JPH0138408B2 - - Google Patents
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- Publication number
- JPH0138408B2 JPH0138408B2 JP57028863A JP2886382A JPH0138408B2 JP H0138408 B2 JPH0138408 B2 JP H0138408B2 JP 57028863 A JP57028863 A JP 57028863A JP 2886382 A JP2886382 A JP 2886382A JP H0138408 B2 JPH0138408 B2 JP H0138408B2
- Authority
- JP
- Japan
- Prior art keywords
- monovalent
- groups
- group
- divalent
- carbon atoms
- 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
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- 229910052751 metal Inorganic materials 0.000 claims description 75
- 239000002184 metal Substances 0.000 claims description 75
- 229920001577 copolymer Polymers 0.000 claims description 40
- 150000003839 salts Chemical class 0.000 claims description 38
- 150000002739 metals Chemical class 0.000 claims description 35
- 125000003277 amino group Chemical group 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 150000003863 ammonium salts Chemical class 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 15
- 150000005690 diesters Chemical class 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 12
- -1 (meth)acrylic acid hydroxyalkyl ester Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- LLLCSBYSPJHDJX-UHFFFAOYSA-M potassium;2-methylprop-2-enoate Chemical compound [K+].CC(=C)C([O-])=O LLLCSBYSPJHDJX-UHFFFAOYSA-M 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- CJGJYOBXQLCLRG-UHFFFAOYSA-M sodium;2-hydroxy-3-prop-2-enoxypropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)COCC=C CJGJYOBXQLCLRG-UHFFFAOYSA-M 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- DZGUJOWBVDZNNF-UHFFFAOYSA-N azanium;2-methylprop-2-enoate Chemical compound [NH4+].CC(=C)C([O-])=O DZGUJOWBVDZNNF-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RLQOUIUVEQXDPW-UHFFFAOYSA-M lithium;2-methylprop-2-enoate Chemical compound [Li+].CC(=C)C([O-])=O RLQOUIUVEQXDPW-UHFFFAOYSA-M 0.000 description 1
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 1
- 150000001451 organic peroxides Chemical class 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
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- ZSZFXZHKVNYPLL-UHFFFAOYSA-M sodium;1-hydroxypropane-1-sulfonate Chemical compound [Na+].CCC(O)S([O-])(=O)=O ZSZFXZHKVNYPLL-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は新規水溶性共重合体及びその製造方法
に関するものである。
従来、水溶性の重合体としてアクリル酸やメタ
クリル酸またはそのアルカリ中和物を重合もしく
は共重合させて得られるポリマー、例えばポリア
クリル酸、ポリアクリル酸アンモニウム、ポリメ
タクリル酸ナトリウム等は公知である。これらの
水溶性共重合体は無機顔料の水系スラリー分散剤
等として広く用いられている。また、これらの改
良として、（メタ）アクリル酸アルキルエステル
とアクリル酸との共重合体、あるいは（メタ）ア
クリル酸ヒドロキシアルキルエステルとアクリル
酸との共重合体等が提案されているが、いまだ充
分な性能を有する水溶性重合体は得られていない
のが現状である。
本発明者等はこのような現状に鑑み、分散剤等
として優れた性能を有する水溶性重合体を得べく
研究を重ねた結果、本発明を完成させるに至つ
た。
即ち、第１の発明は、
一般式
（但し、式中R1は水素又はメチル基を表わし、
Ｘは水素、１価金属、２価金属、アンモニウム
基又は有機アミン基を表わす。）
で示される構造単位（）50〜99.9モル％と
一般式
（但し、式中ｐは１〜４の整数を表わし、
ｑ及びｒはそれぞれ独立に０又は１〜100の整
数を表わし、
R2及びR3はそれぞれ独立に炭素数２〜４のア
ルキレン基を表わし、
Ｙ及びＺは、それぞれ水酸基、炭素数１〜４
のアルコキシ基、１価のリン酸基（但し、１価金
属、２価金属、アンモニウム基若しくは有機アミ
ン基の塩又は炭素数１〜４のアルキル基のモノ若
しくはジエステルを含む。）、１価のスルホン酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）又は１価の硫酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）を表わし且つＹ及び
Ｚの少なくとも一方が必ず１価のリン酸基（但
し、１価金属、２価金属、アンモニウム基若しく
は有機アミン基の塩又は炭素数１〜４のアルキル
基のモノ若しくはジエステルを含む。）及び１価
のスルホン酸基（但し、１価金属、２価金属、ア
ンモニウム塩若しくは有機アミン基の塩又は炭素
数１〜４のアルキル基のエステルを含む。）から
なる群より選ばれた１種であるか、あるいはＹ
とＺは一緒に２価のリン酸基又は２価のスルホン
酸基を表わす。）
で示される構造単位（）0.1〜50モル％（但し、
両者の合計は100モル％である。）とからなる数平
均分子量1000〜10000の新規水溶性共重合体（以
下、新規水溶性共重合体(A)という。）に関するも
のである。
また、第２の発明は、
一般式
（但し、式中R1は水素又はメチル基を表わし、
Ｘは水素、１価金属、２価金属、アンモニウム
基又は有機アミン基を表わす。）
