JPH01254718A - Production of styrenesulfonated product-maleic acid copolymer - Google Patents
Production of styrenesulfonated product-maleic acid copolymerInfo
- Publication number
- JPH01254718A JPH01254718A JP63081401A JP8140188A JPH01254718A JP H01254718 A JPH01254718 A JP H01254718A JP 63081401 A JP63081401 A JP 63081401A JP 8140188 A JP8140188 A JP 8140188A JP H01254718 A JPH01254718 A JP H01254718A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- maleic acid
- formulas
- acid group
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 23
- 239000011976 maleic acid Substances 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 6
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004568 cement Substances 0.000 abstract description 4
- 239000004570 mortar (masonry) Substances 0.000 abstract description 4
- 230000000996 additive effect Effects 0.000 abstract description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000004342 Benzoyl peroxide Substances 0.000 abstract description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 abstract description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 abstract description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract description 2
- 229960003328 benzoyl peroxide Drugs 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal carboxylic acid Chemical class 0.000 description 4
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 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
- 239000000843 powder Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- JBJWASZNUJCEKT-UHFFFAOYSA-M sodium;hydroxide;hydrate Chemical compound O.[OH-].[Na+] JBJWASZNUJCEKT-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はスチレンスルホン化物−マレイン酸共重合体の
製造方法に関する。この共重合体は、セメントペースト
、モルタル、コンクリート等の添加削として広範囲の用
途に応用可能な樹脂である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a styrene sulfonate-maleic acid copolymer. This copolymer is a resin that can be used in a wide range of applications as an additive to cement paste, mortar, concrete, etc.
［従来の技術］
従来スチレン−マレイン酸共重合体のスルホン化物を得
る方法としては、例えば特開昭６１−５３３０５号公報
に記載のようにスチレン−マレイン酸共重合体をクロル
硫酸を用いて製造する方法が知られている。[Prior Art] Conventionally, as a method for obtaining a sulfonated product of a styrene-maleic acid copolymer, a styrene-maleic acid copolymer is produced using chlorosulfuric acid as described in JP-A No. 61-53305. There are known ways to do this.
また、スチレンスルホン酸ナトリウムとマレイン酸とを
共重合体させることにより製造する方法も知られている
。Also known is a method of producing by copolymerizing sodium styrene sulfonate and maleic acid.
［発明が解決しようとする課題］
しかしながら前者の方法ではクロル硫酸のような危険な
試薬を用いなければならず、したがって安全性、設備面
での問題等工業化には不利である。[Problems to be Solved by the Invention] However, the former method requires the use of dangerous reagents such as chlorosulfuric acid, and is therefore disadvantageous for industrialization, such as safety and equipment problems.
また後者の方法では、スチレンスルホン酸ナトリウム対
マレイン酸のモル比を１：９のマレイン酸大過剰に仕込
んでも共重合体中にマレイン酸の繰返し単位は、３３モ
ル％しか含有させることができず、例えば無機質との親
和性向上をカルボン酸基数の増加によりはかることがで
きなかった。したがって現在まで高マレイン酸含有率の
スチレンスルホン化物−マレイン酸共重合体を製造する
方法はいずれも工業的な製造方法としては安全性や原料
のロス等の問題があった。In addition, in the latter method, even if the molar ratio of sodium styrene sulfonate to maleic acid is 1:9, which is a large excess of maleic acid, only 33 mol% of maleic acid repeating units can be contained in the copolymer. For example, it has not been possible to improve the affinity with inorganic substances by increasing the number of carboxylic acid groups. Therefore, until now, all methods for producing styrene sulfonated product-maleic acid copolymers with a high maleic acid content have had problems such as safety and loss of raw materials as industrial production methods.
［課題を解決するための手段］
本発明者らは、上記問題点を解決するために鋭意努力し
た結果、本発明を完成した。[Means for Solving the Problems] The present inventors have completed the present invention as a result of diligent efforts to solve the above problems.
