JPH0391508A - Production of acrylamide polymer - Google Patents
Production of acrylamide polymerInfo
- Publication number
- JPH0391508A JPH0391508A JP22848789A JP22848789A JPH0391508A JP H0391508 A JPH0391508 A JP H0391508A JP 22848789 A JP22848789 A JP 22848789A JP 22848789 A JP22848789 A JP 22848789A JP H0391508 A JPH0391508 A JP H0391508A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- acrylamide
- sulfonic acid
- monomer
- acid
- 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
- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical group COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 150000001447 alkali salts Chemical class 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 150000007513 acids Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002978 peroxides Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 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 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 preferably K2COs Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- WRKRMDNAUJERQT-UHFFFAOYSA-N cumene hydroxyperoxide Chemical compound OOOO.CC(C)C1=CC=CC=C1 WRKRMDNAUJERQT-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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、アクリルアミド系ポリマーの製造法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an acrylamide polymer.
［従来の技術］
従来、アクリルアミドモノマー単位／アクリル酸（塩）
モノマー単位／スルホン酸（塩）基を有するモノマー単
位を有するアクリルアミド系ポリマーの製造法として、
アクリルアミド、アクリル酸（塩）、スルホン酸（塩）
基を有する七ツマ−を共重合する製造法がある。（例え
ば、時開５５−５５４８８号公報）。[Conventional technology] Conventionally, acrylamide monomer unit/acrylic acid (salt)
As a method for producing an acrylamide polymer having a monomer unit/monomer unit having a sulfonic acid (salt) group,
Acrylamide, acrylic acid (salt), sulfonic acid (salt)
There is a production method that involves copolymerizing a heptamer having a group. (For example, Jikai Publication No. 55-55488).
［発明が解決しようとする課Ｍ］
しかし、上記製造法で製造したポリマーは水及び塩水に
対する溶解性が悪く、不溶解分が、１％を超える等の課
題がある。[Problem M to be Solved by the Invention] However, the polymer produced by the above production method has problems such as poor solubility in water and salt water, and the insoluble content exceeds 1%.
［課題を解決するための手段］
本発明者らは、水及び塩水に対する溶解性の向上したア
クリルアミド系ポリマーの製造法につき鋭意検討した結
果、本発明に到達した。[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of intensive studies on a method for producing an acrylamide polymer with improved solubility in water and salt water.
すなわち本発明は、アクリルアミドとスルホン酸（塩）
基を有するモノマーをアルカリ性物質をあらかじめ加え
た系中で共重合させ、重合率が少なくとも９５％に達し
た段階で、ｐＨ８〜１０１温度７０〜１００℃で熟成し
、アクリルアミド単位を、加水分解することにより、水
および塩水に対する溶解性のよいアクリルアミド系ポリ
マーを製造する方法である。That is, the present invention uses acrylamide and sulfonic acid (salt).
A monomer having a group is copolymerized in a system to which an alkaline substance has been added in advance, and when the polymerization rate reaches at least 95%, the acrylamide unit is hydrolyzed by aging at a pH of 8 to 101 and a temperature of 70 to 100°C. This is a method for producing an acrylamide-based polymer with good solubility in water and salt water.
本発明において使用されるスルホン酸（塩）基を有する
モノマーとしては、特に限定されず、例えば、脂肪族ビ
ニル炭化水素スルホン酸（ビニルスルホン酸）、芳香族
ビニル炭化水素スルホン酸（スチレンスルホン酸）、脂
肪族アミドスルホン酸（２−アクリルアミド−２−メチ
ルプロパンスルホン酸）およびこれらの塩等が挙げられ
る。好ましくは脂肪族アミドスルホン酸（塩）であり、
特に好ましくは、２−アクリルアミド−２−メチルプロ
パンスルホン酸ＣＦＡ） である。The monomer having a sulfonic acid (salt) group used in the present invention is not particularly limited, and includes, for example, aliphatic vinyl hydrocarbon sulfonic acid (vinyl sulfonic acid), aromatic vinyl hydrocarbon sulfonic acid (styrene sulfonic acid) , aliphatic amidosulfonic acid (2-acrylamido-2-methylpropanesulfonic acid) and salts thereof. Preferred is aliphatic amidosulfonic acid (salt),
Particularly preferred is 2-acrylamido-2-methylpropanesulfonic acid (CFA).
