JPS61118404A - Production of low molecular-weight water-soluble polymer - Google Patents
Production of low molecular-weight water-soluble polymerInfo
- Publication number
- JPS61118404A JPS61118404A JP24144284A JP24144284A JPS61118404A JP S61118404 A JPS61118404 A JP S61118404A JP 24144284 A JP24144284 A JP 24144284A JP 24144284 A JP24144284 A JP 24144284A JP S61118404 A JPS61118404 A JP S61118404A
- Authority
- JP
- Japan
- Prior art keywords
- water
- group
- polymerization
- soluble
- salts
- 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.)
- Granted
Links
- 229920003169 water-soluble polymer Polymers 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- -1 mercapto compound Chemical class 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 7
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 6
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 25
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000002269 spontaneous effect Effects 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 abstract 1
- 150000003926 acrylamides Chemical class 0.000 abstract 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- CKSURTJJJBWBOU-UHFFFAOYSA-N 3-[(3-amino-3-imino-2-methylpropyl)diazenyl]-2-methylpropanimidamide;hydrochloride Chemical compound Cl.NC(=N)C(C)CN=NCC(C)C(N)=N CKSURTJJJBWBOU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Polymerisation Methods In General (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）
本発明はスケール抑制剤、顔料分散剤、金属イオン封鎖
剤、洗剤ビルダー、増粘剤、バインダーなど多くの用途
に有用な低分子量水溶性重合体の製法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a low molecular weight water-soluble polymer useful in many applications such as scale inhibitors, pigment dispersants, sequestrants, detergent builders, thickeners, and binders. Concerning the manufacturing method of coalescence.
従来より低分子量水溶性重合体が製造され、使用されて
いる。BACKGROUND OF THE INVENTION Low molecular weight water-soluble polymers have been produced and used.
低分子量水溶性重合体の代表的な製法としては、
■ １０〜２０％（重量％、以下同様）のモノマー濃度
で多量の重合開始剤を使用して重合させる方法
■ ９０〜１００℃の高温水中へ重合開始剤とともにモ
ノマーを滴下して重合させる方法
■ 連鎖移動剤としてオクチルメルカプタンやドデシル
メルカプタンを使用して重合させる方法
■ 七ツマー濃度５〜３０％でアクリル酸とチオグリコ
ール酸とを重合反応させたのち、過硫酸アンモニウムを
添加して重合を完結させる方法（米国特許第３６６５０
３５号明細書）■ 実質的に水不溶性のメルカプタンと
界面活性剤とを併用して七ツマ−を重合させる方法（特
開昭５７−２８１０５号公報）
などがあげられる。Typical manufacturing methods for low molecular weight water-soluble polymers include: ■ Polymerization using a large amount of polymerization initiator at a monomer concentration of 10 to 20% (wt%, same hereinafter) ■ In high temperature water at 90 to 100°C A method of polymerizing by dropping a monomer together with a polymerization initiator into a polymer. A method of polymerizing using octyl mercaptan or dodecyl mercaptan as a chain transfer agent. Afterwards, ammonium persulfate is added to complete the polymerization (U.S. Pat. No. 36,650).
(Specification No. 35) (1) A method of polymerizing nanatsumer using a combination of a substantially water-insoluble mercaptan and a surfactant (Japanese Unexamined Patent Publication No. 57-28105).
〔発明が解決しようとする問題点〕
低分子量水溶性重合体を■〜■の方法で製造しようとす
ると、つぎのような問題がある。すなわち、
■の方法では重合完結までに長時間を要し、高濃度の製
品がえられない
■の方法では操作が煩雑であり、生成ポリマーの重合度
に再現性かえられにくく、また製品が着色する
■の方法では製品ト濁りが生じ、透明なものがえられな
い
■の方法ではチオグリコール酸を加えた段階で自然重合
が進行し、重合反応をコントロールしがたく、ときには
暴走反応の危険がある上、高ｍ度製品をえようとすると
水の留去という付加的操作が必要となる
■の方法では純粋な形での水溶性重合体がえられない
などの問題がある。[Problems to be Solved by the Invention] When attempting to produce a low molecular weight water-soluble polymer by the methods (1) to (2), the following problems arise. In other words, method (2) takes a long time to complete the polymerization and does not produce a highly concentrated product.Method (2) requires complicated operations, is difficult to reproducibly change the degree of polymerization of the resulting polymer, and may result in colored products. In the method (■), the product becomes cloudy and a transparent product cannot be obtained.In the method (■), spontaneous polymerization progresses at the stage of adding thioglycolic acid, making it difficult to control the polymerization reaction, and sometimes there is a risk of a runaway reaction. In addition, in order to obtain a high-molecular weight product, the method (2) requires an additional operation of distilling off water, and there are problems such as the inability to obtain a water-soluble polymer in a pure form.
