JPS6063210A - Manufacture of sulfonic acid group-containing acrylamide polymer - Google Patents

Abstract

PURPOSE:To efficiently obtain the titled polymer of ultrahigh molecular weight free from impurity component, by plasma-irradiation on acrylamide-methylpropane sulfonic acid followed by polymerization, in the absence of plasma, in an aqueous medium. CONSTITUTION:(A) A monomer selected from 2-acrylamide-2-metylpropane sulfonic acid, its ammonium salt and its alkalimetal salts is exposed to ionized gas plasma rays, normally following deaeration under a high vacuum. Next, in the absence of plasma, the monomer (A) or a combination of this monomer with (B) a vinyl monomer copolymerizable therewith (pref. of water-soluble type such as acrylamide) is polymerized in an aqueous medium (pref. water) to obtain the objective polymer. EFFECT:Obtainable at low cost in an energy-saving manner.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a sulfonic acid group-containing acrylamide polymer.

It has a wide range of uses as an acrylamide derivative and as a monomer with glaze characteristics. A
MPS is used as a copolymerizable dyeing agent for fibers and plastics, and its homopolymer or its copolymer is used as a polymer flocculant with excellent flocculating action, and is also used in kites, pulp industry, etc. It is widely used as a wastewater treatment agent and as a sludge dewatering agent in sewage treatment.

Furthermore, since it is an anionic polymer with a high degree of sulfonation, it is an extremely versatile polymer that is used as an ion exchange resin, a scale inhibitor, a sludge dispersant, and a polymer for oil recovery. The sulfonic acid group-containing acrylamide polymer C used as a flocculant is generally requested as specified in the specification, and the higher the molecular weight, the stronger the flocculating effect. Recently, there has been a demand for ultra-high molecular weight polymers with a molecular weight of, for example, 10 million or more.

Many methods have been developed to produce homopolymers, copolymers, etc. from 2-acrylamido-2-methylpropanesulfonic acid and its salts. For example, as a polymerization initiator, benzoyl peroxide, azobisisobutyronitrile,
Suspension polymerization or emulsion polymerization, and further solution polymerization using radical polymerization catalysts such as ammonium persulfate, redox polymerization catalysts such as potassium persulfate and acidic sodium jpijite, ammonium persulfate and monoethanolamine, etc. I can do it. In such methods, radical initiators, suspension agents, emulsifiers, solvents, etc. tend to remain in the polymer;
For that purpose, colored p, scales that are easy to understand, III
(It is also unfavorable in terms of tactility, inspection resistance, and weather resistance.Also,
In order to obtain a polymer with a high molecular weight, it is common to use a small amount of polymerization initiator and lower the polymerization temperature, but since the polymerization rate is slow in this method, the polymerization is
It is extremely difficult and impractical to do so in close proximity.

On the other hand, the present inventors have established a technology to obtain a linear water-soluble polymer with a much larger molecular weight than conventional polymers by polymerizing each vinyl chloride monomer using a plasma-initiated polymerization method. . 2-acrylamide-2 as its mB form
-A super absorbent polymer was obtained using methylpropanesulfonic acid, and this was proposed in Japanese Patent Application No. 57-49166.

Thereafter, the present inventors conducted various studies to make the technology more industrially unambiguous. Among these, the inventors discovered a phenomenon in which active species are generated by irradiating ionized gas plasma onto a solid material, and then instantaneously polymerizes when a water-based solvent is heated, and as a result of extensive research, the present invention was completed.

The purpose of the present invention is to provide a completely new polymerization method), and another purpose is to efficiently produce a sulfonic acid group-containing acrylamide polymer that is substantially free of impurities and has an extremely large molecular weight. We have found a way to manufacture it at low cost.
It's in there.

That is, the method of the present invention comprises at least one monomer (1
) is irradiated with an ionized gas plasma, and then, in the absence of the plasma, monomer (1) or a vinyl monocarrier copolymerizable with monomer (1) and an aqueous medium are mixed and post-polymerized. 1- It is characterized by:

The plasma used in the present invention refers to a so-called low-temperature plasma, which ionized gas plasma can be generated by any of the known methods C) for generating a powerful plasma. For example, J.

R, Ho1lahan and A, T, Bei+
・(Be1l) version "Application technology of plasma chemistry", Soi 1
No., New York 1974 and M.S.: r, y (
1, i.e., the monomer is placed under vacuum between parallel plate electrodes connected to a high frequency generator, and the monomer is placed under vacuum between parallel plate electrodes connected to a high frequency generator, and the monomer is placed under vacuum between parallel plate electrodes connected to a high frequency generator. Plasma can be generated using any of the parallel plates. Alternatively, an electric field may be created by an external induction coil to generate a plasma of ionized gas, or a plasma may be generated by placing oppositely charged electrodes spaced apart directly into a vacuum chamber.