アクリルアミドとスルホン酸基を有するモノマーの割合
は、通常アクリルアミド／スルホン酸基を有するモノマ
ーの比がモル比で９９． ９１０゜１〜７０／３０、好
ましくは９９／１〜９０／１０である。The molar ratio of acrylamide to the monomer having a sulfonic acid group is usually 99. 910°1 to 70/30, preferably 99/1 to 90/10.
本発明・の製造法では、さらに他のモノマーを加えるこ
とができる。共重合されるモノマーは、不飽和炭化水素
（スチレン、メチルスチレン、エチレン、ノネン等）、
ビニル化合物（酢酸ビニル、ビニルピロリドン等）、（
メタ）アクリル酸誘導体（メチル（メタ）アクリレート
、エチル（メタ）アクリレート、ヒドロキシエチル（メ
タ）アクリレート、アクリロニトリル等）等が挙げられ
る。In the production method of the present invention, other monomers can be added. Monomers to be copolymerized include unsaturated hydrocarbons (styrene, methylstyrene, ethylene, nonene, etc.),
Vinyl compounds (vinyl acetate, vinyl pyrrolidone, etc.), (
Examples include meth)acrylic acid derivatives (methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, acrylonitrile, etc.).
これらの共重合量は、通常は全体の２０モル％以下であ
る。The amount of these copolymerized materials is usually 20 mol% or less of the total amount.
本発明に使用されるアルカリ性物質は、特に限定されず
、アルカリ金属水酸化物（ＮａＯＨ１ＫＯＨ等）、アル
カリ土類金属水酸化物（Ｍｇ （ＯＨ）２、Ｃａ（ＯＨ
）２等）、弱酸の強アルカリ塩（Ｎ ａｔｃ Ｏｓｓ
ＨｓＣＯｓｓ ＣＨｓＣＯＯＮ ａｓ ＣＨｓ
ＣＯＯＫ等）等である。好ましくは、弱酸の強アルカリ
塩であり、特に好ましくは、Ｋ２ＣＯｓ、 Ｎａ ２
ＣＯａである。添加量は、特に限定なく使用されるが、
通常、アクリルアミドモノマーに対し０〜３０ｍｏ １
％であり、好ましくは、Ｏ〜１５ｍｏ１％である。The alkaline substances used in the present invention are not particularly limited, and include alkali metal hydroxides (NaOH1KOH, etc.), alkaline earth metal hydroxides (Mg(OH)2, Ca(OH)2,
)2, etc.), strong alkali salts of weak acids (N atc Oss
HsCOss CHsCOON as CHs
COOK, etc.). Preferably, strong alkaline salts of weak acids, particularly preferably K2COs, Na2
COa. The amount added is not particularly limited, but
Usually 0 to 30 mo 1 to acrylamide monomer
%, preferably 0 to 15 mo1%.
重合に使用する開始剤としては公知の物が使用でき、例
としては、水溶性アゾ触媒（アゾビスアミジノプロパン
塩、アゾピスシアノバレリックアシッド、およびこの塩
等）、油溶性アゾ触媒（アゾビスイソバレロニトリル、
アゾビスイソブチロニトリル等）、水溶性過酸化物（過
酸化水素、過酢酸等）、油溶性過酸化物（ベンゾイルパ
ーオキシド、クメンヒドロキシパーオキシド等）、無機
過酸化物（過硫酸アンモニウム、過硫酸ナトリウム等）
等が挙げられる。また上記のような過酸化物と還元剤と
でレドックス系を形成しても良く、アゾ触媒、過酸化物
触媒、ないしレドックス触媒を適宜併用してもよい。こ
れらの中でアゾ触媒の単独使用ないしは、これとレドッ
クス触媒の併用が好ましく、特にアゾ触媒とレドックス
触媒の併用が目的のポリマーを得やすく好ましい。Known initiators can be used for polymerization; examples include water-soluble azo catalysts (azobisamidinopropane salt, azopiscyanovaleric acid, salts thereof, etc.), oil-soluble azo catalysts (azobisamidinopropane salt, azopiscyanovaleric acid, and salts thereof, etc.), isovaleronitrile,
azobisisobutyronitrile, etc.), water-soluble peroxides (hydrogen peroxide, peracetic acid, etc.), oil-soluble peroxides (benzoyl peroxide, cumene hydroxyperoxide, etc.), inorganic peroxides (ammonium persulfate, peroxide, etc.), sodium sulfate, etc.)