本発明は前記のごとき諸問題を解決するためになされた
ものであり、容易に分子量のコントロールが行なえ、自
然重合の危険がなく、操作が簡単で、着色およびにごり
のない高濃度製品をうる低分子量水溶性重合体の製法を
開発することを目的とするものである。The present invention was made in order to solve the above-mentioned problems, and it is possible to easily control the molecular weight, eliminate the risk of spontaneous polymerization, be easy to operate, and produce high-concentration products without coloring or clouding. The purpose of this research is to develop a method for producing high molecular weight water-soluble polymers.
本発明は、アクリルアミド、メタクリルアミド、ヒドロ
キシエチルアクリレート、ヒドロキシエチルメタクリレ
ート、ヒドロキシプロピルアクリレート、ヒドロキシプ
ロピルメタクリレート、アクリル酸、メタクリル酸、ア
クリル酸の１価金属塩、アミン塩、アンモニウム塩およ
びメタクリル酸の１価金属塩、アミン塩、アンモニウム
塩よりなる群からえらばれた水溶性モノマーの１種以上
を重合して低分子量水溶性重合体をうる際に、分子中に
１〜４囮のメルカプト基ならびにカルボキシル基、カル
ボキシル基がエステルに変換された基および水酸基より
なる群からえらばれた１種または２種の基を合計１〜４
個有しており、かつカルボキシル基を形成する炭素原子
を除く炭素原子の数が該メルカプト基当り２〜４個のメ
ルカプト化合物（以下、本発明に用いるメルカプト化合
物という）の存在下で重合させることを特徴とする低分
子量水溶性重合体の製造方法に関する。The present invention relates to acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, monovalent metal salts of acrylic acid, amine salts, ammonium salts, and monovalent metal salts of methacrylic acid. When polymerizing one or more water-soluble monomers selected from the group consisting of metal salts, amine salts, and ammonium salts to obtain a low molecular weight water-soluble polymer, 1 to 4 decoy mercapto groups and carboxyl groups are added to the molecule. , a total of 1 to 4 of one or two groups selected from the group consisting of a group in which a carboxyl group is converted to an ester and a hydroxyl group.
Polymerization in the presence of a mercapto compound (hereinafter referred to as a mercapto compound used in the present invention) having 2 to 4 carbon atoms per mercapto group, excluding carbon atoms forming a carboxyl group. The present invention relates to a method for producing a low molecular weight water-soluble polymer characterized by:
本発明においては、アクリルアミド、メタクリルアミド
、ヒドロキシエチルアクリレート、ヒドロキシエチルメ
タクリレート、ヒドロキシプロピルアクリレート、ヒド
ロキシプロピルメタクリレート、アクリル酸、メタクリ
ル酸、アクリル酸またはメタクリル酸のＮａ、になどの
１価の金属塩、アミン塩、アンモニウム塩などからなる
水溶性モノマーの１種以上を重合して水溶性重合体がえ
られる。In the present invention, monovalent metal salts such as acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, Na of acrylic acid or methacrylic acid, amines, etc. A water-soluble polymer can be obtained by polymerizing one or more water-soluble monomers such as salts and ammonium salts.
前記水溶性モノマーの重合は、本発明に用いるメルカプ
ト化合物の存在下で重合開始剤を添加することにより行
なわれる。The water-soluble monomer is polymerized by adding a polymerization initiator in the presence of the mercapto compound used in the present invention.
