JPH04268304A - Production of low-molecular weight (meth)acrylic acid salt polymer - Google Patents
Production of low-molecular weight (meth)acrylic acid salt polymerInfo
- Publication number
- JPH04268304A JPH04268304A JP5019991A JP5019991A JPH04268304A JP H04268304 A JPH04268304 A JP H04268304A JP 5019991 A JP5019991 A JP 5019991A JP 5019991 A JP5019991 A JP 5019991A JP H04268304 A JPH04268304 A JP H04268304A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- molecular weight
- polymerization
- polymer
- low
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 28
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 11
- 150000002978 peroxides Chemical class 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000012986 chain transfer agent Substances 0.000 abstract description 6
- 101100366942 Mus musculus Ston1 gene Proteins 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 229940047670 sodium acrylate Drugs 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229940048053 acrylate Drugs 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- ZFHOULOIWZOZQS-UHFFFAOYSA-N hexane;hydrogen peroxide Chemical compound OO.CCCCCC ZFHOULOIWZOZQS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- BESWQAXCVAOXFV-UHFFFAOYSA-N octyl hydroperoxide Chemical compound CCCCCCCCOO BESWQAXCVAOXFV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は低分子量（メタ）アクリ
ル酸塩系重合体の製造方法に関するもので、着色の少な
い低分子量（メタ）アクリル酸塩系重合体を、高濃度の
水溶液として、高い生産性で得られることを特長とし、
得られた低分子量（メタ）アクリル酸塩系重合体は、顔
料の分散剤として製紙又は塗料業界で、清缶剤として水
処理業界で、ビルダーとして洗剤業界でという様に利用
されるものであり、本発明はこれらの業界及びその製造
を行う化学業界で幅広く利用されるものである。[Industrial Application Field] The present invention relates to a method for producing a low molecular weight (meth)acrylate polymer, in which a low molecular weight (meth)acrylate polymer with little coloring is prepared as a highly concentrated aqueous solution. It is characterized by high productivity,
The resulting low molecular weight (meth)acrylate-based polymers are used in the paper and paint industries as pigment dispersants, in the water treatment industry as can cleaners, and as builders in the detergent industry. The present invention is widely used in these industries and the chemical industry that manufactures them.
【０００２】0002
【従来技術】一般に、低分子量（メタ）アクリル酸塩系
重合体（以下代表的な化合物であるアクリル酸ソーダ低
重合体で代表させて説明する）は、アクリル酸を水溶液
重合することによりアクリル酸低重合体水溶液を得た後
に、該水溶液を苛性ソーダで中和するという方法やアク
リル酸エステル類を有機溶媒中で重合し、その後、溶媒
除去とケン化とを行う方法により製造されている。[Prior Art] In general, low molecular weight (meth)acrylate-based polymers (described below using a typical compound, sodium acrylate low polymer) are produced by polymerizing acrylic acid in an aqueous solution. They are produced by obtaining an aqueous low polymer solution and then neutralizing the aqueous solution with caustic soda, or by polymerizing acrylic esters in an organic solvent, followed by solvent removal and saponification.
【０００３】前記方法により高濃度のアクリル酸低重合
体水溶液を得ることは難しく、例えば、高濃度のアクリ
ル酸水溶液で重合を行うと、分子量の高いアクリル酸重
合体が得られるだけであり、溶媒中で重合する方法は、
高価な有機溶媒を必要とするうえ、有機溶媒の完全な除
去は殆ど不可能であるため、有機溶媒が重合体水溶液中
に残存し臭気発生の原因となるばかりでなく、低重合度
化も十分とはいえないものである。It is difficult to obtain a highly concentrated acrylic acid low polymer aqueous solution using the above method. For example, if polymerization is carried out using a highly concentrated acrylic acid aqueous solution, only an acrylic acid polymer with a high molecular weight is obtained, and the solvent The method of polymerization in
In addition to requiring an expensive organic solvent, complete removal of the organic solvent is almost impossible, so not only does the organic solvent remain in the polymer aqueous solution and cause odor, but it is also difficult to reduce the degree of polymerization sufficiently. That cannot be said.