etc. Further, a redox system may be formed with the above-mentioned peroxide and reducing agent, and an azo catalyst, a peroxide catalyst, or a redox catalyst may be used in combination as appropriate. Among these, it is preferable to use an azo catalyst alone or a combination of this and a redox catalyst, and it is particularly preferable to use a combination of an azo catalyst and a redox catalyst because it is easy to obtain the desired polymer.
重合法は、公知の方法が使用でき、例えば、水溶液重合
法、沈澱重合法、懸濁重合法、乳化重合法等の方法が挙
げられる。好ましくは、水溶液重合法である。As the polymerization method, a known method can be used, and examples thereof include methods such as an aqueous solution polymerization method, a precipitation polymerization method, a suspension polymerization method, and an emulsion polymerization method. Preferably, an aqueous solution polymerization method is used.
重合時のモノマー濃度は、特に限定ないが、通常５〜３
０％であり、好ましくは、１０〜２０％である。The monomer concentration during polymerization is not particularly limited, but is usually 5 to 3.
0%, preferably 10-20%.
重合後のポリマーは、含水ゲルとなる。通常これを乾燥
してポリマーを得る。ゲルの乾燥法は、通常は熱風乾燥
を行なう。得られた含水ゲルを切断、破砕し熱風乾燥す
る。乾燥温度は、特に限定ないが通常６０〜１２０℃で
あり、好ましくは７０〜９０℃である。乾燥したゲルは
粉砕し粉末状のポリマーを得る。The polymer after polymerization becomes a hydrogel. This is usually dried to obtain a polymer. The gel is usually dried by hot air drying. The resulting hydrogel is cut, crushed, and dried with hot air. The drying temperature is not particularly limited, but is usually 60 to 120°C, preferably 70 to 90°C. The dried gel is crushed to obtain a powdered polymer.
得られるアクリルアミド単位／アクリル酸単位／スルホ
ン酸基を有するモノマー単位を有するアクリルアミド系
ポリマーはアルカリ性物質存在下では塩の形になってい
る。The resulting acrylamide polymer having monomer units having acrylamide units/acrylic acid units/sulfonic acid groups is in the form of a salt in the presence of an alkaline substance.
［実施例コ
以下実施例により本発明をさらに説明するが、本発明は
これにより限定されるものではない。[Example] The present invention will be further explained with reference to Examples below, but the present invention is not limited thereto.
実施例１〜３
攪拌機を備えたコルベンに、アクリルアミド（以下ＡＡ
ｍと略する）および、２−アクリルアミド−２メチルプ
ロパンスルホン酸（以下ＡＭＰＳと略する）を、表１に
示す割合で加え、これをＡＭＰＳと当量の水酸化ナトリ
ウムで中和した。さらに炭酸ナトリウムを、アクリルア
ミドに対し表１に示す割合で加え、イオン交換水を加え
て、モノマーの全重量が全体の１５％となるように調整
した。次に温度３５℃に温調し、系内を窒素で置換した
。ついで開始剤として、アゾビスシアノバレリックアシ
ッドのソーダ塩の１０％水溶液を、アゾビスシアノバレ
リックアシッドの添加量が全モノマー重量の０．１％と
なるよう攪拌しながら加えた。約１分後に重合が開始し
、発熱が認められ内容物温度７０℃となったので、その
温度を保つよう温度調節し、１０時間熟成を行ない加水
分解を行った。なお、内容物温度が７０℃となったとき
の重合率は９６％、ｐＨは９であった。重合中、内容物
が高粘度となり、撹拌が困難となったため、撹拌は途中
で停止した。加水分解、重合完結後、内容物を取り出し
、切断、破砕し、８０℃で熱風乾燥した。これを、粉砕
し粉末状のアクリルアミド系ポリマーを得た。収率は９
９．８％以上であった。得られたポリマーの分析値を表
２に示す。Examples 1 to 3 Acrylamide (hereinafter referred to as AA) was placed in a colben equipped with a stirrer.