本発明に用いるメルカプト化合物は、分子中に１〜４１
Ｎのメルカプト基ならびにカルボキシル基、カルボキシ
ル
ル、プロパツール、エチレングリコール、プロピレング
リコール、トリメチロールプロパン、ペンタエリスリト
ールなどのアルコール成分とエステルになった基および
水酸基よりなる群からえらばれた１１または２種の基を
合計１〜４個有しており、かつカルボキシル基を形成す
る炭素原子を除く炭素原子の数が該メルカプト基当り２
〜４個の炭素原子を有するメルカプト化合物であり、こ
のようなメルカプト化合物を使用することにより、自然
重合の危険もなく、高濃度で、簡単な操作により重合さ
せることができる。前記メルカプト化合物の具体例とし
ては、β−メルカプドブコピオン酸
（ＨＳ−ＣＬ −Ｃ）ｌａ −ＣＯＯＩＩ ｉ、α−メ
ルカプトプロピオン酸（ＣＨｓ−Ｃｌ−ＣＯＯＨ）、
Ｈ
Ｔ − メ７Ｌ／ トカプト酪１！！ （ＨＳ−ＣＨ２
−ＣＨ２ −ＣＨ２’−ＣＯＯ旧、トリメチロールプ
ロパントリーβ−チオプロピオネート（Ｃ２ ＨｓＣ（
（Ｊｌｚ ＯＣＯＣＨｚＣｔ１２ＳＨ） ３ ）、ペン
タエリスリトールテトラ−β−チオプロピオネート（Ｃ
（Ｃ）（２ ０ＣＯＣ）ｂ ＣＨ２ ８Ｎ ） ａ ）
、トリメチロールプロパントリチオグリコレート（Ｃ２
ＨＳ Ｃ（ＣＬ ＣＯＯＣＨ２ Ｓｌｌ ） ３ ）
、ペンタエリスリトールテトラチオグリコレート（Ｃ（
ＣＨ２０ＣＯＣ）１２ＳＨ） ａ ）、エチレングリコ
ールジチオグリコレートチオグリコール酸メチル（ＨＳ
−ＣＨｚ −ＣＯＯＣＨ３ ）、２−メルカプトエタノ
ール（ＨＳ−ＣＨ２ ＣＨ２−ＯＨ）、３−メルカプト
−ｎ−プロパツール
（ＨＳ−ＣＨｚ −Ｃｆｂ −ＣＨ２ ０Ｈ ）、など
があげられるが、これらに限定されるものではない。The mercapto compound used in the present invention has 1 to 41 atoms in the molecule.
11 or 2 types selected from the group consisting of a mercapto group of N, a group esterified with an alcohol component such as carboxyl group, carboxyl group, propatool, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, and a hydroxyl group. has a total of 1 to 4 groups, and the number of carbon atoms excluding carbon atoms forming a carboxyl group is 2 per mercapto group.
It is a mercapto compound having ~4 carbon atoms, and by using such a mercapto compound, it can be polymerized at high concentration and by simple operations without the risk of spontaneous polymerization. Specific examples of the mercapto compound include β-mercaptobucopionic acid (HS-CL-C)la-COOIIi, α-mercaptopropionic acid (CHs-Cl-COOH), HT-me7L/tocaptobutyric acid 1! ! (HS-CH2
-CH2 -CH2'-COO former, trimethylolpropane tri-β-thiopropionate (C2 HsC(
(Jlz OCOCHzCt12SH) 3 ), pentaerythritol tetra-β-thiopropionate (C
(C) (2 0 COC) b CH2 8N ) a )
, trimethylolpropane trithioglycolate (C2
HS C (CL COOCH2 Sll) 3)
, pentaerythritol tetrathioglycolate (C(
CH20COC)12SH) a), ethylene glycol dithioglycolate methyl thioglycolate (HS
Examples include, but are not limited to, isn't it.
本発明においては前記のごときメルカプト化合物が水溶
性モノマーに対して好ましくは０、０５〜２５％、さら
に好ましくは０．１〜２０％存在する状態で重合せしめ
られる。このような状態で水溶性モノマーを重合せしめ
ることにより、目的とする重合体の分子量＠ ３０００
〜ｓｏｏｏｏｏ、好ましくは５０００〜３０００００の
範囲に調整することができる。In the present invention, the mercapto compound as described above is polymerized in the presence of preferably 0.05 to 25%, more preferably 0.1 to 20%, based on the water-soluble monomer. By polymerizing water-soluble monomers in such a state, the molecular weight of the desired polymer @ 3000
~ sooooo, preferably in the range of 5000 to 300000.
