JPH0459883A - Water-soluble thickener flocculent - Google Patents

Abstract

PURPOSE:To obtain a thickener flocculent having increased molecular weight without increasing the amount of water-insoluble component and having improved shear resistance by polymerizing monomers containing anionic vinyl monomer, acrylamide, etc., as essential monomer components. CONSTITUTION:The objective thickener flocculent is composed of a copolymer produced by the polymerization of monomers containing (A) 0.05-10.0mol% (preferably 0.1-5.0mol%) of methylol (meth)acrylamide or diacetone acrylamide, (B) one or more kinds of anionic vinyl monomers selected from (meth)acrylic acid (salt), 2-acrylamide-2-methylpropane sulfonic acid (salt) and vinylsulfonic acid (salt) and (C) one or more monomers selected from (meth) acrylamide, N-methyl(meth)acrylamide and N,N-dimethyl(meth)acrylamide, as essential components.

Description

[Detailed description of the invention] [Industrial application field]

The present invention aims to increase the water solubility of (meth)acrylic synthetic systems used in applications such as water treatment agents, paper processing agents, soil conditioners, fiber processing agents, oil-water separation agents, oil drilling agents, and oil recovery agents. Adhesive/
It relates to flocculants.

[Conventional technology]

Conventional (meth)acrylic synthetic water-soluble thickeners and flocculants include those with high molecular weight (and high thickening performance, such as polyacrylamide, polyacrylamide partial hydrolyzate, and polyacrylamide/acrylate). Examples include polymers, polyacrylates, and the like.

[Problem to be solved by the invention] When using water-soluble thickeners and flocculants, they provide high performance even when added in small amounts due to their economical efficiency. In many cases, a polymer with a higher molecular weight is selected. However, if an aqueous solution of a thickener is mechanically degraded by shearing during dissolution, the aqueous solution will decrease in viscosity and its thickening effect will deteriorate. Efforts have been made to increase the molecular weight of polymers in order to further increase the viscosity. As a result, the thickening effect was hindered, and the molecular weight could not be increased beyond a certain limit. The purpose of the present invention is to provide a water-soluble thickener/flocculant that can exhibit performance more economically by increasing the molecular weight and improving shear resistance without increasing water-insoluble components. do,. [Measures to solve the problem a]

The present invention has been made by focusing on such conventional problems. i.e. from fat methylolmethacrylamide, methylolacrylamide or diacetone acrylamide, (b) acrylic acid (salt), methacrylic acid (salt), 2-acrylamido-2-methylpropanesulfonic acid (salt) and vinylsulfonic acid (salt) at least one selected anionic vinyl monomer and (c) acrylamide, methacrylamide, N-methyl (meth)acrylamide, N,N
- A water-soluble thickener/flocculant made of a copolymer formed by polymerizing a monomer whose essential component is at least one monomer selected from the group of dimethyl (meth)acrylamide and mixtures thereof. (Requirements constituting the means) The water-soluble thickener/flocculant of the present invention is as follows (al (b)
It consists of a terpolymer containing the three monomers (c) as essential components. As one essential component of fat monomer, one of methylol methacrylamide, methylol acrylamide, and diacetone acrylamide is used. (At least one monomer selected from the group of acrylic acid (salt), methacrylic acid (salt), 2-acrylamido-2-methylpropanesulfonic acid (salt), and vinylsulfonic acid (salt))
It is a species of anionic vinyl monomer and may be in the acid form or as a salt. Salts include alkali, alkali metal salts and alkaline earth metal salts. Monomer [c) At least one monomer selected from the group of acrylamide, methacrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and mixtures thereof is used. In addition to the above three monomers, acrylonitrile, dimethylaminoethyl methacrylate tertiary salt, quaternized products thereof, lower alkyl acrylic acid esters, etc. may be used as copolymerization components within a range that does not impair water solubility. Furthermore, the scope of the present invention is not limited to those produced by the above copolymerization reaction, but also those produced by converting the amide group into other functional groups through various chemical reactions after polymerization, such as those produced by hydrolysis with an alkali or methylolization. Can be used as a thickener or flocculant. Methods for copolymerizing the monomers (a), (b), and lc) include, for example, thermal polymerization using a redox or azo initiator, and photopolymerization using ultraviolet rays, but the method is not limited. The ratio of monomer (a) to the total monomer composition is 0.
05 mol% to 10.0 mol%, preferably 0.1
~5.0 mol%. If this composition ratio becomes too large, the insolubility will conversely increase and the purpose will not be achieved. The water-soluble thickener/flocculant of the present invention can be used as an oil drilling agent, oil recovery agent, soil conditioner, etc. by dissolving a predetermined amount in various (salt) aqueous solutions and liquids.
Used as a thickener or flocculant in fiber processing agents, water treatment agents, etc.