で示される（メタ）アクリル酸系単量体(1)から選
ばれる１種又は２種以上と
一般式
（但し、式中ｐは１〜４の整数を表わし、
ｑ及びｒはそれぞれ独立に０又は１〜100の整
数を表わし、
R2及びR3はそれぞれ独立に炭素数２〜４のア
ルキレン基を表わし、
Ｙ及びＺは、それぞれ水酸基、炭素数１〜４
のアルコキシ基、１価のリン酸基（但し、１価金
属、２価金属、アンモニウム基若しくは有機アミ
ン基の塩又は炭素数１〜４のアルキル基のモノ若
しくはジエステルを含む。）、１価のスルホン酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）又は１価の硫酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）を表わし且つＹ及び
Ｚの少なくとも一方が必ず１価のリン酸基（但
し、１価金属、２価金属、アンモニウム基若しく
は有機アミン基の塩又は炭素数１〜４のアルキル
基のモノ若しくはジエステルを含む。）及び１価
のスルホン酸基（但し、１価金属、２価金属、ア
ンモニウム塩若しくは有機アミン基の塩又は炭素
数１〜４のアルキル基のエステルを含む。）から
なる群より選ばれた１種であるか、あるいはＹ
とＺは一緒に２価のリン酸基又は２価のスルホン
酸基を表わす。）
で示されるアリルエーテル系単量体(2)から選ばれ
る１種又は２種以上とを共重合させることを特徴
とする新規水溶性共重合体(A)の製造方法に関する
ものである。
本発明で用いられる前記一般式で示される（メ
タ）アクリル酸系単量体(1)としては、例えばアク
リル酸、アクリル酸ナトリウム、アクリル酸カリ
ウム、アクリル酸リチウム、アクリル酸アンモニ
ウム、メタクリル酸、メタクリル酸ナトリウム、
メタクリル酸カリウム、メタクリル酸リチウム、
メタクリル酸アンモニウムなどをあげることがで
きる。
また、前記一般式で示されるアリルエーテル系
単量体(2)としては、例えば３−アリロキシ−２−
ヒドロキシプロパンスルホン酸及びその１価金属
塩、２価金属塩、アンモニウム塩もしくは有機ア
ミン塩、又はこれ等の化合物のリン酸エステルも
しくは硫酸エステル及びそれ等の１価金属塩、２
価金属塩、アンモニウム塩又は有機アミン塩；３
−アリロキシ−２−（ポリ）オキシエチレンプロ
パンスルホン酸及びその１価金属塩、２価金属
塩、アンモニウム塩もしくは有機アミン塩、又は
これ等の化合物のリン酸エステルもしくは硫酸エ
ステル及びそれ等の１価金属塩、２価金属塩、ア
ンモニウム塩又は有機アミン塩；３−アリロキシ
−２−（ポリ）オキシプロピレンプロパンスルホ
ン酸及びその１価金属塩、２価金属塩、アンモニ
ウム塩もしくは有機アミン塩、又はこれ等の化合
物のリン酸エステルもしくは硫酸エステル及びそ
れ等の１価金属塩、２価金属塩、アンモニウム塩
又は有機アミン塩；などをあげることができる。
これらのアリルエーテル系単量体(2)の中でも、
前記一般式におけるｐが１又は４のものが工業的
に入手しやすく有利である。
（メタ）アクリル酸系単量体(1)とアリルエーテ
ル系単量体(2)とから新規水溶性共重合体(A)を得る
には、従来公知の方法によることができる。例え
ば水、有機溶剤、あるいは水可溶性有機溶剤と水
との混合溶剤等の溶剤中での重合を挙げることが
できる。この際、水媒体中での重合には重合開始
剤として過硫酸塩や過酸化水素等が用いられ、亜
硫酸水素ナトリウムやアスコルビン酸等の促進剤
を併用することができる。有機溶剤中での重合に
は重合開始剤としてアゾ系化合物が有機過酸化物
等が用いられ、アミン化合物等の促進剤を併用す
ることができる。水可溶性有機溶剤と水との混合
溶剤中での重合には、上記の種々の重合開始剤あ
るいは重合開始剤と促進剤との組合せの中から適
宜選んで用いることができる。
このようにして得られた新規水溶性共重合体(A)
はそのままでも各種用途に用いられるが、必要に
より更にアルカリ性物質で中和して用いることも
できる。このようなアルカリ性物質としては、１
価金属及び２価金属の水酸化物、塩化物及び炭酸
塩：アンモニア；有機アミン等を挙げることがで
きる。
本発明の新規水溶性共重合体(A)は、無機顔料の
水系スラリー分散剤、セメント混和剤、洗剤用ビ
ルダー等の広範な用途に用いられて優れた性能を
発揮する。
新規水溶性共重合体(A)分子中での前記一般式で
示される構造単位（）と前記一般式で示される
構造単位（）との比率は、前者50〜99.9モル％
に対して後者0.1〜50モル％（但し、両者の合計
は100モル％である。）である。構造単位（）と
構造単位（）との比率がこの範囲内であると、
新規水溶性共重合体(A)は、構造単位（）と構造
単位（）との相互作用により、上記の如き用途
に用いられたときに、より一層優れた性能を発揮
する。
（メタ）アクリル酸系単量体(1)とアリルエーテ
ル系単量体(2)とから新規水溶性共重合体(A)を得る
に際して、該共重合体(A)分子中の構造単位（）
と構造単位（）との比率が前者50〜99.9モル％
対後者0.1〜50モル％（但し、両者の合計は100モ
ル％である。）となるよう仕込み比率を選ぶこと
が好ましい。
以下、実施例により本発明を更に詳細に説明す
る。しかし、本発明がこれらの例だけに限定され
るものではないことはいうまでもない。尚、例中
特にことわりのない限り％は重量％を表わすもの
とする。
実施例 １
還流冷却器を備えた内容積1lの４口フラスコに
純水142ｇを仕込み、90℃にて撹拌しながらアク
リル酸ナトリウムの30％水溶液600ｇ、３−アリ
ロキシ−２−ヒドロキシプロパンスルホン酸ナト
リウムの60％水溶液38ｇ及び過硫酸アンモニウム
の３％水溶液200ｇをそれぞれ3.5時間で滴下して
共重合反応させ、水溶性共重合体(1)の水溶液を得
た。未反応モノマーを臭素付加法及びポーラログ
ラフ法で測定（以下の実施例でも同様）したとこ
ろ、重合率は96％であつた。ゲルパーミエーシヨ
ンクロマトグラフで測定（以下の実施例でも同
様）したこの水溶性共重合体(1)の数平均分子量は
4400であつた。また、メタノールで沈殿精製し、
乾燥して得たこの水溶性共重合体(1)の赤外線吸収
スペクトル分析では、−Ｏ−、−CO−、−OHに基
づく吸収が確認された（赤外線吸収スペクトルは
第１図に示す。）。さらに、この乾燥した水溶性共
重合体(1)をD2Oに溶解し、NMR分析して
The present invention relates to a novel water-soluble copolymer and a method for producing the same. BACKGROUND ART Polymers obtained by polymerizing or copolymerizing acrylic acid, methacrylic acid, or their alkali neutralized products, such as polyacrylic acid, ammonium polyacrylate, and sodium polymethacrylate, are conventionally known as water-soluble polymers. These water-soluble copolymers are widely used as aqueous slurry dispersants for inorganic pigments. In addition, copolymers of (meth)acrylic acid alkyl ester and acrylic acid, or copolymers of (meth)acrylic acid hydroxyalkyl ester and acrylic acid, etc. have been proposed as improvements to these, but they are still insufficient. At present, no water-soluble polymer with such performance has been