JPH09151217A - Anionic water-soluble polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an anionic water-soluble vinyl polymer which has a high molecular weight, is uniformly dissolved in a water solution of a salt particularly the one containing a large amount of a multi-valency metal and exhibits an excellent aggregating and thickening effect by subjecting 2 kinds of specified vinyl monomers to copolymerization. SOLUTION: This anionic water-soluble vinyl polymer is a copolymer consisting of (A) a vinyl monomer as expressed by the formula CH2 =C(R)- COOZSO3 X (R is a hydrogen atom or a methyl group; X is an alkali metal or an alkaline earth metal; Z is a 7 or less C hydrocarbon group) and (B) a vinyl monomer as expressed by the formula CH2 =C(R)-CONHZSO3 X (R is a hydrogen atom or a methyl group; X is an alkali metal or an alkaline earth metal; Z is a 7 or less C hydrocarbon group). Preferably the molar number of A is 10-90% of the total molar number of A and B. This anionic water-soluble vinyl polymer has usually an intrinsic viscosity of 4 or more measured at 30 deg.C in 1N-NaNo3 .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dispersant for oil well drilling, a polymer for secondary and tertiary recovery of crude oil, a polymer flocculant for treating wastewater, a conductive agent for electrostatic recording paper, an antistatic agent, a retention aid for papermaking. And a novel anionic water-soluble polymer useful as a sticky agent for papermaking.

[0002]

2. Description of the Related Art Conventionally, as anionic water-soluble polymers, acrylamide without polyacrylamide hydrolyzate, sodium acrylate copolymer, and terpolymers obtained by copolymerizing sulfone monomers such as polystyrene sulfonate and poly Sodium salts of sulfobutyl (meth) acrylamide, sodium polystyrene sulfonate, etc. were known.

[0003]

However, conventional water-soluble polymers have drawbacks such as low molecular weight, poor solubility in an aqueous solution containing a large amount of salts, especially polyvalent metal salts, and low viscosity and cohesiveness. there were.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies to find a method for solving these problems. That is, the present invention is a copolymer (C) comprising a vinyl monomer (A) represented by the following general formula (1) and a vinyl monomer (B) represented by the following general formula (2). Water soluble polymer. _{CH 2 = C (R) -COOZSO} 3 X (1) { wherein, R represents a hydrogen atom or a methyl group, X is an alkali metal or alkaline earth metal, Z is a hydrocarbon group having 7 or less carbon atoms. _{} CH 2 = C (R)} -CONHZSO 3 X (2) { wherein, R represents a hydrogen atom or a methyl group, X is an alkali metal or alkaline earth metal, Z is a hydrocarbon group having 7 or less carbon atoms. ｝

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the vinyl monomer (A) represented by the general formula (1) in the present invention include soda salt, potassium salt, magnesium salt and sulfopropyl (meth) acrylate of sulfoethyl (meth) acrylate. Examples thereof include soda salt, potassium salt, magnesium salt and the like.
Of these, preferred are sulfoethyl (meth) acrylate soda salts, potassium salts, and magnesium salts from the industrial viewpoint.

Examples of the vinyl monomer (B) represented by the general formula (2) in the present invention include sulfoethyl (meth) acrylamide soda salt, potassium salt, magnesium salt, sulfobutyl (meth) acrylamide soda salt and potassium salt. , Magnesium salts and the like. Of these, from the industrial viewpoint, preferred are sulfobutyl (meth) acrylamide soda salt, potassium salt, and magnesium salt.

In the present invention, the number of moles of (A) with respect to the total number of moles of (A) and (B) can be arbitrarily selected according to the purpose, but usually 20 to 90% is preferable from the viewpoint of performance and cost. If it is less than 20%, the cost usually increases, and 90%
If it exceeds, performance may decrease.

In the present invention, the copolymer (C) is
In addition to (A) and (B), other vinyl monomers may be appropriately copolymerized. Examples of the type and the amount of copolymerization are disclosed in, for example, Japanese Patent Publication No. 6-92447. Among the other vinyl monomers, among them, (meth) acrylamide monomers and / or (meth) acrylic acid or salts thereof are preferred. This is because the copolymerization of these makes it easier to increase the molecular weight of the resulting water-soluble polymer. In addition, there is no limitation on the amount of these to be copolymerized, but in general, from the viewpoint of performance (meth)
Acrylamide monomers account for 98 mol% or less of all monomers, and (meth) acrylic acid (or its salt) accounts for 97 mol% or less of all monomers. If the copolymerization amount of these exceeds these, it is difficult to obtain the effect intended by the present invention.

