Acrylate macromonomer and preparation thereof |
| JPH01245001A (en) * | 1988-03-28 | 1989-09-29 | Toagosei Chem Ind Co Ltd | Production of macromonomer and graft polymer |
| JP2780722B2 (en) * | 1989-10-02 | 1998-07-30 | 三井化学株式会社 | Acrylic copolymer, its production method and its use |
| US5618898A (en) * | 1992-02-10 | 1997-04-08 | Toagosei Chemical Industry Co., Ltd. | Weather-resistant solvent-based coating obtained by polymerization with thioether bond converted to sulfone bond |
| JP3906493B2 (en) * | 1996-05-29 | 2007-04-18 | 東亞合成株式会社 | Method for producing macromonomer dispersion |
| FR2750321B1 (en) * | 1996-06-28 | 1998-07-31 | Oreal | USE IN COSMETICS OF FLEXIBLE SKELETON COPOLYMERS, GRAFT BY HYDROPHOBIC AND RIGID MACROMONOMERS; COMPOSITIONS IMPLEMENTED |
| US6388026B1 (en) | 1997-08-05 | 2002-05-14 | S. C. Johnson Commercial Markets, Inc. | Process for the preparation of macromers |
| TWI403838B (en) | 2007-04-11 | 2013-08-01 | Lg Chemical Ltd | Photosensitive resin composition comprising a polymer prepared by using macromonomer as alkaly soluble resin |
| JP5347115B2 (en) | 2007-04-24 | 2013-11-20 | 綜研化学株式会社 | Manufacturing method of adhesive |
| WO2012093689A1 (en) | 2011-01-06 | 2012-07-12 | 三菱レイヨン株式会社 | Modifier for polyvinylidene fluoride, binder resin composition for batteries, secondary cell electrode, and battery |
| EP2937367B1 (en) | 2012-12-18 | 2018-06-27 | Mitsubishi Chemical Corporation | Polymer and production method thereof, molding material and molded product |
| JP5768928B2 (en) | 2012-12-20 | 2015-08-26 | 三菱レイヨン株式会社 | POLYMER COMPOSITION FOR FORMING POROUS MEMBRANE AND POROUS MEMBRANE |
| WO2014142311A1 (en) | 2013-03-15 | 2014-09-18 | 三菱レイヨン株式会社 | Resin composition, membrane-forming stock solution, porous membrane, and hollow fiber membrane, water treatment device, electrolyte support, and separator using porous membrane |
| EP3059269B1 (en) | 2013-10-16 | 2021-03-31 | Mitsubishi Chemical Corporation | Polymer, production method for same, and molded article |
| JP6868979B2 (en) * | 2016-07-06 | 2021-05-12 | 株式会社日本触媒 | Acrylic acid ester polymer and its manufacturing method |
| KR102526940B1 (en) | 2017-03-27 | 2023-05-02 | 미쯔비시 케미컬 주식회사 | Porous membrane, membrane module, water treatment device, and method for producing porous membrane |
| JP7099467B2 (en) | 2017-09-25 | 2022-07-12 | 三菱ケミカル株式会社 | Hollow fiber membrane |
| US11498994B2 (en) | 2017-11-24 | 2022-11-15 | Mitsubishi Chemical Corporation | Block copolymer composition and production method therefor |
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| CN115210279A (en) | 2020-03-26 | 2022-10-18 | 三菱化学株式会社 | Copolymer, resin composition, molded body, film-shaped molded body, and method for producing copolymer |
| JP7472001B2 (en) | 2020-11-13 | 2024-04-22 | 日産自動車株式会社 | Multi-layer coating method |
| WO2022114157A1 (en) | 2020-11-30 | 2022-06-02 | 三菱ケミカル株式会社 | Resin composition, molded article, and macromonomer copolymer |
| JPWO2023068375A1 (en) | 2021-10-22 | 2023-04-27 | ||
| TW202336104A (en) | 2021-12-10 | 2023-09-16 | 日商三菱化學股份有限公司 | Curable composition, molded body, silicone hydrogel, method for producing silicone hydrogel, and macromonomer |
-
1983
- 1983-12-20 JP JP23883383A patent/JPS60133007A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60133007A (en) | 1985-07-16 |
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