obtained. In view of the current situation, the present inventors have conducted repeated research to obtain a water-soluble polymer having excellent performance as a dispersant, etc., and as a result, have completed the present invention. That is, the first invention has the general formula (However, in the formula, R 1 represents hydrogen or a methyl group, and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group.) general formula (However, in the formula, p represents an integer of 1 to 4, q and r each independently represent an integer of 0 or 1 to 100, and R 2 and R 3 each independently represent an alkylene group having 2 to 4 carbon atoms. The expression Y and Z are each a hydroxyl group and a carbon number of 1 to 4.
alkoxy groups, monovalent phosphoric acid groups (including salts of monovalent metals, divalent metals, ammonium groups, or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms), monovalent phosphoric acid groups, A sulfonic acid group (including a monovalent metal, a divalent metal, an ammonium salt, a salt of an organic amine group, or an ester of an alkyl group having 1 to 4 carbon atoms) or a monovalent sulfuric acid group (including a monovalent metal, (including divalent metals, ammonium salts, salts of organic amine groups, or esters of alkyl groups having 1 to 4 carbon atoms), and at least one of Y and Z must be a monovalent phosphoric acid group (however, if a monovalent metal , salts of divalent metals, ammonium groups or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms) and monovalent sulfonic acid groups (however, monovalent metals, divalent metals, ammonium salts) or a salt of an organic amine group or an ester of an alkyl group having 1 to 4 carbon atoms.
and Z together represent a divalent phosphoric acid group or a divalent sulfonic acid group. ) 0.1 to 50 mol% (however,
The total of both is 100 mol%. ) and having a number average molecular weight of 1,000 to 10,000 (hereinafter referred to as novel water-soluble copolymer (A)). Moreover, the second invention is based on the general formula (However, in the formula, R 1 represents hydrogen or a methyl group, and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group.) One or more types selected from 1) and general formula (However, in the formula, p represents an integer of 1 to 4, q and r each independently represent an integer of 0 or 1 to 100, and R 2 and R 3 each independently represent an alkylene group having 2 to 4 carbon atoms. The expression Y and Z are each a hydroxyl group and a carbon number of 1 to 4.
alkoxy groups, monovalent phosphoric acid groups (including salts of monovalent metals, divalent metals, ammonium groups, or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms), monovalent phosphoric acid groups, A sulfonic acid group (including a monovalent metal, a divalent metal, an ammonium salt, a salt of an organic amine group, or an ester of an alkyl group having 1 to 4 carbon atoms) or a monovalent sulfuric acid group (including a monovalent metal, (including divalent metals, ammonium salts, salts of organic amine groups, or esters of alkyl groups having 1 to 4 carbon atoms), and at least one of Y and Z must be a monovalent phosphoric acid group (however, if a monovalent metal , salts of divalent metals, ammonium groups or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms) and monovalent sulfonic acid groups (however, monovalent metals, divalent metals, ammonium salts) or a salt of an organic amine group or an ester of an alkyl group having 1 to 4 carbon atoms.