・本発明における水溶性モノマーの濃度は３０〜６０％
、好ましくは３５〜５０％である。前記濃度が３０％未
満でも重合は可能であるが、重合完結に時間がかかる。・The concentration of water-soluble monomer in the present invention is 30 to 60%
, preferably 35 to 50%. Polymerization is possible even if the concentration is less than 30%, but it takes time to complete the polymerization.
また前記濃度が６０％をこえると、えられる重合体は粘
稠で流動性がなくなり、重合体の取扱いが困難になる。When the concentration exceeds 60%, the resulting polymer becomes viscous and has no fluidity, making it difficult to handle the polymer.
本発明に用いる重合開始剤とは、熱または酸化還元系で
遊１基を発生する重合開始剤であればとくに限定なく使
用することができるが、水溶性の重合開始剤であること
が好ましい。このような重合開始剤の具体例としては、
たとえば過硫酸カリウム、過硫酸アンモニウム、過酸化
水素、ｔ−ブチルハイドロパーオキサイド、２、２°−
アゾビス（２−アミジノプロパン）・塩酸塩または酢酸
塩、２，２°−アゾビス（２．４−ジメチルバレロニト
リル）などがあげられる。The polymerization initiator used in the present invention can be used without particular limitation as long as it is a polymerization initiator that generates a free radical under heat or redox system, but it is preferably a water-soluble polymerization initiator. Specific examples of such polymerization initiators include:
For example, potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, 2,2°-
Examples include azobis(2-amidinopropane) hydrochloride or acetate, 2,2°-azobis(2,4-dimethylvaleronitrile), and the like.
前記重合開始剤の添加量や添加方法にはとくに限定はな
く、水溶性モノマーに対して通常使用される、たとえば
０．００ＳＨ２％程度の濃度になるように、冷却による
重合熱の除去を行ないつつ、重合温度を３５〜９５℃程
度の範囲に保持するように断続的または連続的に添加す
ればよい。There are no particular limitations on the amount or method of adding the polymerization initiator, and the polymerization initiator is added while removing the heat of polymerization by cooling so that the concentration is, for example, about 0.00SH2%, which is normally used for water-soluble monomers. , may be added intermittently or continuously so as to maintain the polymerization temperature in the range of about 35 to 95°C.
前記添加量が０． ００５％未満になると重合率が充分
でなくなりがちであり、２％をこえると経済的でなくな
る。The amount added is 0. If it is less than 0.005%, the polymerization rate tends to be insufficient, and if it exceeds 2%, it becomes uneconomical.
一般に重合は、着色を防止する、酸素を除去して重合を
円滑に進行させるなどの目的で、チッ素雰囲気中で行な
われる。Generally, polymerization is carried out in a nitrogen atmosphere for the purposes of preventing coloration and removing oxygen to allow polymerization to proceed smoothly.
以上説明したような方法により、分子量が３０００〜５
ｏｏｏｏｏの所定の範囲に調整された着色およびにごり
のない水溶性重合体が３０〜６０％という高濃度で、自
然重合の危険もなく、簡単な操作でうろことができる。By the method explained above, the molecular weight is 3000-5.
The water-soluble polymer, which is adjusted to a predetermined range of oooooo and has no coloration or cloudiness, can be dispersed in a high concentration of 30 to 60% with simple operations without the risk of spontaneous polymerization.
このようにしてえられた水溶性重合体の１Ｍ食塩水中３
０℃で測定した極限粘度数は０．０２〜３ｄｌ／ｇを示
す。3 of the thus obtained water-soluble polymer in 1M saline.
The intrinsic viscosity measured at 0°C is 0.02 to 3 dl/g.
なお本川ＩＱ！にいう分子量は、ポリエチレンオキサイ
ドを標準物質として用いたゲルパーミェーションクロマ
トグラフィー（ＧＰＣ）により測定した分子量である。Furthermore, Honkawa IQ! The molecular weight referred to in 2 is the molecular weight measured by gel permeation chromatography (GPC) using polyethylene oxide as a standard substance.
つぎに本発明の方法を実施例にもとづき説明する。Next, the method of the present invention will be explained based on examples.