即ち、本発明は、下記一般式（Ｉ）及び（ＩＩ）（Ｘは
水素、アルカリ金属又はアンモニウム基を表す）
（Ｙは水素又はアルカリ金属を表す）
で示される繰返し単位よりなるスチレンスルホン化物−
マレイン酸共重合体を製造するにあたり、下記一般式（
ＩＩＩ）
０３Ｘ
（Ｘはアルカリ金属又はアンモニウム基を表す）で示さ
れるスチレンスルホン酸塩と無水マレイン酸とをラジカ
ル開始剤の存在下、含水溶媒中で反応させ、必要に応じ
てスルホン酸塩基をスルホン酸基に、カルボン酸基をカ
ルボン酸アルカリ金属塩基に転換させることを特徴とす
るスチレンスルホン化物−マレイン酸共重合体の製造方
法に関する。That is, the present invention provides styrene sulfonated compounds comprising repeating units represented by the following general formulas (I) and (II) (X represents hydrogen, an alkali metal, or an ammonium group) (Y represents hydrogen or an alkali metal).
In producing the maleic acid copolymer, the following general formula (
III) A styrene sulfonate represented by 03X (X represents an alkali metal or an ammonium group) and maleic anhydride are reacted in a water-containing solvent in the presence of a radical initiator, and if necessary, the sulfonate group is converted into a sulfonate. The present invention relates to a method for producing a styrene sulfonate-maleic acid copolymer, which comprises converting a carboxylic acid group into an alkali metal carboxylic acid base.
本発明のスチレンスルホン化物−マレイン酸共重合体に
あっては式（Ｉ）の繰り返し単位を１個又位が複数個適
宜に直鎖状に連結して成る連結体とが互いに無秩序に又
は秩序立って直線状に連結して構成されている。In the styrene sulfonated product-maleic acid copolymer of the present invention, the repeating unit of formula (I) is formed by connecting one or more repeating units in a linear chain as appropriate, and the repeating units are arranged in a disordered or ordered manner. It is constructed by standing and connecting in a straight line.
スチレンスルホン化物−マレイン酸共重合体において、
各繰返し単位（Ｉ＞及び（ＩＩ＞の繰返し単位数をそれ
ぞれに、１とすると、本発明によれば０．１≦に／（ｋ
＋１）≦０．９の関係を満足する共重合体を得ることが
できる。In the styrene sulfonate-maleic acid copolymer,
If the number of repeating units of each repeating unit (I> and (II>) is 1, then according to the present invention, 0.1≦/(k
A copolymer satisfying the relationship +1)≦0.9 can be obtained.
本発明で用いるスチレンスルホン酸塩（Ｉ［［）の陽イ
オンとしては、ナトリウムイオン、カリウムイオンのア
ルカリ金属イオンやアンモニウムイオンをあげることが
できる。Examples of the cations of the styrene sulfonate (I[[) used in the present invention include alkali metal ions such as sodium ions and potassium ions, and ammonium ions.
本発明で用いられる溶媒としては、１，４−ジオキサン
、ジメチルスルホキシド、ジメチルホルムアミド、Ｎ−
メチルピロリドン、テトラハイドロフラン等水との相溶
性があるものであれば特に制限はない。Solvents used in the present invention include 1,4-dioxane, dimethyl sulfoxide, dimethylformamide, N-
There is no particular restriction as long as it is compatible with water, such as methylpyrrolidone and tetrahydrofuran.
溶媒中の水の含有量は使用する無水マレイン酸の当量以
上が好ましい。水の含有量が使用する無水マレイン酸の
当量未満であると、無水マレイン酸がマレイン酸に加水
分解されないことがある。The content of water in the solvent is preferably equal to or greater than the equivalent amount of maleic anhydride used. If the water content is less than the equivalent amount of maleic anhydride used, maleic anhydride may not be hydrolyzed to maleic acid.
本発明で用いられる重合開始剤としては過硫酸アンモニ
ウム、過硫酸カリウム等の過硫酸塩、アゾビスイソブチ
ロニトリル、アゾビスイソバレロニトリル等のアゾ化合
物、過酸化ベンゾイル、１−ブチルハイドロパーオキサ
イド等の過酸化物などラジカル重合に使用される開始剤
であれば特に制限はない。Examples of the polymerization initiator used in the present invention include persulfates such as ammonium persulfate and potassium persulfate, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, benzoyl peroxide, and 1-butyl hydroperoxide. There is no particular restriction as long as it is an initiator used for radical polymerization such as peroxide.
また反応は０〜１５０℃の温度で０．５〜２４時間行う
のが好ましい。Further, the reaction is preferably carried out at a temperature of 0 to 150°C for 0.5 to 24 hours.