After degassing the 1 L enclosure (IH: 1: solid at room temperature, and degassing the solid under a high vacuum (usually 10 to 10 Torr (10° to 1 opa) σ), it is irradiated with the above-mentioned ionized gas plasma. .

Ionized gas plasma is usually 20 to 200 watts, preferably 1
Glow release% at 40 to 100 watts Sase * 7
h body (1) h (i') M, injection lIi usually 1-36
A short time of 00 seconds, preferably 10 to 60 seconds is sufficient.

Most of the polymerization of the vehicle body (1) occurs during plasma irradiation, and even if it occurs, the amount is at most 2 weight.

If the polymerization rate of the monomer after irradiation is high, the polymer has a crosslinked structure, so when mixed with an aqueous medium and subjected to post-polymerization, the solubility may decrease, the polymerization may not proceed, or Kozuki-
The product may not have sufficient IJ properties or may become non-uniform.

After plasma irradiation, monomer (1) and an aqueous medium or monomer (1) and copolymerization E are carried out in the absence of plasma.
The J-functional vinyl AH compound and water are mixed and post-polymerized.

The 417 substance (1) applied to the present invention is 2-acrylamido-2-methylpropanesulfonic acid, or its ammonium salt, or any one or more of its alkali metal salts, which may be used. The choice of whether to use it or not should be made as appropriate depending on the purpose and performance.

The details of the active sites generated in monomer (1) by plasma irradiation are unknown, but since they are in a solid state, they do not initiate polymerization, but their activity is preserved and υ, Polymerization begins at a very rapid rate only when 6 is combined with the aqueous medium and dissolved.

Before mixing the aqueous medium and the plasma-irradiated monomer (1), or during or after mixing at t:1, a vinyl monomer capable of copolymerizing 5I with the monomer (1) is added. It is also possible to obtain a copolymer.

With the dome body (1)? The aqueous medium for mixing is water or a mixture of water and alcohols such as methanol, ethanol, butanol, ketones such as acetone, etc.
Gerari and Ru, but for reasons unknown, Mizuzumedoku is preferable in terms of polymerization rate and molecular weight. The monomer concentration in the aqueous medium is usually at most 90% by weight, preferably from 1υ to 60% by weight, preferably from 5 to 75% by weight. Although the polymerization rate is high when the monomer concentration is high or when the mixture is mixed, the polymerized product becomes extremely viscous and difficult to handle.When the monomer concentration is low, it is not efficient.10 Organic solvents such as dimethylsulfamide can also be used as a medium, but In general, an aqueous medium is preferable unless the polymerization rate is slow and q1 is specifically required. The aqueous medium may be added immediately after the plasma is irradiated with heat, or may be added after the plasma is irradiated and left as is for a while.

The present inventors have confirmed that even if soaked water that has been left for 10 hours after plasma irradiation is added, extremely good incorporation properties are exhibited.

In addition, when leaving it after plasma irradiation, it is best to leave it in 14 air, but it may also be in an inert gas such as nitrogen or argon. is saved.

The vinyl B, it isomer copolymerizable with Kishi b1 isomer (1) is not particularly limited as long as it undergoes radical polymerization. Generally, acrylonitrile, acrylic ester, methacrylic ester, styrene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylamide, methacrylamide.

Neutral monomers such as 11-vinylpyrrolidone, acrylic acid, methacrylic acid, P-styrenesulfonic acid, vinylsulfonic acid, 2-methacryloylmexyethylsulfonic acid, 6-methacryloyloxy-2-hydroxypropylsulfonic acid, allylsulfone acid, acidic monomers such as methallylsulfonic acid, ammonium salts and alkali metal salts thereof, and 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, 2-vinylpyridine and cyclic monomers such as 4-vinylpyridine, and hydrochloric acid thereof,
Examples include silicic acid, dimethyl sulfate, diethyl sulfate, and quaternized products such as ilt ethyl chloride.

The vinyl nail repellent is preferably water-soluble,
More preferably acrylamide, methacrylamide, N
-Vinylpyrrolidones, acrylic acid, methacrylic acid, P
-Styrenesulfonic acid, vinylsulfonic acid, 2-methacryloylmexyethylsulfonic acid, 3-methacryloyloxy-2-hydroxypropylsulfone fJ,
7! J Lux Sulfonic acid, methallylsulfonic acid, and their ammonium salts, alkali metal salts,
2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl acrylate, and diethylaminoethyl methacrylate, 2-vinylpyridine and 4-vinylpyridine and their salts, nitric acid, dimethyl sulfate, diethyl sulfate or ethyl chloride These are quaternary compounds of

Prazu-r initiated polymerization according to the method of the present invention proceeds well in a system in which monomer (1) is present, but if all copolymerizable vinyl polymers are added at the same time, the amount used depends on the polymerizability and the intended use. need to be considered. Monomer (1
) and acrylamide, methacrylamide, etc. If monomer (1) is 5% by weight or more and acrylamide or methacrylamide is less than 95% by weight, a polymer with a good polymerization rate and a very large molecular weight can be obtained. can get.