【０００４】そのため、高濃度のアクリル酸ソーダ低重
合体水溶液を得る方法として各種の方法が提案されてき
ている。例えば、■ 重合時間を長くする。■ 重
合開始剤を増量する。■ 連鎖移動剤を使用する。■
重合温度を高くする。■ アクリル酸ソーダ水溶
液としてから重合する。■ アクリル酸ソーダ水溶液
に空気を吹き込みながら重合する。などである。[0004] Therefore, various methods have been proposed to obtain a highly concentrated aqueous solution of sodium acrylate low polymer. For example, ■ Increase the polymerization time. ■ Increase the amount of polymerization initiator. ■ Use chain transfer agents. ■
Increase the polymerization temperature. ■ Polymerize after forming an aqueous solution of sodium acrylate. ■ Polymerize while blowing air into the sodium acrylate aqueous solution. etc.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、前記の
提案のいずれも解決しなければならない以下の様な課題
を有しているものである。■ 重合時間を長くするこ
とは製造施設・装置の面から制限を受けるだけでなく、
当然に製造費の上昇を招く。■ 多量の重合開始剤の
使用は重合開始剤の断片等、例えば過硫酸塩の場合は芒
硝、による製品純分の低下を招く。■ 連鎖移動剤の
使用は製品に臭気を付加する、例えばメルカプト系連鎖
移動剤による臭気、或いはアルコール等の有機溶媒を用
いた場合には重合終了後に該アルコールを除去する工程
が必要になる。■ 高温での重合の場合は耐圧装置を
用い加圧下に行わなければならず、設備面での制限や、
得られる製品が着色する傾向にある。■ アクリル酸
ソーダを使用する場合はアクリル酸ソーダの溶解度の関
係から濃縮工程を採用しなければ３６％以上のものは得
られない。
■ 上記■と同じ問題を有する他、アクリル酸に応用
した場合は、アクリル酸や開始剤、連鎖移動剤等の飛散
が伴い、製造操作の面で種々の問題を生ずる。However, all of the above proposals have the following problems that must be solved. ■ Prolonging the polymerization time is not only limited by manufacturing facilities and equipment;
Naturally, this will lead to an increase in manufacturing costs. (2) Use of a large amount of polymerization initiator causes a decrease in product purity due to fragments of the polymerization initiator, such as mirabilite in the case of persulfate. (2) The use of a chain transfer agent adds odor to the product, for example, the odor caused by a mercapto chain transfer agent, or when an organic solvent such as alcohol is used, a step is required to remove the alcohol after completion of polymerization. ■ In the case of polymerization at high temperatures, it must be carried out under pressure using pressure-resistant equipment, and there are restrictions in terms of equipment and
The resulting product tends to be colored. ■ When using sodium acrylate, it is impossible to obtain a concentration higher than 36% unless a concentration process is adopted due to the solubility of sodium acrylate. (2) In addition to having the same problems as (2) above, when applied to acrylic acid, the acrylic acid, initiator, chain transfer agent, etc. are scattered, causing various problems in terms of manufacturing operations.
【０００６】本発明者等は、これらの問題を解決し、着
色の少ない高濃度のアクリル酸ソーダ低重合体水溶液を
得るべく種々検討を行ったのである。The present inventors have conducted various studies in order to solve these problems and obtain a highly concentrated aqueous solution of sodium acrylate low polymer with little coloring.