and Z together represent a divalent phosphoric acid group or a divalent sulfonic acid group. ) The present invention relates to a method for producing a novel water-soluble copolymer (A) characterized by copolymerizing one or more selected from the allyl ether monomers (2) shown in (A). Examples of the (meth)acrylic acid monomer (1) represented by the general formula used in the present invention include acrylic acid, sodium acrylate, potassium acrylate, lithium acrylate, ammonium acrylate, methacrylic acid, and methacrylate. acid sodium,
Potassium methacrylate, lithium methacrylate,
Examples include ammonium methacrylate. Further, as the allyl ether monomer (2) represented by the above general formula, for example, 3-allyloxy-2-
Hydroxypropanesulfonic acid and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts thereof, or phosphoric acid esters or sulfuric acid esters of these compounds and monovalent metal salts thereof, 2
valent metal salt, ammonium salt or organic amine salt; 3
-Allyloxy-2-(poly)oxyethylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, or phosphoric acid ester or sulfuric acid ester of these compounds, and their monovalent metal salts Metal salt, divalent metal salt, ammonium salt or organic amine salt; 3-allyloxy-2-(poly)oxypropylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, or this Examples include phosphoric acid esters or sulfuric acid esters of compounds such as, monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts thereof. Among these allyl ether monomers (2),
Those in which p in the general formula is 1 or 4 are advantageous because they are easily available industrially. The novel water-soluble copolymer (A) can be obtained from the (meth)acrylic acid monomer (1) and the allyl ether monomer (2) by a conventionally known method. Examples include polymerization in a solvent such as water, an organic solvent, or a mixed solvent of a water-soluble organic solvent and water. At this time, a persulfate, hydrogen peroxide, etc. are used as a polymerization initiator for polymerization in an aqueous medium, and a promoter such as sodium bisulfite or ascorbic acid can be used in combination. For polymerization in an organic solvent, an azo compound, an organic peroxide, or the like is used as a polymerization initiator, and a promoter such as an amine compound can be used in combination. For polymerization in a mixed solvent of a water-soluble organic solvent and water, an appropriate selection can be used from among the various polymerization initiators or combinations of polymerization initiators and accelerators described above. New water-soluble copolymer thus obtained (A)
It can be used as it is for various purposes, but if necessary, it can be further neutralized with an alkaline substance before use. Such alkaline substances include 1
Hydroxides, chlorides and carbonates of valent metals and divalent metals: ammonia; organic amines, etc. can be mentioned. The novel water-soluble copolymer (A) of the present invention exhibits excellent performance when used in a wide range of applications such as an aqueous slurry dispersant for inorganic pigments, a cement admixture, and a builder for detergents. The ratio of the structural unit ( ) represented by the above general formula to the structural unit ( ) represented by the above general formula in the molecule of the new water-soluble copolymer (A) is 50 to 99.9 mol% of the former.
The latter is 0.1 to 50 mol% (however, the total of both is 100 mol%). If the ratio of structural units () to structural units () is within this range,
The new water-soluble copolymer (A) exhibits even better performance when used in the above applications due to the interaction between the structural units (). When obtaining a new water-soluble copolymer (A) from a (meth)acrylic acid monomer (1) and an allyl ether monomer (2), the structural unit ( )
The ratio of the former to the structural unit () is 50 to 99.9 mol%
It is preferable to select the charging ratio so that the latter is 0.1 to 50 mol% (however, the total of both is 100 mol%). Hereinafter, the present invention will be explained in more detail with reference to Examples. However, it goes without saying that the present invention is not limited to these examples. In the examples, % represents weight % unless otherwise specified. Example 1 142 g of pure water was charged into a 4-necked flask with an internal volume of 1 liter equipped with a reflux condenser, and while stirring at 90°C, 600 g of a 30% aqueous solution of sodium acrylate and sodium 3-allyloxy-2-hydroxypropanesulfonate were added. 38 g of a 60% aqueous solution of ammonium persulfate and 200 g of a 3% aqueous solution of ammonium persulfate were each added dropwise over 3.5 hours to cause a copolymerization reaction, thereby obtaining an aqueous solution of water-soluble copolymer (1). When the unreacted monomer was measured by the bromine addition method and the polarographic method (the same applies to the following examples), the polymerization rate was 96%. The number average molecular weight of this water-soluble copolymer (1) measured by gel permeation chromatography (the same applies to the following examples) is
It was 4400. Also, precipitate and purify with methanol,
Infrared absorption spectrum analysis of this water-soluble copolymer (1) obtained by drying confirmed absorption based on -O-, -CO-, and -OH (the infrared absorption spectrum is shown in Figure 1). . Furthermore, this dried water-soluble copolymer (1) was dissolved in D 2 O and analyzed by NMR.
【式】及び−CH2−の吸収を確認した。
実施例 ２
実施例１で使用したと同様の重合反応器に純水
150ｇを仕込み、３−アリロキシ−２−ヒドロキ
シプロパンスルホン酸ナトリウムに水酸化ナトリ
ウムを触媒に用いてエチレンオキサイドを５モル
付加させて得られるアリルエーテル系単量体140
ｇを溶解したのち、100℃にて撹拌しながらメタ
クリル酸カリウム35％水溶液170ｇ、過硫酸アン
モニウム６％水溶液150ｇ及び過酸化水素６％水
溶液50ｇをそれぞれ3.5時間で滴下して重合反応
を行ない、水溶性共重合体(2)の水溶液を得た。重
合率は90％であり、水溶性共重合体(2)の数平均分
子量は1600であつた。
実施例 ３
実施例１で使用したと同様の重合反応器に純水
132ｇを仕込んだ後、３−アリロキシ−２−ヒド
ロキシプロパンスルホン酸ナトリウムに水酸化ナ
トリウムを触媒に用いてプロピレンオキサイドを
２モル付加させたのちさらに５酸化リンを当量反
応させて得られたアリルエーテル系単量体95ｇを
仕込み、100℃にて撹拌しながらアクリル酸カリ
ウム35％水溶液300ｇ、過硫酸アンモニウム６％
水溶液150ｇ及び過酸化水素６％水溶液50ｇをそ
れぞれ3.5時間で滴下して水溶性共重合体(3)の水
溶液を得た。重合率は94％であり、水溶性共重合
体(3)の数平均分子量は2200であつた。
実施例 ４〜６
次の手順により水溶性共重合体の無機顔料分散
剤としての性能を調べた。容量1000mlのステンレ
ス製ビーカーにサチンホワイト（スルホアルミン
酸カルシウム６水塩）25％ペースト400ｇを入れ、
実施例１〜３で得られた水溶性共重合体(1)〜(3)を
別々に固形分として2.0ｇ（固形／固形、2.0％）
加え、デイゾルバー型羽根を取り付けたデイスパ
ーを用いて2000rpmで15分間撹拌し、25℃で粘度
を測定した。結果は表１に示した。
比較例 １
市販の分子量5000のポリアクリル酸ナトリウム
40％水溶液5.0ｇを用いる他は実施例４と同様に
してサチンホワイトの分散液を調製し、粘度を測
定した。結果は表１に示した。Absorption of [Formula] and -CH 2 - was confirmed. Example 2 Pure water was added to a polymerization reactor similar to that used in Example 1.