The water-soluble polymer of the present invention is usually 1N-N
The intrinsic viscosity (dl / g) measured at 30 ° C. in aNO ₃ is 4 or more, preferably 12 or more. If the intrinsic viscosity is low, the molecular weight may be insufficient and the effect may be insufficient.

The product form of the water-soluble polymer of the present invention is powder, film, aqueous solution, w / o emulsion,
A known arbitrary shape such as a suspension shape may be used.

The water-soluble polymer of the present invention is usually used as it is in an aqueous solution, but depending on the purpose, a thickener,
You may use together with other materials, such as a neutralizer, a weighting agent, a dispersant, an antiseptic | preservative, an inorganic salt, and a polymer coagulant suitably. When the water-soluble polymer of the present invention is used in an aqueous system such as a dispersant for oil well drilling, a crude oil secondary and tertiary recovery polymer, a coagulant for wastewater treatment, a retention aid for papermaking, and a sticky agent for papermaking, the present invention is more suitable. In order to enhance the effect of the water-soluble polymer,
If possible, it is desirable to keep it neutral (pH about 5 to about 8).

In the present invention, the method of copolymerizing (A), (B) and, if necessary, other monomers is not particularly limited, and examples thereof include Japanese Patent Publication No. 6-92447 and Japanese Patent Laid-Open No. 7-92447.
No. 242702, for example.

[0013]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Examples 1 to 4 and Comparative Examples 1 to 4 Monomers having various compositions shown in Table 1 were added to ion-exchanged water at a concentration of 1
Dissolve to 3% by weight, replace with nitrogen, adjust the temperature to 40 ° C, and add potassium persulfate and sodium bisulfite as polymerization catalysts in this order at 0.01% by weight per monomer to polymerize. It was The obtained polymerization liquid (gel) was freeze-dried to isolate the polymer as a powder, and the intrinsic viscosity and salt aqueous solution characteristics of the obtained polymer were tested. Regarding the salt aqueous solution characteristics, polymer powder was added to concentrated calcium chloride aqueous solution (concentration 26%) so that the polymer concentration was 1%, and the mixture was stirred at room temperature for 1 hour. First, the solubility was examined, and when dissolved, Brookfield was used. The viscosity was measured. The test results are shown in Table 1. All of the anionic water-soluble polymers of the present invention (Examples 1 to 4) had a high intrinsic viscosity and were uniformly dissolved in salt water to show a high viscosity. In No. 4, the intrinsic viscosity was low, and the one that was not dissolved in salt water or was dissolved was also low in viscosity.

[0015]

[Table 1] NaSEA: Sulfoethyl (meth) acrylate soda salt NaAMPS: Sulfobutyl (meth) acrylamide soda salt AAm: Acrylamide NaAC: Sodium acrylate

[0016]

The anionic water-soluble polymer of the present invention is
Not only has a high molecular weight, but it is also highly soluble in aqueous solutions containing large amounts of salts, especially polyvalent metals.
Gives high aggregation performance. Therefore, the anionic water-soluble polymer of the present invention is used for oil well drilling dispersants, crude oil second and third recovery polymers, wastewater treatment polymer flocculants, electrostatic recording paper conductive agents, antistatic agents, and papermaking. It is extremely useful as a retention aid and a sticky agent for papermaking.

Claims (4)

[Claims] 1. An anion which is a copolymer (C) comprising a vinyl monomer (A) represented by the following general formula (1) and a vinyl monomer (B) represented by the following general formula (2). Water-soluble polymer. _{CH 2 = C (R) -COOZSO} 3 X (1) { wherein, R represents a hydrogen atom or a methyl group, X is an alkali metal or alkaline earth metal, Z is a hydrocarbon group having 7 or less carbon atoms. _{} CH 2 = C (R)} -CONHZSO 3 X (2) { wherein, R represents a hydrogen atom or a methyl group, X is an alkali metal or alkaline earth metal, Z is a hydrocarbon group having 7 or less carbon atoms. ｝ 2. The polymer according to claim 1, wherein the number of moles of (A) is 20 to 90% with respect to the total number of moles of (A) and (B). 3. The polymer according to claim 1, wherein (C) is a copolymer of (meth) acrylamide monomer and / or (meth) acrylic acid or a salt thereof. 4. The polymer according to claim 1, which has an intrinsic viscosity of 4 or more measured in 1N-NaNO ₃ at 30 ° C.