【０００７】[0007]
【課題を解決するための手段】本発明者等は種々検討し
た結果、アクリル酸を原料として、有機溶媒等の連鎖移
動剤を使用せず、着色の極めて少ない、分子量２００か
ら１０，０００の間の任意の分子量のアクリル酸ソーダ
低重合体の高濃度、例えば４０％以上の水溶液を、中和
工程、加水分解工程或いは脱溶媒工程等を別途設けずに
、生産性よく製造し得る方法を見出して本発明を完成し
たのである。[Means for Solving the Problems] As a result of various studies, the present inventors have developed a method using acrylic acid as a raw material, without using a chain transfer agent such as an organic solvent, with extremely little coloring, and with a molecular weight between 200 and 10,000. Discovered a method that can produce a highly concentrated aqueous solution of a sodium acrylate low polymer of any molecular weight, for example, 40% or more, with good productivity without separately providing a neutralization step, a hydrolysis step, a desolvation step, etc. Thus, the present invention was completed.
【０００８】すなわち、本発明は、アクリル酸又はメタ
クリル酸を主体とする単量体を過酸化物系重合開始剤と
ともに加熱アルカリ水溶液中に添加しながら重合させる
ことを特徴とする低分子量（メタ）アクリル酸塩系重合
体の製造方法に関するものである。That is, the present invention is characterized in that a monomer mainly consisting of acrylic acid or methacrylic acid is polymerized while being added to a heated alkaline aqueous solution together with a peroxide polymerization initiator. The present invention relates to a method for producing an acrylate-based polymer.
【０００９】本発明において用いられるアクリル酸又は
メタクリル酸を主体とする単量体とは、アクリル酸又は
メタクリル酸の単独又はそれらの混合物或いはそれらに
イタコン酸、マレイン酸等の水溶性ビニル単量体、水溶
性を損なわない範囲のその他のビニル単量体との混合物
であってよく、最終の製品に求められる特性に応じて選
択され、それらの使用及び割合は、当業者にとり公知の
ものである。The monomer mainly composed of acrylic acid or methacrylic acid used in the present invention refers to acrylic acid or methacrylic acid alone or a mixture thereof, or a water-soluble vinyl monomer such as itaconic acid or maleic acid. , may be a mixture with other vinyl monomers to the extent that they do not impair water solubility, and are selected depending on the properties desired in the final product, and their use and proportions are known to those skilled in the art. .
【００１０】重合は、アクリル酸又はメタクリル酸を主
体とする単量体を加熱アルカリ水溶液中に添加しながら
行うのであり、加熱アルカリ水溶液の温度としては、好
ましくは８０〜１００℃、より好ましくは９０〜１００
℃である。８０℃未満の温度であると重合が円滑に行わ
れない恐れもあり、又、分子量を十分に低くすることが
困難になる。[0010] Polymerization is carried out while adding a monomer mainly composed of acrylic acid or methacrylic acid to a heated aqueous alkaline solution, and the temperature of the heated aqueous alkaline solution is preferably 80 to 100°C, more preferably 90°C. ~100
It is ℃. If the temperature is lower than 80°C, polymerization may not be carried out smoothly, and it may be difficult to lower the molecular weight sufficiently.
【００１１】アルカリとしては、苛性ソーダ、苛性カリ
が具体的に挙げられ、加熱アルカリ水溶液としての濃度
は、得られる重合体の分子量に大きく作用するので、５
重量％以上、好ましくは１０重量％以上であり、上限と
しては飽和水溶液であっても良いが、余り高濃度である
と腐食性が強まり、反応器等に格別な仕様が必要になる
ため、その点からは３５重量％以下が好ましい。Specific examples of the alkali include caustic soda and caustic potash, and the concentration of the heated aqueous alkali solution has a large effect on the molecular weight of the resulting polymer;
% by weight or more, preferably 10% by weight or more, and a saturated aqueous solution may be used as an upper limit, but if the concentration is too high, the corrosivity will increase and special specifications will be required for the reactor, etc. From this point of view, the content is preferably 35% by weight or less.