Allyl ether monomer 140 obtained by adding 5 moles of ethylene oxide to sodium 3-allyloxy-2-hydroxypropanesulfonate using sodium hydroxide as a catalyst.
After dissolving 1.5 g of 35% potassium methacrylate, 170 g of a 35% aqueous solution of potassium methacrylate, 150 g of a 6% aqueous solution of ammonium persulfate, and 50 g of a 6% aqueous hydrogen peroxide solution were each added dropwise over 3.5 hours while stirring at 100°C to perform a polymerization reaction. An aqueous solution of copolymer (2) was obtained. The polymerization rate was 90%, and the number average molecular weight of water-soluble copolymer (2) was 1,600. Example 3 Pure water was added to a polymerization reactor similar to that used in Example 1.
After charging 132 g, 2 moles of propylene oxide was added to sodium 3-allyloxy-2-hydroxypropanesulfonate using sodium hydroxide as a catalyst, and then an equivalent amount of phosphorus pentoxide was further reacted. Add 95g of monomer and add 300g of potassium acrylate 35% aqueous solution and 6% ammonium persulfate while stirring at 100℃.
150 g of an aqueous solution and 50 g of a 6% hydrogen peroxide aqueous solution were each added dropwise over 3.5 hours to obtain an aqueous solution of water-soluble copolymer (3). The polymerization rate was 94%, and the number average molecular weight of water-soluble copolymer (3) was 2,200. Examples 4 to 6 The performance of water-soluble copolymers as inorganic pigment dispersants was investigated by the following procedure. Pour 400g of Sachin White (calcium sulfoaluminate hexahydrate) 25% paste into a stainless steel beaker with a capacity of 1000ml.
2.0 g of water-soluble copolymers (1) to (3) obtained in Examples 1 to 3 separately as solid content (solid/solid, 2.0%)
In addition, the mixture was stirred at 2000 rpm for 15 minutes using a disper equipped with a dissolver type blade, and the viscosity was measured at 25°C. The results are shown in Table 1. Comparative example 1 Commercially available sodium polyacrylate with a molecular weight of 5000
A dispersion of Sachin White was prepared in the same manner as in Example 4, except that 5.0 g of the 40% aqueous solution was used, and the viscosity was measured. The results are shown in Table 1.
【表】
表１に示した如く、本発明の新規水溶性共重合
体は優れた顔料分散能を有している。
実施例 ７
還流冷却器を備えた内容積１の四つ口フラス
コに純水70ｇを仕込み、90℃にて攪拌しながらア
クリル酸ナトリウムの37％水溶液486.5ｇ、３−
アリロキシ−２−ヒドロキシプロパンスルホン酸
ナトリウムの60％水溶液38ｇ及び過硫酸アンモニ
ウムの６％水溶液100ｇをそれぞれ3.5時間で滴下
して共重合反応させ、水溶性共重合体(4)の水溶液
を得た。未反応モノマーを臭素付加法及びポーラ
ログラフ法で測定したところ、重合率は98％であ
つた。またゲルパーミエーシヨンクロマトグラフ
で測定した水溶性共重合体(4)の数平均分子量は
10000であつた。
実施例 ８
還流冷却器を備えた内容積１の四つ口フラス
コに純水150ｇを仕込み、３−アリロキシ−２−
ヒドロキシプロパンスルホン酸ナトリウムに水酸
化ナトリウムを触媒に用いてエチレンオキサイド
を５モル付加させて得られたアリルエーテル系単
量体140ｇを溶解したのち、100℃にて攪拌しなが
らメタクリル酸カリウム35％水溶液170ｇ、過硫
酸アンモニウム12％水溶液150ｇ及び過酸化水素
12％水溶液50ｇをそれぞれ3.5時間で滴下して重
合反応を行い、水溶性共重合体(5)の水溶液を得
た。重合率は94％であり、水溶性共重合体(5)の数
平均分子量は1000であつた。
実施例 ９〜10
次の手順により水溶性共重合体(4)及び(5)の無機
顔料分散剤としての性能を調べた。容量1000mlの
ステンレス製ビーカーにサチンホワイト（スルホ
アルミン酸カルシウム６水塩）25％ペースト400
ｇを入れ、実施例７〜８で得られた水溶性共重合
体(4)〜(5)を別々に固形分として2.0ｇ（固形／固
形、2.0％）加え、デイゾルバー型羽根を取り付
けたデイスパーを用いて2000rpmで15分間攪拌
し、25℃で粘度を測定した。その結果を第２表に
示した。[Table] As shown in Table 1, the novel water-soluble copolymer of the present invention has excellent pigment dispersion ability. Example 7 70 g of pure water was charged into a four-necked flask with an internal volume of 1 equipped with a reflux condenser, and while stirring at 90°C, 486.5 g of a 37% aqueous solution of sodium acrylate, 3-
38 g of a 60% aqueous solution of sodium allyloxy-2-hydroxypropanesulfonate and 100 g of a 6% aqueous solution of ammonium persulfate were each added dropwise over 3.5 hours to cause a copolymerization reaction, thereby obtaining an aqueous solution of water-soluble copolymer (4). When unreacted monomers were measured by the bromine addition method and polarographic method, the polymerization rate was 98%. In addition, the number average molecular weight of water-soluble copolymer (4) measured by gel permeation chromatography is
It was 10,000. Example 8 150 g of pure water was charged into a four-necked flask with an internal volume of 1 equipped with a reflux condenser, and 3-allyloxy-2-
After dissolving 140 g of allyl ether monomer obtained by adding 5 moles of ethylene oxide to sodium hydroxypropanesulfonate using sodium hydroxide as a catalyst, a 35% potassium methacrylate aqueous solution was dissolved at 100°C with stirring. 170g, 150g of ammonium persulfate 12% aqueous solution and hydrogen peroxide
A polymerization reaction was carried out by dropping 50 g of a 12% aqueous solution over 3.5 hours to obtain an aqueous solution of water-soluble copolymer (5). The polymerization rate was 94%, and the number average molecular weight of water-soluble copolymer (5) was 1,000. Examples 9-10 The performance of water-soluble copolymers (4) and (5) as inorganic pigment dispersants was investigated by the following procedure. Sachin White (calcium sulfoaluminate hexahydrate) 25% paste 400 in a stainless steel beaker with a capacity of 1000ml
g, and 2.0 g (solid/solid, 2.0%) of the water-soluble copolymers (4) to (5) obtained in Examples 7 to 8 were added separately as a solid content, and a disper equipped with dissolver type blades was prepared. The mixture was stirred at 2000 rpm for 15 minutes using a 2000 rpm, and the viscosity was measured at 25°C. The results are shown in Table 2.