実施例１
撹拌棒、温度計、チッ素導入管、滴下漏斗、還流冷却器
を備えた１ｊの５つロフラスコに、水２５０９、アクリ
ルアミド２５０ｇおよび２−メルカプトエタノール２０
ｇを仕込み、均一に溶解した。そののちチッ素導入管を
通じてチッ素ガスを吹き込み、系内の酸素を除去した。Example 1 In a 1J 5-Low flask equipped with a stirring bar, thermometer, nitrogen inlet tube, dropping funnel, and reflux condenser, 2509 g of water, 250 g of acrylamide, and 20 g of 2-mercaptoethanol were added.
g was added and uniformly dissolved. Thereafter, nitrogen gas was blown into the system through the nitrogen introduction tube to remove oxygen from the system.
ついで水浴により温度を４０℃に調温したのち、過硫酸
アンモニウムの１％水溶液３０ｍの滴下を開始した。Next, the temperature was adjusted to 40° C. using a water bath, and then dropwise addition of 30 m of a 1% aqueous solution of ammonium persulfate was started.
滴下開始後しばらくすると発熱が認められ、温度が６５
℃に上昇した。水浴または水浴による冷却を行ない、温
度が６５±３℃を維持するように重合開始剤溶液の滴下
速度と冷却とを調節しながら、３時間重合反応を継続し
た。After a while after starting dropping, heat generation was observed, and the temperature reached 65.
The temperature rose to ℃. The polymerization reaction was continued for 3 hours while cooling with a water bath or a water bath and controlling the dropwise addition rate of the polymerization initiator solution and cooling so that the temperature was maintained at 65±3°C.
えられた水溶性重合体のＧＰＣによる分子量測定値は、
１２００Ｇであった。また該水溶性重合体の１Ｍ食塩水
中３０℃での極限粘度数は０．１１旧／Ｊであった。The molecular weight measured by GPC of the obtained water-soluble polymer is:
It was 1200G. Further, the intrinsic viscosity of the water-soluble polymer in 1M saline at 30° C. was 0.11/J.
実施例２
実施例１で用いたのと同様の装置に、水２７０９、メタ
クリルアミド１１７０９、アクリル酸ソーダ１６ＧＳＦ
およびチオグリセリン６６ｇを仕込み、均一に溶解した
。そののちチッ素ガスを吹き込み系内の酸素を除去した
。ついで水浴により温度を５０℃に調温したのち、１０
％過酸化水素水３〇−の滴下を開始した。滴下開始後し
ばらくすると発熱が認められ、温度が８０℃に上昇した
。水浴または水浴による冷却を行ない、温度が８０±５
℃を維持するように重合開始剤溶液の滴下速度と冷却と
を調節しながら４時間重合反応を継続した。Example 2 In a device similar to that used in Example 1, 2709 water, 11709 methacrylamide, and 16 GSF of sodium acrylate were added.
and 66 g of thioglycerin were charged and uniformly dissolved. Thereafter, nitrogen gas was blown into the system to remove oxygen from the system. Next, the temperature was adjusted to 50°C in a water bath, and then
Dropwise addition of 30% hydrogen peroxide solution was started. A while after the start of dropping, heat generation was observed, and the temperature rose to 80°C. Cool with a water bath or a water bath until the temperature reaches 80±5.
The polymerization reaction was continued for 4 hours while controlling the dropping rate of the polymerization initiator solution and cooling so as to maintain the temperature.
えられた水溶性重合体のＧＰＣによる分子量測定値は、
５０００であった。また該水溶性重合体の１Ｎ食塩水中
３０℃で°の極限粘度数は０．０４旧／ｇであった。The molecular weight measured by GPC of the obtained water-soluble polymer is:
It was 5000. Further, the intrinsic viscosity of the water-soluble polymer in 1N saline at 30° C. was 0.04/g.