【００１２】媒体としての水は、高濃度と低重合度化と
いう矛盾する二つの要求を同時に満足させるために、単
量体と略同量（重量比）になる様に管理して重合するの
が望ましい。[0012] In order to simultaneously satisfy the two contradictory demands of high concentration and low degree of polymerization, water as a medium must be controlled so that the amount (weight ratio) is approximately the same as that of the monomer during polymerization. is desirable.
【００１３】アクリル酸又はメタクリル酸を主体とする
単量体と過酸化物系重合開始剤は、反応の進行具合を見
ながら、連続又は断続的に、且つ同時に又は別々に上記
の様な温度に加熱されたアルカリ水溶液中に添加し重合
させる。The monomer mainly composed of acrylic acid or methacrylic acid and the peroxide polymerization initiator are heated to the above temperature continuously or intermittently, simultaneously or separately, while monitoring the progress of the reaction. Add to heated aqueous alkaline solution and polymerize.
【００１４】過酸化物系重合開始剤としては、アクリル
酸又はメタクリル酸の重合で用いられている公知のもの
が同様に適用されが、本発明にとり好ましいものは、ク
ミルハイドロパーオキサイド、ヘキサンハイドロパーオ
キサイド、オクタンハイドロパーオキサイド、過酸化水
素等のハイドロパーオキサイドであり、特に過酸化水素
が好ましい。As the peroxide polymerization initiator, known ones used in the polymerization of acrylic acid or methacrylic acid can be similarly applied, but preferred ones for the present invention are cumyl hydroperoxide and hexane hydroperoxide. Hydroperoxides such as peroxide, octane hydroperoxide, and hydrogen peroxide are preferred, with hydrogen peroxide being particularly preferred.
【００１５】過酸化物系重合開始剤の使用量としては、
単量体１００重量部あたり２〜１０重量部が好ましく、
重合時間や目的とする分子量を考慮して決定される。[0015] The amount of peroxide polymerization initiator used is as follows:
It is preferably 2 to 10 parts by weight per 100 parts by weight of the monomer,
It is determined in consideration of polymerization time and target molecular weight.
【００１６】重合時間としては４〜１０時間掛けるのが
最適である。The optimum polymerization time is 4 to 10 hours.
【００１７】[0017]
【作用】本発明の製造方法は、加熱アルカリ水溶液にア
クリル酸又はメタクリル酸を主体とする単量体と過酸化
物系重合開始剤を添加しながら重合させる方法であり、
加熱アルカリ水溶液の温度が８０℃以上という高温及び
強アルカリ性という腐食性の条件下での重合反応である
にもかかわらず、理由は不明であるが、予想される重合
開始剤の失活、分解が少なく、得られる重合体は殆ど分
解されず、着色も極めて少なく、有機溶媒或いは連鎖移
動剤を使用しないにもかかわらず、十分に低重合度のも
のになり、又、濃縮という別工程を設けずとも濃度の高
い水溶液として製品が得られるのである。[Function] The production method of the present invention is a method of polymerizing a heated alkaline aqueous solution while adding a monomer mainly composed of acrylic acid or methacrylic acid and a peroxide polymerization initiator,
Although the polymerization reaction was carried out under corrosive conditions such as high temperature of the heated alkaline aqueous solution of 80°C or higher and strong alkalinity, the expected deactivation and decomposition of the polymerization initiator were observed, although the reason is unknown. The resulting polymer is hardly decomposed, has very little coloring, has a sufficiently low degree of polymerization even though no organic solvent or chain transfer agent is used, and does not require a separate process of concentration. In both cases, the product can be obtained as a highly concentrated aqueous solution.
【００１８】この様な結果がどの様な作用機構により奏
されるのかは不明であるが、従来の常識では考え得なか
った方法で、優れた製品が得られるのである。[0018] Although it is unclear what kind of action mechanism is responsible for achieving such a result, an excellent product can be obtained by a method that was inconceivable according to conventional common sense.