m) and 2-acrylamido-2methylpropanesulfonic acid (hereinafter abbreviated as AMPS) were added in the proportions shown in Table 1, and this was neutralized with sodium hydroxide in an amount equivalent to AMPS. Further, sodium carbonate was added to the acrylamide in the ratio shown in Table 1, and ion-exchanged water was added to adjust the total weight of the monomer to 15% of the total weight. Next, the temperature was adjusted to 35° C., and the inside of the system was purged with nitrogen. Then, as an initiator, a 10% aqueous solution of soda salt of azobiscyanovaleric acid was added with stirring so that the amount of azobiscyanovaleric acid added was 0.1% of the total monomer weight. Polymerization started after about 1 minute, heat generation was observed, and the temperature of the contents reached 70°C. The temperature was adjusted to maintain this temperature, and the mixture was aged for 10 hours to perform hydrolysis. The polymerization rate was 96% and the pH was 9 when the temperature of the contents reached 70°C. During polymerization, the contents became highly viscous and stirring became difficult, so stirring was stopped midway. After completion of hydrolysis and polymerization, the contents were taken out, cut, crushed, and dried with hot air at 80°C. This was pulverized to obtain a powdery acrylamide polymer. Yield is 9
It was 9.8% or more. Table 2 shows the analytical values of the obtained polymer.
比較例１〜３
撹拌機を備えたコルベンに、ＡＡｍ、ＡＭＰＳＮおよび
、アクリル酸を表１に示す割合で、モノマーの合計重量
が１５％となるようにイオン交換水を加えた。これを、
水酸化ナトリウムで中和した後、温度３５℃に調整し、
系内を窒素で置換した。Comparative Examples 1 to 3 AAM, AMPSN, and acrylic acid were added to a colben equipped with a stirrer in the proportions shown in Table 1, and ion-exchanged water was added so that the total weight of the monomers was 15%. this,
After neutralizing with sodium hydroxide, the temperature was adjusted to 35°C,
The atmosphere in the system was replaced with nitrogen.
ついで開始剤として、アゾビスシアノバレリックアシッ
ドのソーダ塩の１０％水溶液をアゾビスシアニバレリッ
クアシッドの添加量が全モノマー重量の０． １％とな
る様撹拌しながら加えた。約１分後に重合が開始し、発
熱が認められ内容物温度が７０℃となったので、その温
度を保つよう温度調節し１０時間重合を行なった。なお
、重合中内容物が高粘度となり、攪拌が困難となったた
め、攪拌は、途中で停止した。重合完結後、内容物を取
り出し、切断、破砕し、８０℃で熱風乾燥した。Next, as an initiator, a 10% aqueous solution of the soda salt of azobiscyanovaleric acid was added until the amount of azobiscyanivaleric acid added was 0.0% based on the total monomer weight. It was added while stirring so that the concentration was 1%. Polymerization started after about 1 minute, heat generation was observed, and the temperature of the contents reached 70°C, so the temperature was adjusted to maintain that temperature and polymerization was carried out for 10 hours. Note that during polymerization, the contents became highly viscous and stirring became difficult, so stirring was stopped midway. After the polymerization was completed, the contents were taken out, cut, crushed, and dried with hot air at 80°C.
これを粉砕し、粉末状のポリマーを得た。収率は、９９
．８％以上であった。得られたポリマーの分析値を、表
２に示す。This was pulverized to obtain a powdered polymer. The yield is 99
．． It was 8% or more. Table 2 shows the analytical values of the obtained polymer.
表１
表２
本発明の製造法は、アクリルアミド系ポリマーの不溶解
骨を大幅に減少することができる。Table 1 Table 2 The production method of the present invention can significantly reduce undissolved bone in acrylamide-based polymers.