実施例３
撹拌棒、温度計、チッ素導入管、滴下漏斗、還流冷却器
を備えた１Ｎの５つロフラスコに、水２５０ｇ、アクリ
ル酸１５０９およびβ−メルカプトプロピオン＠ ｏ、
１ｓｇを仕込み、均一に溶解した。そののちチッ素導入
管を通じてチッ素ガスを吹き込み系内の酸素を除去した
。ついで水浴により温度を４０℃に調温したのち、２，
２゛−アゾビス（２−アミジノプロパン）・塩酸塩のｏ
、５％水溶液３０Ｍ１の滴下を開始した。滴下開始後し
ばらくすると発熱が認められ、温度が６５℃に上昇した
。水浴または水浴による冷却を行ない、温度が６５±３
℃を維持するように重合開始剤溶液の滴下速度と冷却と
を調節しながら、３時間重合反応を継続した。Example 3 In a 1N 5-bottle flask equipped with a stirring bar, thermometer, nitrogen inlet tube, addition funnel, and reflux condenser, 250 g of water, acrylic acid 1509, and β-mercaptopropion @ o,
1 sg was charged and uniformly dissolved. Thereafter, nitrogen gas was blown into the system through the nitrogen introduction tube to remove oxygen from the system. Then, after adjusting the temperature to 40℃ in a water bath, 2.
2゛-azobis(2-amidinopropane) hydrochloride o
, the dropwise addition of 30M1 of a 5% aqueous solution was started. A while after the start of dropping, heat generation was observed and the temperature rose to 65°C. Cooling with a water bath or water bath until the temperature is 65±3
The polymerization reaction was continued for 3 hours while controlling the dropping rate of the polymerization initiator solution and cooling so as to maintain the temperature.
えられた水溶性重合体のＧＰＣによる分子量測定値は、
２５０００Ｇであった。また該水溶性重合体の１Ｍ食塩
水中３０℃での極限粘度数は１．６ｄｌ／ｇであった。The molecular weight measured by GPC of the obtained water-soluble polymer is:
It was 25,000G. Further, the intrinsic viscosity of the water-soluble polymer in 1M saline at 30°C was 1.6 dl/g.
（発明の効果）
本発明の方法を用いると、容易に分子量のコントロール
が行なえ、自然重合の危険がなく、操作が簡単で、着色
およびにこりのない高濃度な低分子量水溶性重合体かえ
られる。(Effects of the Invention) By using the method of the present invention, the molecular weight can be easily controlled, there is no risk of spontaneous polymerization, the operation is simple, and a highly concentrated low molecular weight water-soluble polymer without coloring or staining can be obtained.
手続補正書（自発）
昭和５９年１２月１３日
１事件の表示
昭和５９年特許願第２４１４４２号
２発明の名称
低分子量水溶性重合体の製法
３補正をする者
事件との関係 特許出願人
住 所 京都市下京区西七条東久保町５５番地名 称
（３５０）第−工業製薬株式会社代表者三浦隆彦
４代理人 〒５４０
５補正の対象
（１）明ｉｌｌ書の「特許請求の範囲」の欄６補正の内
容
（１）明細書の「特許請求の範囲」を別Ｍ１［補正され
た特許請求の範囲」のとおり補正する。Procedural amendment (voluntary) December 13, 1980 1. Indication of the case 1988 Patent Application No. 241442 2. Name of the invention 3. Process for producing low molecular weight water-soluble polymers 3. Relationship with the case Patent applicant residence Address: 55 Nishi-shichi-jo Higashikubo-cho, Shimogyo-ku, Kyoto City Name (350) Dai-Kogyo Seiyaku Co., Ltd. Representative Takahiko Miura 4 Agent Address: 540 5. Subject of amendment (1) “Scope of Claims” column of Letter of Ill. 6 Contents of amendment (1) The "Claims" of the specification will be amended as shown in Separate M1 [Amended Scope of Claims].