【００１９】[0019]
【実施例】以下に本発明を更に具体的に説明するために
本発明者等が行った実施例について示す。[Examples] Examples carried out by the present inventors will be shown below in order to explain the present invention more specifically.
【００２０】実施例１
５Ｌのステンレス製反応器にイオン交換水６３．６部と
濃度４８ｗｔ％の苛性ソーダ１１２．２部入れ（苛性ソ
ーダ濃度２８．７２％）、９０℃まで加熱した後、９８
％アクリル酸１００部、過酸化水素７．５部（１００％
換算）、過硫酸ソーダ３．７部を連続的に８時間掛けて
供給し重合させた。得られた重合体水溶液の固形分は４
６％、粘度は１１９ ｃｐｓ（ＢＭ型粘度計）であり、
数平均分子量はゲル浸透クロマトグラフ（ＧＰＣ）で測
定した結果、２１８であった。又、残存する単量体をガ
スクロマトグラフ（ＧＣ）で分析した結果、重合率は９
９．９９であった。
又、該重合体の赤外線吸収スペクトルは図１のとおりで
あり、熱アルカリ内で重合したにも係わらず、該重合体
は殆ど分解されることなく、アクリル酸ソーダ重合体の
構造を有している。尚、重合率、数平均分子量の測定は
、以下の例においても同様に行った。Example 1 63.6 parts of ion-exchanged water and 112.2 parts of caustic soda with a concentration of 48 wt% (caustic soda concentration of 28.72%) were placed in a 5L stainless steel reactor, and heated to 90°C.
% acrylic acid, 7.5 parts of hydrogen peroxide (100%
(converted) and 3.7 parts of sodium persulfate were continuously fed over 8 hours to polymerize. The solid content of the obtained polymer aqueous solution was 4
6%, the viscosity is 119 cps (BM type viscometer),
The number average molecular weight was 218 as measured by gel permeation chromatography (GPC). In addition, as a result of analyzing the remaining monomer by gas chromatography (GC), the polymerization rate was 9.
It was 9.99. In addition, the infrared absorption spectrum of the polymer is shown in Figure 1, and even though it was polymerized in a hot alkali, the polymer was hardly decomposed and had the structure of a sodium acrylate polymer. There is. The polymerization rate and number average molecular weight were measured in the same manner in the following examples.
【００２１】実施例２
反応器内の苛性ソーダ濃度を２０％とし、苛性ソーダ残
量は単量体等と同様に連続添加した以外は、実施例１と
同様に重合を行った。得られた重合体の重合率は９９．
９８％、数平均分子量は５２５で、粘度は２９７ ｃｐ
ｓ（ＢＭ型粘度計）、固形分は４５％であった。Example 2 Polymerization was carried out in the same manner as in Example 1, except that the caustic soda concentration in the reactor was 20%, and the remaining amount of caustic soda was added continuously in the same manner as the monomers. The polymerization rate of the obtained polymer was 99.
98%, number average molecular weight is 525, viscosity is 297 cp
s (BM type viscometer), the solid content was 45%.
【００２２】実施例３
反応器内の苛性ソーダ濃度を１０％とし、苛性ソーダ残
量は単量体等と同様に連続添加した以外は、実施例１と
同様に重合を行った。得られた重合体の重合率は９９．
９８％、数平均分子量は１１５５で、粘度は３０９０
ｃｐｓ（ＢＭ型粘度計）、固形分は４５％であった。Example 3 Polymerization was carried out in the same manner as in Example 1, except that the caustic soda concentration in the reactor was 10%, and the remaining amount of caustic soda was added continuously in the same manner as the monomers. The polymerization rate of the obtained polymer was 99.
98%, number average molecular weight is 1155, viscosity is 3090
cps (BM type viscometer), the solid content was 45%.