第１図は実施例１で得た水溶性共重合体(1)の赤
外線吸収スペクトル図である。
FIG. 1 is an infrared absorption spectrum diagram of the water-soluble copolymer (1) obtained in Example 1.
Claims (1)
Ｘは水素、１価金属、２価金属、アンモニウム基
又は有機アミン基を表わす。） で示される構造単位（）50〜99.9モル％と 一般式 （但し、式中ｐは１〜４の整数を表わし、 ｑ及びｒはそれぞれ独立に０又は１〜100の整
数を表わし、 R2及びR3はそれぞれ独立に炭素数２〜４のア
ルキレン基を表わし、 Ｙ及びＺは、それぞれ水酸基、炭素数１〜４
のアルコキシ基、１価のリン酸基（但し、１価金
属、２価金属、アンモニウム基若しくは有機アミ
ン基の塩又は炭素数１〜４のアルキル基のモノ若
しくはジエステルを含む。）、１価のスルホン酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）又は１価の硫酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）を表わし且つＹ及び
Ｚの少なくとも一方が必ず１価のリン酸基（但
し、１価金属、２価金属、アンモニウム基若しく
は有機アミン基の塩又は炭素数１〜４のアルキル
基のモノ若しくはジエステルを含む。）及び１価
のスルホン酸基（但し、１価金属、２価金属、ア
ンモニウム塩若しくは有機アミン基の塩又は炭素
数１〜４のアルキル基のエステルを含む。）から
なる群より選ばれた１種であるか、あるいはＹ
とＺは１緒に２価のリン酸基又は２価のスルホン
酸基を表わす。） で示される構造単位（）0.1〜50モル％（但し、
両者の合計は100モル％である。）とからなる数平
均分子量1000〜10000の新規水溶性共重合体。 ２ 構造単位（）におけるｐが１である特許請
求の範囲第１項記載の新規水溶性共重合体。 ３ 構造単位（）におけるｐが１であり且つｑ
及びｒがともに０である特許請求の範囲第１項記
載の新規水溶性共重合体。 ４ 構造単位（）におけるｐが４である特許請
求の範囲第１項記載の新規水溶性共重合体。 ５ 構造単位（）におけるｐが４であり且つｑ
及びｒがともに０である特許請求の範囲第１項記
載の新規水溶性共重合体。 ６ 一般式 （但し、式中R1は水素又はメチル基を表わし、
Ｘは水素、１価金属、２価金属、アンモニウム基
又は有機アミン基を表わす。） で示される（メタ）アクリル酸系単量体(1)から選
ばれる１種又は２種以上と 一般式 （但し、式中ｐは１〜４の整数を表わし、 ｑ及びｒはそれぞれ独立に０又は１〜100の整
数を表わし、 R2及びR3はそれぞれ独立に炭素数２〜４のア
ルキレン基を表わし、 Ｙ及びＺは、それぞれ水酸基、炭素数１〜４
のアルコキシ基、１価のリン酸基（但し、１価金
属、２価金属、アンモニウム基若しくは有機アミ
ン基の塩又は炭素数１〜４のアルキル基のモノ若
しくはジエステルを含む。）、１価のスルホン酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）又は１価の硫酸塩
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）を表わし且つＹ及び
Ｚの少なくとも一方が必ず１価のリン酸基（但
し、１価金属、２価金属、アンモニウム基若しく
は有機アミン基の塩又は塩又は炭素数１〜４のア
ルキル基のモノ若しくはジエステルを含む。）及
び１価のスルホン酸基（但し、１価金属、２価金
属、アンモニウム塩若しくは有機アミン基の塩又
は炭素数１〜４のアルキル基のエステルを含む。）
からなる群より選ばれた１種であるか、あるいは
ＹとＺは一緒に２価のリン酸基又は２価のスル
ホン酸基を表わす。） で示されるアリルエーテル系単量体(2)から選ばれ
る１種又は２種以上とを共重合させることを特徴
とする 一般式 （但し、式中R1は水素又はメチル基を表わし、
Ｘは水素、１価金属、２価金属、アンモニウム基
又は有機アミン基を表わす。） で示される構造単位（）と 一般式 （但し、式中ｐは１〜４の整数を表わし、 ｑ及びｒはそれぞれ独立に０又は１〜100の整
数を表わし、 R2及びR3はそれぞれ独立に炭素数２〜４のア
ルキレン基を表わし、 Ｙ及びＺは、それぞれ水酸基、炭素数１〜４
のアルコキシ基、１価のリン酸基（但し、１価金
属、２価金属、アンモニウム基若しくは有機アミ
ン基の塩又は炭素数１〜４のアルキル基のモノ若
しくはジエステルを含む。）、１価のスルホン酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）又は１価の硫酸基
（但し、１価金属、２価金属、アンモニウム塩若
しくは有機アミン基の塩又は炭素数１〜４のアル
キル基のエステルを含む。）を表わし且つＹ及び
Ｚの少なくとも一方が必ず１価のリン酸基（但
し、１価金属、２価金属、アンモニウム基若しく
は有機アミン基の塩又は炭素数１〜４のアルキル
基のモノ若しくはジエステルを含む。）及び１価
のスルホン酸基（但し、１価金属、２価金属、ア
ンモニウム塩若しくは有機アミン基の塩又は炭素
数１〜４のアルキル基のエステルを含む。）から
なる群より選ばれた１種であるか、あるいはＹ
とＺは一緒に２価のリン酸基又は２価のスルホン
酸基を表わす。） で示される構造単位（） とからなる新規水溶性共重合体の製造方法。 ７ 構造単位（）と構造単位（）とが前者５
〜99.9モル％対後者0.1〜95モル％（但し、両者
の合計は100モル％である。）である特許請求の範
囲第６項記載の新規水溶性共重合体の製造方法。 ８ 構造単位（）と構造単位（）とが前者50
〜99.9モル％対後者0.1〜50モル％（但し、両者
の合計は100モル％である。）である特許請求の範
囲第６項記載の新規水溶性共重合体の製造方法。 ９ 構造単位（）におけるｐが１である特許請
求の範囲第６項記載の新規水溶性共重合体の製造
方法。 １０ 構造単位（）におけるｐが１であり且つ
ｑ及びｒがともに０である特許請求の範囲第６項
記載の新規水溶性共重合体の製造方法。 １１ 構造単位（）におけるｐが４である特許
請求の範囲第６項記載の新規水溶性共重合体の製
造方法。 １２ 構造単位（）におけるｐが４であり且つ
ｑ及びｒがともに０である特許請求の範囲第６項
記載の新規水溶性共重合体の製造方法。[Claims] 1. General formula (However, in the formula, R 1 represents hydrogen or a methyl group,
X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) 50 to 99.9 mol% of the structural unit represented by () and the general formula (However, in the formula, p represents an integer of 1 to 4, q and r each independently represent an integer of 0 or 1 to 100, and R 2 and R 3 each independently represent an alkylene group having 2 to 4 carbon atoms. The expression Y and Z are each a hydroxyl group and a carbon number of 1 to 4.