[Effect]

By adding a certain amount of the monomer (a) to the total monomer composition, it is possible to increase the molecular weight and reduce the insoluble content. This is probably because the monomer (a) effectively acts to increase the molecular weight of the thickener component. An aqueous solution using the product of the present invention has effects such as higher shear stability performance than conventional products having the same main component composition.

【Example】

The present invention will be explained in more detail with reference to Examples. 11 and above 21 Box-type polymerization apparatus (100 mm x 100 mm x 10
0 mm1 was placed in a chamber filled with nitrogen gas. Acrylamide, acrylic acid and N-
Methylolmethacrylamide or diacetone acrylamide was mixed in the molar ratio shown in Table 1-1, and each
were dissolved in distilled water, and the monomer solution was polymerized using the following procedure. (Monomer polymerization procedure) The prepared monomer solution is charged, and then nitrogen gas is blown from a nitrogen blowing tube to remove dissolved oxygen contained in the aqueous solution. After adding benzoin methyl ether and stirring uniformly, it was heated inside the cooling jacket at a light intensity of 50 W/m'' (measured by an ultraviolet luminometer) using an ultraviolet irradiation device installed at the top of the polymerization apparatus in the chamber. Polymerization was carried out for 30 minutes while passing water at 20°C into the solution to obtain a polymer. 1 to 5 and Example 1 The polymer with each monomer composition ratio obtained by the above method was treated with ion-exchanged water, 4% NaCJ2 solution, model salt woodworking. (90g/I
2 NaCR+20g712 CaCf22) to prepare a 0.1% polymer solution,
After keeping the temperature constant in a constant temperature bath at 5° C., the viscosity was measured using a B-type viscometer (Brookfield type, hereinafter abbreviated as B-type viscometer), and the results are shown in Table 1-2. Those containing N-methylol methacrylamide and diacetone acrylamide in the monomer composition had a greater thickening effect in all solvent compositions than those containing no monomer composition. (Left below) Box-type polymerization apparatus (100+nm x 100mm x 1) equipped with nitrogen blowing tube, thermometer, and cooling jacket
00 mm1 was placed in a chamber filled with nitrogen gas. In this polymerization apparatus, acrylamide and acrylic acid or 2-
Acrylamido-2-methylpropanesulfonic acid and N-
Methylol acrylamide or diacetone acrylamide was mixed at the molar ratio shown in Table 2-1, each dissolved in 270 mε distilled water, and the monomer solutions were polymerized according to the following procedure. (Monomer polymerization procedure) The prepared monomer solution is charged, and then nitrogen gas is blown from a nitrogen blowing tube to remove dissolved oxygen contained in the aqueous solution. After adding 1.5m℃ of benzoin methyl ether 1% acrylic acid solution and stirring uniformly, the light intensity was 50W/ba (UV illuminometer The polymerization was carried out for 30 minutes while passing water at 20° C. into the cooling jacket to obtain a polymerized product. 6 to 10 and 2 Polymers with each monomer composition ratio obtained by the above method were heated at 500 mI.
2 model salt water IT (150g/42 NaCj2+
35g/I2 CaCj! ,) in terms of solid content 015g
dissolve. Note that a stirrer bar is used for melting at approximately 1100 rpm.
Stirring was continued overnight at a speed of . Thereafter, the obtained polymer solution was filtered through a stainless steel screen of 200 mes, h, and the undissolved matter remaining on the screen was dried for 3 hours in a dryer at 105° C., and the weight was measured. Further, the temperature of the polymer solution that had passed through the screen was kept constant in a constant temperature bath at 25° C., and then the viscosity was measured using a screen viscometer. The screen viscometer is approximately 3
It is a screen viscometer having a fluid volume of 0 m°C and consisting of five 0.25 inch diameter 100 mesh stainless steel wire screens. These results are shown in Table 2-2. It was confirmed that the polymer containing N-methylolacrylamide and diacetone acrylamide in the monomer composition had less insoluble matter and higher viscosity than other polymers. I゛ 13-16 Box-type polymerization apparatus equipped with nitrogen blowing pipe, thermometer and cooling jacket f100mm x 100mm x 10
0 mm1 was placed in a chamber filled with nitrogen gas. In this polymerization apparatus, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, and N-methylolmethacrylamide were mixed in the molar ratio shown in Table 3-1, and
