JP4485237B2 - (メタ)アクリル酸−不飽和二塩基酸共重合体の塩の製造法 - Google Patents
(メタ)アクリル酸−不飽和二塩基酸共重合体の塩の製造法 Download PDFInfo
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- JP4485237B2 JP4485237B2 JP2004105064A JP2004105064A JP4485237B2 JP 4485237 B2 JP4485237 B2 JP 4485237B2 JP 2004105064 A JP2004105064 A JP 2004105064A JP 2004105064 A JP2004105064 A JP 2004105064A JP 4485237 B2 JP4485237 B2 JP 4485237B2
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- acrylic acid
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- 229920001577 copolymer Polymers 0.000 title claims description 25
- 239000002253 acid Substances 0.000 title claims description 23
- 150000003839 salts Chemical class 0.000 title claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000011976 maleic acid Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000012776 electronic material Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- CKKXWJDFFQPBQL-UAIGNFCESA-N diazanium;(z)-but-2-enedioate Chemical compound [NH4+].[NH4+].[O-]C(=O)\C=C/C([O-])=O CKKXWJDFFQPBQL-UAIGNFCESA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
工程2:工程1で得られた反応液に、(C)アクリル酸又はメタアクリル酸を添加し、連鎖移動剤の存在下で重合させる工程
尚、ここで重量平均分子量(Mw)は、実施例に記載された測定法により測定された値である。
GPC(ゲルパーミエーションクロマトグラフィー)により、下記条件で測定した。
カラム:TSK PWXL+G4000PWXL+G2500PWXL(いずれも東ソー株式会社製)
カラム温度:40℃
検出器:RI又はUV(210nm)、RIで重量平均分子量(Mw)を、またUVで主共重合体の割合を測定した。尚主共重合体でないポリアクリル酸共重合体の重量平均分子量(Mw)は5000〜8000である。
溶離液:0.2mol/L リン酸緩衝液/アセトニトリル(9/1)
流速:1.0mL/min
注入量:0.1mL
標準:ポリエチレングリコール
<未反応モノマーの割合>
NMR(核磁気共鳴装置、Varian社製、型番:AS400)にて、反応生成物中の未反応モノマーの割合を測定した。ここでいう未反応モノマーとは主にマレイン酸モノマーである。
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器に、(a)マレイン酸無水物78.5g及び(b)イオン交換水80.0gを仕込み、55℃に加熱後、(c)28重量%アンモニア水溶液24.3gを滴下し、マレイン酸アンモニウム塩水溶液とした。(d)マレイン酸/アンモニア=100/50(モル比)。次に窒素気流下で100℃まで加熱した後、この温度を維持しながら、(e)80重量%アクリル酸水溶液360.5g及び(f)35重量%過酸化水素水溶液153.9gをそれぞれ別の滴下ロートから(g)3.5時間かけて滴下し重合反応を行った。滴下終了後、100℃で(h)10時間熟成し重合反応を完結させた。反応終了後、冷却し、約40℃を保持しながらpHが6〜8となるように(i)28重量%アンモニア水溶液で中和して、(j)アクリル酸―マレイン酸共重合体のアンモニウム塩を得た。
実施例1の(a)〜(j)を表1の通り変更し、(メタ)アクリル酸−マレイン酸共重合体の塩を製造した。
実施例1の(a)〜(j)を表1の通り変更し、(メタ)アクリル酸−マレイン酸共重合体の塩を製造した。
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えた反応容器に、マレイン酸無水物78.5g及びイオン交換水80.0gを仕込み、100℃に昇温後、この温度を維持しながら、80重量%アクリル酸水溶液360.5g及び10重量%過硫酸アンモニウム水溶液47.5gをそれぞれ別の滴下ロートから4時間かけて滴下し重合反応を行った。滴下終了後、100℃で10時間熟成し重合反応を完結させた。反応終了後、冷却し、約40℃を保持しながらpHが6〜8となるように28重量%アンモニア水溶液で中和して、アクリル酸―マレイン酸共重合体のアンモニウム塩を得た。
Claims (5)
- 以下の工程1及び2を有する、アクリル酸又はメタクリル酸と不飽和二塩基酸との共重合体の塩(以下、(メタ)アクリル酸−不飽和二塩基酸共重合体の塩という)の製造法。
工程1:(A)不飽和二塩基酸と、(B)アンモニア、アミン、それらの塩及び4級アンモニウム塩からなる群から選ばれる少なくとも1種とを、(A)成分/(B)成分(モル比)=100/30〜100/70で反応させる工程
工程2:工程1で得られた反応液に、(C)アクリル酸又はメタアクリル酸を添加し、過酸化水素の存在下で重合させる工程であって、(C)成分を(A)成分に対し(C)成分/(A)成分(モル比)=74/26〜91/9の割合で反応させ、且つ(A)成分と(C)成分の合計仕込みモル数に対して30〜60モル%の過酸化水素を添加する、工程 - (メタ)アクリル酸−不飽和二塩基酸共重合体の塩の重量平均分子量(Mw)が25000〜60000である請求項1記載の製造法。
- (A)成分が、マレイン酸無水物及びマレイン酸から選ばれる少なくとも1種である、請求項1又は2記載の製造法。
- (B)成分がアンモニア又はその塩である請求項1〜3いずれかに記載の製造法。
- 電子材料用分散剤として用いられる請求項1〜4いずれか記載の(メタ)アクリル酸−不飽和二塩基酸共重合体の塩の製造法
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JP2004105064A JP4485237B2 (ja) | 2004-03-31 | 2004-03-31 | (メタ)アクリル酸−不飽和二塩基酸共重合体の塩の製造法 |
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JP2004105064A JP4485237B2 (ja) | 2004-03-31 | 2004-03-31 | (メタ)アクリル酸−不飽和二塩基酸共重合体の塩の製造法 |
Publications (2)
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JP2005290125A JP2005290125A (ja) | 2005-10-20 |
JP4485237B2 true JP4485237B2 (ja) | 2010-06-16 |
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JP2004105064A Expired - Lifetime JP4485237B2 (ja) | 2004-03-31 | 2004-03-31 | (メタ)アクリル酸−不飽和二塩基酸共重合体の塩の製造法 |
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Families Citing this family (1)
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JP6814616B2 (ja) | 2015-12-17 | 2021-01-20 | 花王株式会社 | 粉体用分散剤組成物 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5966407A (ja) * | 1982-09-11 | 1984-04-14 | バスフ アクチエンゲゼルシヤフト | モノエチレン性不飽和のモノ−及びジカルボン酸からの共重合物の連続的製法 |
JPS60212412A (ja) * | 1984-04-06 | 1985-10-24 | Kao Corp | 共重合体の製造方法 |
-
2004
- 2004-03-31 JP JP2004105064A patent/JP4485237B2/ja not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5966407A (ja) * | 1982-09-11 | 1984-04-14 | バスフ アクチエンゲゼルシヤフト | モノエチレン性不飽和のモノ−及びジカルボン酸からの共重合物の連続的製法 |
JPS60212412A (ja) * | 1984-04-06 | 1985-10-24 | Kao Corp | 共重合体の製造方法 |
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