alkoxy groups, monovalent phosphoric acid groups (including salts of monovalent metals, divalent metals, ammonium groups, or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms), monovalent phosphoric acid groups, A sulfonic acid group (including a monovalent metal, a divalent metal, an ammonium salt, a salt of an organic amine group, or an ester of an alkyl group having 1 to 4 carbon atoms) or a monovalent sulfuric acid group (including a monovalent metal, (including divalent metals, ammonium salts, salts of organic amine groups, or esters of alkyl groups having 1 to 4 carbon atoms), and at least one of Y and Z must be a monovalent phosphoric acid group (however, if a monovalent metal , salts of divalent metals, ammonium groups or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms) and monovalent sulfonic acid groups (however, monovalent metals, divalent metals, ammonium salts) or a salt of an organic amine group or an ester of an alkyl group having 1 to 4 carbon atoms.
and Z together represent a divalent phosphoric acid group or a divalent sulfonic acid group. ) 0.1 to 50 mol% (however,
The total of both is 100 mol%. ) A new water-soluble copolymer with a number average molecular weight of 1000 to 10000. 2. The novel water-soluble copolymer according to claim 1, wherein p in the structural unit () is 1. 3 p in the structural unit () is 1 and q
The novel water-soluble copolymer according to claim 1, wherein both of and r are 0. 4. The novel water-soluble copolymer according to claim 1, wherein p in the structural unit () is 4. 5 p in the structural unit () is 4 and q
The novel water-soluble copolymer according to claim 1, wherein both of and r are 0. 6 General formula (However, in the formula, R 1 represents hydrogen or a methyl group,
X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) One or more selected from (meth)acrylic acid monomers (1) represented by the general formula (However, in the formula, p represents an integer of 1 to 4, q and r each independently represent an integer of 0 or 1 to 100, and R 2 and R 3 each independently represent an alkylene group having 2 to 4 carbon atoms. The expression Y and Z are each a hydroxyl group and a carbon number of 1 to 4.
alkoxy groups, monovalent phosphoric acid groups (including salts of monovalent metals, divalent metals, ammonium groups, or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms), monovalent phosphoric acid groups, Sulfonic acid groups (including monovalent metals, divalent metals, ammonium salts, salts of organic amine groups, or esters of alkyl groups having 1 to 4 carbon atoms) or monovalent sulfates (however, monovalent metals, (including divalent metals, ammonium salts, salts of organic amine groups, or esters of alkyl groups having 1 to 4 carbon atoms), and at least one of Y and Z must be a monovalent phosphoric acid group (however, if a monovalent metal , divalent metals, salts of ammonium groups or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms) and monovalent sulfonic acid groups (however, monovalent metals, divalent metals, (Includes ammonium salts, salts of organic amine groups, and esters of alkyl groups having 1 to 4 carbon atoms.)