The monomer solution was dissolved in 70rnJ2 of distilled water, and the monomer solution was polymerized according to the following procedure. (Monomer polymerization procedure) The prepared monomer solution is charged, and then nitrogen gas is blown from a nitrogen blowing tube to remove dissolved oxygen contained in the aqueous solution. After adding 1.5 ml of benzoin methyl ether 1% acrylic acid solution and stirring uniformly, a light intensity of 50 W/g (according to an ultraviolet luminometer) was set using an ultraviolet irradiation device installed at the top of the polymerization apparatus in the chamber. The polymerization was carried out for 30 minutes while passing water at 20° C. into the cooling jacket (measured value) to obtain a polymer. 11-15 and ratio 3 The polymer obtained above and the polymer of Production Example N○11.12 were added to 500 mβ of model salt water 11 (150 g/42
N a CI2+ 35 g / 12 Ca C1
Dissolve 0.5g in terms of solid content in 22). Undissolved matter was removed from the dissolved polymer solution according to the procedures of Examples 6 to 10,
Maintain temperature at 25°C. Add 200mJ2 of the above polymer solution to a tube with an inner diameter of 6cm and a height of 15cm.
Place it in a cylindrical glass container with a diameter of 4 cm and a width of 1.5 cm.
The polymer solution is subjected to shear aging at 200 rpm for 5 minutes using a stirring blade of 50 m. The results of Brookfield type viscosity measurements before and after shear deterioration were as shown in Table 3-2. Those containing N-methylol methacrylamide and diacetone acrylamide in the monomer composition were more stable against shearing than those containing no monomer. 1' Notification Vfi 17~l 9 Methacrylamide, sodium acrylate and N-methylolacrylamide or N-methylolmethacrylamide are dissolved in pure water at the molar ratio shown in Table 4-1 and 100g
Then, ammonium persulfate was added as a polymerization initiator, and thermal polymerization was carried out at 40° C. while purging with nitrogen. The obtained polymer was poured into a large amount of methanol, and the precipitate was filtered and dried to obtain a powdered polymer. Examples 16 to 19 and Example 4 Monomer polymers obtained by the above method and production example No. 011.
12 polymers were dissolved in artificial seawater to prepare a C1.1% polymer solution for each, and filtered through a 200 mesh stainless steel screen. The filtered solution was kept at a constant temperature in a 25°C thermostat, and then transferred to a screen viscometer. The viscosity was measured. The results are shown in Table 4-2. (The following is a blank space) It was confirmed that a polymer containing N-methylol acrylamide, N-methylol methacrylamide, and diacetone acrylamide in the monomer composition had a higher viscosity than a polymer containing no monomer. 20 to 24 and 5 Using the polymers of production No. 1 to 6 listed in Table 1-1, a flocculation test of river gravel washing wastewater was conducted, and the results are shown in Table 1-1.
5. (Agglutination test method) Collect a sample into a test tube with a 100rnj2 volume scale. 1 ml of 0.04% by weight each polymer solution is added. After stirring this test tube by inverting it 10 times, the following evaluation is performed. Furthermore, the 5usspendedSolid of river gravel is 6
．． 0%, pH is 7.0. (Agglomeration effect evaluation items) Sedimentation rate: Immediately after stirring by inverting, measure the height at which the aggregates settle in 1 minute. Flock diameter: Visually compare the floc diameter. This is a relative comparison using the comparative example as the standard, with 10 being larger than the standard.
++ indicates even larger value. Table 5 From the results in Table 5, it can be seen that the samples of Examples have a greater aggregation effect.

【Effect of the invention】

By using the water-soluble thickener/flocculant according to the present invention, aqueous solutions with high +11 viscosity can be economically prepared, higher molecular weight polymers can be prepared, and the flocculation effect is greater. (2) Since the amount of insoluble matter is smaller than that of conventional products, it is easy to remove insoluble matter. (3) Since it has excellent stability against shearing, there is little decrease in viscosity and cohesive performance even when high shearing force is applied during use. Effects such as this can be obtained.

Claims (1)

[Scope of Claims] (a) Methylolmethacrylamide, methylolacrylamide or diacetone acrylamide (b) Acrylic acid (salt), methacrylic acid (salt), 2-acrylamide-2-methylpropanesulfonic acid (salt) and vinylsulfone At least one anionic vinyl monomer selected from acids (salts) and (c) from the group of acrylamide, methacrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and mixtures thereof. A water-soluble thickener/flocculant made of a copolymer obtained by polymerizing monomers containing at least one selected monomer as an essential component.