これにより、本発明により得られたポリマーを高分子凝
集剤として使用する場合、凝集性、脱水性等が大幅にア
ップする。また、石油の３次回収用ポリマーとして使用
する場合、油層への圧入性が良好になり、石油の回収率
が大幅にアップする効果を持っている。As a result, when the polymer obtained according to the present invention is used as a polymer flocculant, cohesive properties, dehydration properties, etc. are greatly improved. Furthermore, when used as a polymer for tertiary oil recovery, the injectability into the oil layer is improved and the oil recovery rate is significantly increased.
１：・１・ど。1:・1・Do.
Claims (1)
マーをアルカリ性物質をあらかじめ加えた系中で共重合
させ、重合率が少なくとも９５％に達した段階で、ｐＨ
８〜１０、温度７０〜１００℃で熟成し、アクリルアミ
ド単位を、加水分解することによりアクリルアミド単位
／アクリル酸単位／スルホン酸基を有するモノマー単位
を有するアクリルアミド系ポリマーを製造することを特
徴とするアクリルアミド系ポリマーの製造法。 ２、アルカリ性物質が、アルカリ金属水酸化物、アルカ
リ土類金属水酸化物、または弱酸の強アルカリ塩である
請求項１記載の製造法。 ３、スルホン酸（塩）基を有するモノマーが、脂肪族ビ
ニル炭化水素スルホン酸（塩）、芳香族ビニル炭化水素
スルホン酸（塩）、または脂肪族アミドスルホン酸（塩
）である請求項１または２記載の製造法。[Claims] 1. Copolymerize acrylamide and a monomer having a sulfonic acid (salt) group in a system to which an alkaline substance has been added in advance, and when the polymerization rate reaches at least 95%, the pH
8 to 10, an acrylamide characterized by producing an acrylamide polymer having monomer units having acrylamide units/acrylic acid units/sulfonic acid groups by aging at a temperature of 70 to 100°C and hydrolyzing the acrylamide units. Production method of polymers. 2. The method according to claim 1, wherein the alkaline substance is an alkali metal hydroxide, an alkaline earth metal hydroxide, or a strong alkali salt of a weak acid. 3. Claim 1 or 3, wherein the monomer having a sulfonic acid (salt) group is an aliphatic vinyl hydrocarbon sulfonic acid (salt), an aromatic vinyl hydrocarbon sulfonic acid (salt), or an aliphatic amidosulfonic acid (salt). 2. The manufacturing method described in 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1228487A JPH0692447B2 (en) | 1989-09-04 | 1989-09-04 | Method for producing acrylamide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1228487A JPH0692447B2 (en) | 1989-09-04 | 1989-09-04 | Method for producing acrylamide polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0391508A true JPH0391508A (en) | 1991-04-17 |
| JPH0692447B2 JPH0692447B2 (en) | 1994-11-16 |
Family
ID=16877235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1228487A Expired - Lifetime JPH0692447B2 (en) | 1989-09-04 | 1989-09-04 | Method for producing acrylamide polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692447B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112014001581B4 (en) * | 2013-03-22 | 2017-02-23 | The Yokohama Rubber Co., Ltd | Use of an emulsion coagulant and this benefit of the puncture repair kit |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61126113A (en) * | 1984-11-22 | 1986-06-13 | Lion Corp | Production of partially hydrolyzed polyacrylamide polymer |
-
1989
- 1989-09-04 JP JP1228487A patent/JPH0692447B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61126113A (en) * | 1984-11-22 | 1986-06-13 | Lion Corp | Production of partially hydrolyzed polyacrylamide polymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112014001581B4 (en) * | 2013-03-22 | 2017-02-23 | The Yokohama Rubber Co., Ltd | Use of an emulsion coagulant and this benefit of the puncture repair kit |
| US9657164B2 (en) | 2013-03-22 | 2017-05-23 | The Yokohama Rubber Co., Ltd. | Emulsion coagulant and tire puncture repair kit using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0692447B2 (en) | 1994-11-16 |
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