７添付四類の目録
（１）補正された特許請求の範囲 １通
［１アクリルアミド、メタクリルアミド、ヒドロキシエ
チルアクリレート、ヒドロキシエチルメタクリレート、
ヒドロキシプロピルアクリレート、ヒドロキシプロピル
メタクリレート、アクリル酸、メタクリル酸、アクリル
酸の１価金属塩、アミン塩、アンモニウム塩およびメタ
クリル酸の１価金属塩、アミン塩、アン［ニウム塩−よ
りなる群からえらばれた水溶性七ツマ−の１種以上を重
合して低分子山水溶性重合体をうる際に、分子中に１〜
４個のメルカプト基ならびにカルボキシル基、カルボキ
シル基がエステルに変換された基および水酸基よりなる
群からえらばれた１種または２種の基を合計１〜４個有
しており、かつカルボキシル基を形成する炭素原子を除
く炭素原子の数が該メルカプト配当り２〜４個のメルカ
プト化合物の存在下で重合させることを特徴とする低分
子１水溶性重合体の製法。7 Attached list of four categories (1) Amended claims 1 copy [1 Acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate,
Hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, monovalent metal salts of acrylic acid, amine salts, ammonium salts, and monovalent metal salts of methacrylic acid, amine salts, an[nium salts] When one or more types of water-soluble hexamers are polymerized to obtain a low-molecular-weight water-soluble polymer, one to
It has a total of 1 to 4 groups selected from the group consisting of 4 mercapto groups, a carboxyl group, a group in which a carboxyl group is converted to an ester, and a hydroxyl group, and forms a carboxyl group. 1. A method for producing a low-molecular-weight mono-water-soluble polymer, which is characterized in that the polymerization is carried out in the presence of a mercapto compound having 2 to 4 carbon atoms, excluding the carbon atoms mentioned above.
２ 水溶性モノマーがアクリルアミドである特許請求の
範囲第１項記載の製法。2. The manufacturing method according to claim 1, wherein the water-soluble monomer is acrylamide.
３ 水溶性七ツマ−がアクリル酸である特許請求の範囲
第１項記載の製法。3. The manufacturing method according to claim 1, wherein the water-soluble hexamer is acrylic acid.
４ 水溶性七ツマ−がアクリルアミドであり、メルカプ
１−化合物が２−メルカプトエタノールまたはチオグリ
セリンである特許請求の範囲第１項記載の製法。4. The method according to claim 1, wherein the water-soluble hexamer is acrylamide and the mercap-1 compound is 2-mercaptoethanol or thioglycerin.
５ 水溶性モノマーがアクリル酸であり、メルカプ１−
化合物がβ−メルカプトプロピオン酸である特許請求の
範囲第１項記載の製法。ｊ以 上5 The water-soluble monomer is acrylic acid, and mercap 1-
The method according to claim 1, wherein the compound is β-mercaptopropionic acid. J or more
Claims (1)
チルアクリレート、ヒドロキシエチルメタクリレート、
ヒドロキシプロピルアクリレート、ヒドロキシプロピル
メタクリレート、アクリル酸、メタクリル酸、アクリル
酸の１価金属塩、アミン塩、アンモニウム塩およびメタ
クリル酸の１価金属塩、アミン塩、アンモニウム塩およ
びメタクリル酸の１価金属塩、アミン塩、アンモニウム
塩よりなる群からえらばれた水溶性モノマーの１種以上
を重合して低分子量水溶性重合体をうる際に、分子中に
１〜４個のメルカプト基ならびにカルボキシル基、カル
ボキシル基がエステルに変換された基および水酸基より
なる群からえらばれた１種または２種の基を合計１〜４
個有しており、かつカルボキシル基を形成する炭素原子
を除く炭素原子の数が該メルカプト基当り２〜４個のメ
ルカプト化合物の存在下で重合させることを特徴とする
低分子量水溶性重合体の製法。 ２ 水溶性モノマーがアクリルアミドである特許請求の
範囲第１項記載の製法。 ３ 水溶性モノマーがアクリル酸である特許請求の範囲
第１項記載の製法。 ４ 水溶性モノマーがアクリルアミドであり、メルカプ
ト化合物が２−メルカプトエタノールまたはチオグリセ
リンである特許請求の範囲第１項記載の製法。 ５ 水溶性モノマーがアクリル酸であり、メルカプト化
合物がβ−メルカプトプロピオン酸である特許請求の範
囲第１項記載の製法。[Claims] 1. Acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate,
Hydroxypropyl acrylate, hydroxypropyl methacrylate, acrylic acid, methacrylic acid, monovalent metal salts of acrylic acid, amine salts, ammonium salts and monovalent metal salts of methacrylic acid, amine salts, ammonium salts and monovalent metal salts of methacrylic acid, When polymerizing one or more water-soluble monomers selected from the group consisting of amine salts and ammonium salts to obtain a low molecular weight water-soluble polymer, 1 to 4 mercapto groups, carboxyl groups, and carboxyl groups are added to the molecule. A total of 1 to 4 groups of one or two selected from the group consisting of a group in which is converted into an ester and a hydroxyl group