【００２３】実施例４
反応器に最初に張る水の量を４９．８部、過酸化水素を
９．７部（１００％換算）にした以外は、実施例２と同
様に重合を行った。得られた重合体の重合率は９９．９
８％、数平均分子量は１７３０で、粘度は９６０ ｃｐ
ｓ（ＢＭ型粘度計）、固形分は４６．１％であった。Example 4 Polymerization was carried out in the same manner as in Example 2, except that the amount of water initially charged in the reactor was 49.8 parts and the amount of hydrogen peroxide was 9.7 parts (calculated as 100%). The polymerization rate of the obtained polymer was 99.9
8%, number average molecular weight is 1730, viscosity is 960 cp
s (BM type viscometer), the solid content was 46.1%.
【００２４】実施例５
重合温度を８０℃にした以外は、実施例２と同様に重合
を行った。得られた重合体の重合率は９９．９８％、数
平均分子量は２５７６で、粘度は２０３０ｃｐｓ（ＢＭ
型粘度計）、固形分は４５．７％であった。Example 5 Polymerization was carried out in the same manner as in Example 2, except that the polymerization temperature was 80°C. The polymerization rate of the obtained polymer was 99.98%, the number average molecular weight was 2576, and the viscosity was 2030 cps (BM
type viscometer), and the solid content was 45.7%.
【００２５】実施例６
反応器に最初に張る水の量を７０．２部、過酸化水素を
３．３部（１００％換算）過硫酸ソーダを１．７部にし
た以外は、実施例２と同様に重合を行った。得られた重
合体の重合率は９９．９９％、数平均分子量は１００２
で、粘度は５４７．５ ｃｐｓ（ＢＭ型粘度計）、固形
分は４５．９％であった。Example 6 Example 2 except that the amount of water initially charged in the reactor was 70.2 parts, hydrogen peroxide was 3.3 parts (100% conversion), and sodium persulfate was 1.7 parts. Polymerization was carried out in the same manner. The polymerization rate of the obtained polymer was 99.99%, and the number average molecular weight was 1002.
The viscosity was 547.5 cps (BM type viscometer) and the solid content was 45.9%.
【００２６】実施例７
添加する苛性ソーダの添加開始時間を重合開始後２．５
時間とした以外は、実施例２と同様に重合を行った。得
られた重合体の重合率は９９．９９％、数平均分子量は
２３７で、粘度は６５８ ｃｐｓ（ＢＭ型粘度計）、固
形分は４４．９％であった。Example 7 The addition start time of caustic soda was set at 2.5 minutes after the start of polymerization.
Polymerization was carried out in the same manner as in Example 2, except for changing the time. The polymerization rate of the obtained polymer was 99.99%, the number average molecular weight was 237, the viscosity was 658 cps (BM type viscometer), and the solid content was 44.9%.
【００２７】[0027]
【発明の効果】本発明によれば、低重合度で、重合度分
布も狭く、且つ着色の少ない低分子量（メタ）アクリル
酸塩系重合体が高濃度水溶液として生産性よく製造する
ことができ、得られた重合体は、その有する優れた特性
即ち分散能やキレート能の故に、顔料分散剤、洗剤、清
缶剤に広く使用されるものであるため、本発明はそれら
を製造する或いは使用する業界において非常に有効なも
のである。[Effects of the Invention] According to the present invention, a low molecular weight (meth)acrylate-based polymer having a low degree of polymerization, a narrow distribution of the degree of polymerization, and little coloring can be produced with high productivity as a highly concentrated aqueous solution. The obtained polymers are widely used in pigment dispersants, detergents, and can cleaners due to their excellent properties, such as dispersion ability and chelating ability. This is extremely effective in industries where
【図１】図１は実施例１で得られた低分子量アクリル酸
ソーダ重合体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 low molecular weight sodium acrylate polymer obtained in Example 1.