The postpolymerization temperature and time vary depending on the type of monomer used and are not particularly limited, but usually a temperature of at most 100°C and a time of 1 to 25 hours are sufficient. Depending on the type of monomer, if the temperature exceeds 60°C, thermal polymerization may occur and a low molecular weight polymer may be produced, so care must be taken.

A major feature different from other polymerization methods is that the acrylamide polymer containing sulfonic acid groups obtained by the method of the present invention does not contain anything other than monomer components.

Other JR methods use radical initiators and suspending agents.

Although emulsifiers and the like tend to remain and are difficult to completely remove, the method of the present invention does not use these additives and therefore does not contain these impurity components.

The sulfonic acid group-containing acrylamide polymer obtained by the method of the present invention is ultra-high molecular weight and does not contain any impurities. It is also an innovative method that has a high polymerization rate and requires less raw materials and energy.

The present invention will be explained in detail below with reference to Examples.

The intrinsic viscosity was determined by leaving the polymer or its polymer in an aqueous U or IN NacQ solution overnight, dissolving it to a constant concentration, and measuring the viscosity at 50° C. using an Ostold viscometer.

Example 1 2-acrylamido-2-methylpropanesulfonic acid 1
．． After putting 5 fl into a 20 mQ ampoule and degassing at 10-5 Torr, the ZAMCO INTERNATIONAL MPD-2L7) outputs up to 150 watts. 10 ampoules
A glow discharge plasma generated at 0 watts of power was applied for 50 seconds.

Next, 4.0 g of water degassed under reduced pressure was added, and the tube was sealed.
It was immersed in a constant temperature bath at 25° C. and polymerization was carried out after a predetermined period of time. The polymer was taken out from the ampoule, and the polymerization rate and viscosity of this polymer were measured.

In addition, after dissolving 1.5 g of the above 2-acrylamido-2-methylpropanesulfonic acid in 4.0 Ii of water, 20 m
After degassing with 1O-5)-l in an ampoule of n, the polymer was frozen with liquid nitrogen, degassed three times, irradiated with the above plasma for 50 seconds, sealed the tube, and polymerized after 5 hours at 25°C. The results are shown for reference.

The limiting viscosity of Table 1 A6 and Mu7 is 115.5 dμ force 1, respectively.
It was 15.5clJ4/9.

Example 2

Claims (1)

[Claims] 1) After irradiating at least one monomer (1) selected from 2-acrylamido-2-methylpropanesulfonic acid, its ammonium salt, and its alkali metal salt with ionized gas plasma. , a sulfone characterized in that monomer (1), or a vinyl monomer copolymerizable therewith, and an aqueous medium are mixed and post-polymerized in the absence of the plasma. A method for producing an acid group-containing acrylamide polymer. 2) The manufacturing method according to claim 1, wherein the ionized gas plasma is obtained by degassing under a vacuum of 10'' to 10 Torr and then irradiating at 20 to 200 Watts for 1 to 3,600 seconds. 5) The ionized gas plasma can be obtained by degassing under a vacuum of 10-1 to 10-1, and then irradiating at 40 to 100 watts for 10 to 60 seconds. Manufacturing method described. 4) The process according to claim 1, wherein the postpolymerization in the absence of an ionized gas plasma is carried out at a temperature of at most 100°C. 6) Claim 1 in which the vinyl monomer is water-soluble
The manufacturing method described in item or g35. 7) The production method according to claim 1, 5, or 6, wherein the vinyl monomer is acrylamide, methacrylamide, or N-vinylpyrrolidone. 8) A patent claim in which the vinyl monomer is acrylic acid, methacrylic acid, vinylsulfonic acid, 2-methacryloyloxyethylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, and ammonium salts and alkali metal salts of these acids. The manufacturing method according to item 1, item 5, or item 6. 9) Vinyl monomers are 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2
- A method for producing diethylaminoethyl acrylate, 2-diethylaminoethyl methacrylate, 2-vinylpyridine, and 4-vinylpyridine, and basic monomers thereof such as hydrochloric acid, nitric acid, dimethyl sulfate, and diethyl sulfur. 11) The production method according to claim 1, wherein the monomer concentration in the aqueous medium is at most 20% by weight. 12) The manufacturing method according to claim 1 or 11, wherein the monomer concentration in the aqueous medium is 5 to 75% by weight. 1'5) Monomer humidity in aqueous medium is 10-600-6
0% by weight Claim 1 or 11 f-1:
The manufacturing method according to item 12.