原料濃度は一般には５０〜５００ ｇ／β溶媒の範囲が
選択される。開始剤濃度は一般には０．００１ｇ〜０．
１ｇ／ｇ原料の範囲が選択される。The raw material concentration is generally selected within the range of 50 to 500 g/β solvent. The initiator concentration is generally between 0.001g and 0.01g.
A range of 1 g/g raw material is selected.
またこのようにして得られた共重合体はその後必要に応
じて常法によりスルホン酸塩基をスルホン酸基にカルボ
ン酸基をカルボン酸アルカリ金属塩基に置換することが
できる。Further, in the copolymer thus obtained, the sulfonic acid groups can be subsequently replaced with sulfonic acid groups and the carboxylic acid groups with carboxylic acid alkali metal bases by a conventional method, if necessary.
このようにして得られる式（Ｉ＞および式（ＩＩ）で表
されるスチレンスルホン化物−マレイン酸共重合体はセ
メントペースト、モルタル、コンクリート等の添加剤と
してだけでなく水溶性ポリマーとしてのその他店範囲の
用途に応用可能である。The styrene sulfonated compound-maleic acid copolymers represented by formulas (I> and (II)) thus obtained can be used not only as additives for cement paste, mortar, concrete, etc., but also as water-soluble polymers in other applications. Applicable to a range of applications.
［実施例］
以下に本発明の方法を実施例によって示すがこれらによ
って本発明が限定されるものではない。[Examples] The method of the present invention will be illustrated below by examples, but the present invention is not limited to these.
実施例１
撹拌機、温度計、窒素導入管、冷却器を備えた２００ｍ
１の４つロセパラブルフラスコにスチレンスルホン酸ナ
トリウム１０．３１ｇ（５０ｍｍｏり無水マレイン酸４
．９ｇ（５０ｍｍｏり１．４−ジオキサン５００１１を
入れ撹拌し７０゛Ｃに昇温したのち、過硫酸アンモニウ
ム０．３５ｇ （１５ｍｍｏりの５０ｍ１水溶液を加え
６時間加熱撹拌した。室温に冷却後大量のアセトンに投
入しポリマーを析出させろ過した０次いでポリマーを水
に溶解しアセトンに再沈澱させることにより精製し、１
００℃で２４時間真空乾燥し白色粉末１４．５ｇ（収率
８９％）を得た。Example 1 200m equipped with stirrer, thermometer, nitrogen inlet pipe, and cooler
10.31 g (50 mmol) of sodium styrene sulfonate in 4 separable flasks
．． After adding 9 g (50 mmol) of 1,4-dioxane 50011 and stirring and raising the temperature to 70°C, 50 ml of an aqueous solution of 0.35 g (15 mmol) of ammonium persulfate was added and stirred for 6 hours. After cooling to room temperature, a large amount of acetone was added. Then, the polymer was purified by dissolving it in water and reprecipitating it in acetone.
Vacuum drying was performed at 00° C. for 24 hours to obtain 14.5 g of white powder (yield: 89%).
赤外線吸収スペクトルを測定したところ３４５０ＣＩＩ
−ｉにカルボン酸性ＯＨ基、１７２０Ｃ１１１−１にカ
ルボン酸二量体、 １６５０ａｎ−’にカルボン酸陰イ
オン、１２００ａｎ−’にスルホン酸基、 ８３０ｃｘ
ｘ−’ニパラ置換フェニル基が観察された。When the infrared absorption spectrum was measured, it was 3450CII.
-i is a carboxylic acidic OH group, 1720C111-1 is a carboxylic acid dimer, 1650an-' is a carboxylic acid anion, 1200an-' is a sulfonic acid group, 830cx
An x-'nipara-substituted phenyl group was observed.
またＳ元素分析値はＳ：９．９％（９，９％）（括弧内
の数値はに／に＋β＝０．５の場合の理論値）でありこ
の共重合体はに／ （ｋ−１１！ ） ＝０．５である
ことがわかる。In addition, the S elemental analysis value is S: 9.9% (9.9%) (the numerical value in parentheses is the theoretical value when ni/ni+β=0.5), and this copolymer is ni/(k- 11!) = 0.5.
得られたポリマーを水に溶解して２５℃における極限粘
度［η］を測定したところ［η］＝０．５４ （ｄ、ｅ
／ｇ）−’であった。When the obtained polymer was dissolved in water and the intrinsic viscosity [η] at 25°C was measured, [η] = 0.54 (d, e
/g)-'.