Claims (1)
体とする単量体を過酸化物系重合開始剤とともに加熱ア
ルカリ水溶液中に添加しながら重合させることを特徴と
する低分子量（メタ）アクリル酸塩系重合体の製造方法
。[Claim 1] A low-molecular-weight (meth)acrylate salt system characterized by polymerizing a monomer mainly composed of acrylic acid or methacrylic acid together with a peroxide-based polymerization initiator into a heated alkaline aqueous solution. Method for producing polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5019991A JP2929746B2 (en) | 1991-02-25 | 1991-02-25 | Method for producing low molecular weight (meth) acrylate polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5019991A JP2929746B2 (en) | 1991-02-25 | 1991-02-25 | Method for producing low molecular weight (meth) acrylate polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04268304A true JPH04268304A (en) | 1992-09-24 |
| JP2929746B2 JP2929746B2 (en) | 1999-08-03 |
Family
ID=12852466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5019991A Expired - Fee Related JP2929746B2 (en) | 1991-02-25 | 1991-02-25 | Method for producing low molecular weight (meth) acrylate polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2929746B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777385B2 (en) | 2000-07-07 | 2004-08-17 | Nippon Shokubai Co., Ltd. | Low-Molecular (meth)acrylicacid(salt)-based polymer and its production process and uses |
| US6794473B2 (en) | 2001-05-01 | 2004-09-21 | Nippon Shokubai Co., Ltd. | Acrylic acid (salt) polymer, its production process and uses |
| WO2014050817A1 (en) | 2012-09-25 | 2014-04-03 | 三井化学株式会社 | Method for producing olefin polymer, and olefin polymer |
| WO2014050816A1 (en) | 2012-09-25 | 2014-04-03 | 三井化学株式会社 | Transition metal compound, olefin polymerization catalyst, and method for producing olefin polymer |
| CN108892746A (en) * | 2018-06-06 | 2018-11-27 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of novel polypropylene acid salt aqueous solution |
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| KR20190047994A (en) | 2017-10-30 | 2019-05-09 | 주식회사 엘지화학 | Manufacturing method for low molecular weight acrylic resin |
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1991
- 1991-02-25 JP JP5019991A patent/JP2929746B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777385B2 (en) | 2000-07-07 | 2004-08-17 | Nippon Shokubai Co., Ltd. | Low-Molecular (meth)acrylicacid(salt)-based polymer and its production process and uses |
| US6794473B2 (en) | 2001-05-01 | 2004-09-21 | Nippon Shokubai Co., Ltd. | Acrylic acid (salt) polymer, its production process and uses |
| WO2014050817A1 (en) | 2012-09-25 | 2014-04-03 | 三井化学株式会社 | Method for producing olefin polymer, and olefin polymer |
| WO2014050816A1 (en) | 2012-09-25 | 2014-04-03 | 三井化学株式会社 | Transition metal compound, olefin polymerization catalyst, and method for producing olefin polymer |
| KR20150053797A (en) | 2012-09-25 | 2015-05-18 | 미쓰이 가가쿠 가부시키가이샤 | Method for producing olefin polymer, and olefin polymer |
| US9458261B2 (en) | 2012-09-25 | 2016-10-04 | Mitsui Chemicals, Inc. | Transition metal compound, olefin polymerization catalyst, and olefin polymer production process |
| US9458257B2 (en) | 2012-09-25 | 2016-10-04 | Mitsui Chemicals, Inc. | Process for producing olefin polymer and olefin polymer |
| US9796799B2 (en) | 2012-09-25 | 2017-10-24 | Mitsui Chemicals, Inc. | Transition metal compound, olefin polymerization catalyst, and olefin polymer production process |
| US9896526B2 (en) | 2012-09-25 | 2018-02-20 | Mitsui Chemicals, Inc. | Process for producing olefin polymer and olefin polymer |
| CN108892746A (en) * | 2018-06-06 | 2018-11-27 | 山东泰和水处理科技股份有限公司 | A kind of preparation method of novel polypropylene acid salt aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2929746B2 (en) | 1999-08-03 |
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