The low molecular weight water-soluble polymer is polymerized in the presence of a mercapto compound having 2 to 4 carbon atoms per mercapto group, excluding carbon atoms forming a carboxyl group. Manufacturing method. 2. The manufacturing method according to claim 1, wherein the water-soluble monomer is acrylamide. 3. The manufacturing method according to claim 1, wherein the water-soluble monomer is acrylic acid. 4. The production method according to claim 1, wherein the water-soluble monomer is acrylamide and the mercapto compound is 2-mercaptoethanol or thioglycerin. 5. The manufacturing method according to claim 1, wherein the water-soluble monomer is acrylic acid and the mercapto compound is β-mercaptopropionic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24144284A JPS61118404A (en) | 1984-11-15 | 1984-11-15 | Production of low molecular-weight water-soluble polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24144284A JPS61118404A (en) | 1984-11-15 | 1984-11-15 | Production of low molecular-weight water-soluble polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61118404A true JPS61118404A (en) | 1986-06-05 |
| JPH0510362B2 JPH0510362B2 (en) | 1993-02-09 |
Family
ID=17074367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24144284A Granted JPS61118404A (en) | 1984-11-15 | 1984-11-15 | Production of low molecular-weight water-soluble polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61118404A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753608A (en) * | 1993-08-16 | 1995-02-28 | Showa Highpolymer Co Ltd | Emulsion-type adhesive agent and its production |
| WO1998016561A1 (en) * | 1996-10-11 | 1998-04-23 | Nippon Carbide Kogyo Kabushiki Kaisha | Polymer obtained by emulsion polymerization method |
| WO2001025287A1 (en) * | 1999-10-01 | 2001-04-12 | Ecole Polytechnique Federale De Lausanne | Affinity macroligands |
| JP2008127461A (en) * | 2006-11-21 | 2008-06-05 | Fujifilm Corp | Positive type photosensitive composition, polymer compound used for positive type photosensitive composition, method for producing the same, and method for forming pattern by using positive type photosensitive composition |
| JP2011202040A (en) * | 2010-03-26 | 2011-10-13 | Toyo Ink Sc Holdings Co Ltd | Vinyl polymer for dispersing inorganic oxide and dispersion of conductive inorganic oxide including the same |
| JP2016117960A (en) * | 2014-12-18 | 2016-06-30 | 株式会社ミマキエンジニアリング | Pretreatment agent for dye printing and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5778407A (en) * | 1980-09-08 | 1982-05-17 | Rohm & Haas | Manufacture of acrylamide polymer |
-
1984
- 1984-11-15 JP JP24144284A patent/JPS61118404A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5778407A (en) * | 1980-09-08 | 1982-05-17 | Rohm & Haas | Manufacture of acrylamide polymer |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753608A (en) * | 1993-08-16 | 1995-02-28 | Showa Highpolymer Co Ltd | Emulsion-type adhesive agent and its production |
| WO1998016561A1 (en) * | 1996-10-11 | 1998-04-23 | Nippon Carbide Kogyo Kabushiki Kaisha | Polymer obtained by emulsion polymerization method |
| US6197907B1 (en) | 1996-10-11 | 2001-03-06 | Nippon Carbide Kogyo Kabushiki Kaisha | Polymer obtained by emulsion polymerization method |
| JP3390991B2 (en) * | 1996-10-11 | 2003-03-31 | 日本カーバイド工業株式会社 | Polymer obtained by emulsion polymerization method |
| WO2001025287A1 (en) * | 1999-10-01 | 2001-04-12 | Ecole Polytechnique Federale De Lausanne | Affinity macroligands |
| JP2008127461A (en) * | 2006-11-21 | 2008-06-05 | Fujifilm Corp | Positive type photosensitive composition, polymer compound used for positive type photosensitive composition, method for producing the same, and method for forming pattern by using positive type photosensitive composition |
| JP2011202040A (en) * | 2010-03-26 | 2011-10-13 | Toyo Ink Sc Holdings Co Ltd | Vinyl polymer for dispersing inorganic oxide and dispersion of conductive inorganic oxide including the same |
| JP2016117960A (en) * | 2014-12-18 | 2016-06-30 | 株式会社ミマキエンジニアリング | Pretreatment agent for dye printing and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0510362B2 (en) | 1993-02-09 |
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