ただし水溶性ポリマーの極限粘度は縦軸に−１１／２
（ηｓｐ／ｃ） 、横軸に（ｃ） を取り得られ
た直線をＣ＝Ｏに外挿することにより測定した。However, the intrinsic viscosity of the water-soluble polymer was measured by taking −11/2 (ηsp/c) on the vertical axis and (c) on the horizontal axis and extrapolating the obtained straight line to C=O.
またこのポリマーを３Ｎ ＮａＯＨ水に溶解させ、再
び大量のアセトンに投入させる事でスチレンスルホン化
物−マレイン酸共重合体のナトリウム塩を得ることがで
きた。Further, by dissolving this polymer in 3N NaOH water and pouring it into a large amount of acetone again, it was possible to obtain the sodium salt of the styrene sulfonate-maleic acid copolymer.
実施例２
スチレンスルホン酸ナトリウムを１６．５ｇ（８０ｍｍ
ｏβ）無水マレイン酸を２．０ｇ（２０ｍｍｏＲ）使用
した以外は実施例１と同様の方法で重合を行ない１６．
６ｇ（収率９０％）のポリマーを得な。Example 2 16.5 g (80 mm) of sodium styrene sulfonate
oβ) Polymerization was carried out in the same manner as in Example 1 except that 2.0 g (20 mmoR) of maleic anhydride was used. 16.
Obtain 6 g (90% yield) of polymer.
Ｓ元素分析値はＳ：１３％（１４％）（括弧内の数値は
に／に＋β＝０．８の場合の理論値）でありこの共重合
体はに／に−ｔＪ＝０．７６であることがわかる。得ら
れたポリマーを水に溶解して２５°Ｃにおける極限粘度
［ηコを測定したところ実施例３
スチレンスルホン酸ナトリウムを４，１ｇ＜２０ｍｍｏ
ｆ）無水マレイン酸を７．８ｇ（８０ｍｎｎｏり使用し
た以外は実施例１と同様の方法で重合を行ない９．３ｇ
（収率７８％）のポリマーを得た。The S elemental analysis value is S: 13% (14%) (the numerical value in parentheses is the theoretical value when Ni/ni+β=0.8), and this copolymer has Ni/ni−tJ=0.76. I understand that there is something. The obtained polymer was dissolved in water and the intrinsic viscosity [η] at 25°C was measured.
f) Polymerization was carried out in the same manner as in Example 1 except that 7.8 g (80 mnno) of maleic anhydride was used.
(yield 78%) of the polymer was obtained.
Ｓ元素分析値はＳ：５２％（４，８％）（括弧内の数値
はに／に＋！−０，２の場合の理論値）でありこの共重
合体はに／に＋！＝０．２２であることがわかる、得ら
れたポリマーを水に溶解して２５°Ｃにおける極限粘度
［η］を測定したところ［η］＝０．３０ （ｄＪ２／
ｇ）−’であった。The S elemental analysis value is S: 52% (4.8%) (the numerical value in parentheses is the theoretical value in the case of ni/ni+!-0,2), and this copolymer has ni/ni+! When the resulting polymer was dissolved in water and the intrinsic viscosity [η] at 25°C was measured, it was found that [η] = 0.30 (dJ2/
g)-'.
［発明の効果］
以上の説明で明らかなように本発明の製造法によりスチ
レンスルホン化物−マレイン酸共重合体は危険な試薬を
用いる事なく高マレイン酸含有のポリマーを高収率で合
成することができ、このポリマーはセメントペースト、
モルタル、コンクリート等の添加剤としての良質な素材
として広範囲の用途に応用可能である。[Effects of the Invention] As is clear from the above explanation, the styrene sulfonate-maleic acid copolymer can be synthesized in high yield with high maleic acid content without using dangerous reagents by the production method of the present invention. This polymer can be used as cement paste,
It can be used in a wide range of applications as a high-quality material as an additive for mortar, concrete, etc.