or Y and Z together represent a divalent phosphoric acid group or a divalent sulfonic acid group. ) General formula characterized by copolymerizing one or more selected from allyl ether monomers (2) represented by (However, in the formula, R 1 represents hydrogen or a methyl group,
X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) Structural unit shown by () and general formula (However, in the formula, p represents an integer of 1 to 4, q and r each independently represent an integer of 0 or 1 to 100, and R 2 and R 3 each independently represent an alkylene group having 2 to 4 carbon atoms. The expression Y and Z are each a hydroxyl group and a carbon number of 1 to 4.
alkoxy groups, monovalent phosphoric acid groups (including salts of monovalent metals, divalent metals, ammonium groups, or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms), monovalent phosphoric acid groups, A sulfonic acid group (including a monovalent metal, a divalent metal, an ammonium salt, a salt of an organic amine group, or an ester of an alkyl group having 1 to 4 carbon atoms) or a monovalent sulfuric acid group (including a monovalent metal, (including divalent metals, ammonium salts, salts of organic amine groups, or esters of alkyl groups having 1 to 4 carbon atoms), and at least one of Y and Z must be a monovalent phosphoric acid group (however, if a monovalent metal , salts of divalent metals, ammonium groups or organic amine groups, or mono- or diesters of alkyl groups having 1 to 4 carbon atoms) and monovalent sulfonic acid groups (however, monovalent metals, divalent metals, ammonium salts) or a salt of an organic amine group or an ester of an alkyl group having 1 to 4 carbon atoms.
and Z together represent a divalent phosphoric acid group or a divalent sulfonic acid group. ) A method for producing a novel water-soluble copolymer consisting of the structural unit (). 7 Structural unit () and structural unit () are the former 5
99.9 mol % of the latter and 0.1 to 95 mol % of the latter (however, the total of both is 100 mol %). 8 Structural unit () and structural unit () are the former 50
99.9 mol% of the latter and 0.1 to 50 mol% of the latter (however, the total of both is 100 mol%). 9. The method for producing a novel water-soluble copolymer according to claim 6, wherein p in the structural unit () is 1. 10. The method for producing a novel water-soluble copolymer according to claim 6, wherein p in the structural unit () is 1, and both q and r are 0. 11. The method for producing a novel water-soluble copolymer according to claim 6, wherein p in the structural unit () is 4. 12. The method for producing a novel water-soluble copolymer according to claim 6, wherein p in the structural unit () is 4, and both q and r are 0.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2886382A JPS58147412A (en) | 1982-02-26 | 1982-02-26 | Novel water-soluble copolymer and its preparation |
| US06/614,695 US4500693A (en) | 1981-07-07 | 1984-05-25 | Water soluble copolymer method for manufacture therefore and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2886382A JPS58147412A (en) | 1982-02-26 | 1982-02-26 | Novel water-soluble copolymer and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58147412A JPS58147412A (en) | 1983-09-02 |
| JPH0138408B2 true JPH0138408B2 (en) | 1989-08-14 |
Family
ID=12260209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2886382A Granted JPS58147412A (en) | 1981-07-07 | 1982-02-26 | Novel water-soluble copolymer and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58147412A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2536758A1 (en) * | 1982-11-30 | 1984-06-01 | Coatex Sa | NON-POLLUTANT FLUIDIFYING ADJUVANT FOR SALTWATER AND / OR FRESHWATER WATER-BASED DRILLING SLUDGE |
| US4980433A (en) * | 1983-10-26 | 1990-12-25 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
| US4906383A (en) * | 1983-10-26 | 1990-03-06 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
| US4944885A (en) * | 1983-10-26 | 1990-07-31 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4898684A (en) * | 1983-10-26 | 1990-02-06 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
| US4869845A (en) * | 1983-10-26 | 1989-09-26 | Betz Laboratories, Inc. | Water treatment compositions |
| US4863614A (en) * | 1983-10-26 | 1989-09-05 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4929362A (en) * | 1983-10-26 | 1990-05-29 | Betz Laboratories, Inc. | Calcium phosphate scale control methods |
| US4895664A (en) * | 1983-10-26 | 1990-01-23 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4895916A (en) * | 1983-10-26 | 1990-01-23 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4868263A (en) * | 1983-10-26 | 1989-09-19 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
| US4929695A (en) * | 1983-10-26 | 1990-05-29 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4849129A (en) * | 1988-05-06 | 1989-07-18 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4895663A (en) * | 1986-05-16 | 1990-01-23 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| JP2507743B2 (en) * | 1987-06-10 | 1996-06-19 | 古河電気工業株式会社 | Copper alloy for flexible printing |
| EP0337694B1 (en) | 1988-04-11 | 1993-12-29 | Nippon Shokubai Co., Ltd. | Process for producing acid-type maleic acid polymer and water-treating agent and detergent additive containing said polymer |
| JPH1121586A (en) * | 1997-07-07 | 1999-01-26 | Asahi Denka Kogyo Kk | Detergent composition |
| US6451952B2 (en) | 2000-05-26 | 2002-09-17 | Nippon Shokubai Co., Ltd. | Production process for allyl ether-based polymer |
| CA2425618C (en) | 2002-04-17 | 2007-10-23 | Nippon Shokubai Co., Ltd. | Specific polymer-compounded detergent composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS587415A (en) * | 1981-07-07 | 1983-01-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | Novel water-soluble copolymer and its preparation |
-
1982
- 1982-02-26 JP JP2886382A patent/JPS58147412A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS587415A (en) * | 1981-07-07 | 1983-01-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | Novel water-soluble copolymer and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58147412A (en) | 1983-09-02 |
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