Claims (1)
マレイン酸共重合体を製造するにあたり、下記一般式（
III） ▲数式、化学式、表等があります▼（III） （Ｘはアルカリ金属又はアンモニウム基を表す） で示されるスチレンスルホン酸塩と無水マレイン酸とを
ラジカル開始剤の存在下、含水溶媒中で反応させ、必要
に応じてスルホン酸塩基をスルホン酸基に、カルボン酸
基をカルボン酸アルカリ金属塩基に転換させることを特
徴とするスチレンスルホン化物−マレイン酸共重合体の
製造方法。(1) General formulas (I) and (II) below ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (X represents hydrogen, alkali metal, or ammonium group) ▲There are mathematical formulas, chemical formulas, tables, etc.▼( II) Styrene sulfonated product consisting of repeating units represented by (Y represents hydrogen or alkali metal)
In producing the maleic acid copolymer, the following general formula (
III) ▲Mathematical formulas, chemical formulas, tables, etc.▼(III) (X represents an alkali metal or ammonium group) A styrene sulfonate and maleic anhydride are mixed in a water-containing solvent in the presence of a radical initiator. A method for producing a styrene sulfonate-maleic acid copolymer, which comprises reacting and optionally converting a sulfonic acid group into a sulfonic acid group and a carboxylic acid group into an alkali metal carboxylic acid group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63081401A JPH01254718A (en) | 1988-04-04 | 1988-04-04 | Production of styrenesulfonated product-maleic acid copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63081401A JPH01254718A (en) | 1988-04-04 | 1988-04-04 | Production of styrenesulfonated product-maleic acid copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01254718A true JPH01254718A (en) | 1989-10-11 |
Family
ID=13745294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63081401A Pending JPH01254718A (en) | 1988-04-04 | 1988-04-04 | Production of styrenesulfonated product-maleic acid copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01254718A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007023454A (en) * | 2005-07-21 | 2007-02-01 | Jsr Corp | Copolymer for fiber-sizing agent, fiber-sizing agent, fiber bundle, and fiber-reinforced resin |
-
1988
- 1988-04-04 JP JP63081401A patent/JPH01254718A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007023454A (en) * | 2005-07-21 | 2007-02-01 | Jsr Corp | Copolymer for fiber-sizing agent, fiber-sizing agent, fiber bundle, and fiber-reinforced resin |
| JP4701893B2 (en) * | 2005-07-21 | 2011-06-15 | Ｊｓｒ株式会社 | Copolymer for fiber sizing agent, fiber sizing agent, fiber bundle, and fiber reinforced resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4484259B2 (en) | Copolymers based on unsaturated dicarboxylic acid derivatives and oxyalkylene glycol-alkenyl ethers, processes for their preparation and their use | |
| EP3398979A1 (en) | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof | |
| JP2507280B2 (en) | Dispersant for cement | |
| EP0590983A1 (en) | Cement dispersion agents | |
| EP0303747B1 (en) | Acrylic polymer and cement composition containing it | |
| CN106866895A (en) | A kind of high-performance poly carboxylic acid series water reducer and preparation method thereof | |
| JP2011525546A (en) | Aqueous solutions containing copolymers having polyether side chains | |
| CN110760037A (en) | Amino acid modified mud-resistant polycarboxylate superplasticizer and preparation method thereof | |
| KR100990861B1 (en) | pH-SENSITIVE POLYETHYLENE OXIDE CO-POLYMER AND SYNTHETIC METHODE THEREOF | |
| US7390855B2 (en) | Concrete admixture additive | |
| CN102503221A (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| JPH01254718A (en) | Production of styrenesulfonated product-maleic acid copolymer | |
| JPS5867706A (en) | Manufacture of copolymer from monoethylenically unsaturated mono- and dicarboxylic acid | |
| CN107286288B (en) | Preparation method of retarding polycarboxylate superplasticizer | |
| JPH0518849B2 (en) | ||
| CN104926184A (en) | Polycarboxylic acid type water reducer and preparation method thereof | |
| CN109694446B (en) | Synthesis method of solid polycarboxylate superplasticizer | |
| CN114516938A (en) | Non-chlorine double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof | |
| CN103420495A (en) | Preparation method for antisludging agent of central air-conditioning circulating water and application thereof | |
| JP2734072B2 (en) | Method for producing amphoteric copolymer | |
| CN101224959B (en) | Preparation method of carboxylic acid polymer water reducing agent improving esterification yield | |
| JPH0469141B2 (en) | ||
| JP2612174B2 (en) | Method for producing stable aqueous liquid of water-insoluble hydrazide group-containing copolymer | |
| KR20040044610A (en) | Manufacturing methods of high range water reducing agent having polyacrylic acid group | |
| SU1047912A1 (en) | Method of producing polymer compounds of tetraalkylammonium |