JPH0229082B2 - AKURIRUAMIDOKEIKACHIONSEIKOBUNSHIRYOJUGOTAINOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an acrylamide cationic high molecular weight polymer. Since acrylamide-based cationic polymers are water-soluble polymers, they have many uses such as polymer flocculants, oil recovery aids, and fiber and paper processing agents. The polymers used for these are often
Those with high molecular weight are desirable. In particular, when used as a cationic polymer flocculant, a high molecular weight of several million or more is usually required. While it is desired to increase the molecular weight of acrylamide-based cationic polymers, a combination of initiators has been proposed as a method for increasing the molecular weight of acrylamide-based cationic polymers using N-aminoalkyl-substituted (meth)acrylamide as a monomer. Although methods by improving polymerization conditions such as the above have been studied, the reality is that a satisfactory increase in molecular weight has not been achieved by this method alone. In this specification, (meth)acrylic refers to acrylic and methacrylic.
It means either or both of the two types of compounds. We present N-aminoalkyl-substituted (meth)
As a result of extensive research into the polymerization of acrylamide, we have come to invent a new method for relatively easily obtaining a high molecular weight acrylamide-based cationic polymer. That is, in order to obtain an acrylamide-based cationic high molecular weight polymer, the raw material monomer N-
The present invention was completed by discovering that the method for producing aminoalkyl-substituted (meth)acrylamide greatly affects the molecular weight of the polymer. As a method for producing N-aminoalkyl-substituted (meth)acrylamide, (meth)acrylic acid or (meth)acrylic acid ester and a fatty acid are prepared in the presence of a tin-based catalyst as described in JP-A-56-100749. A method of manufacturing by directly reacting with a group or aromatic amine in a liquid phase (direct method). Japanese Patent Publication No. 57-50949
The method for producing β-aminopropionamide by thermal decomposition (β-aminopropionamide method) described in Japanese Patent Publication No. 49-66625 and the 5-N-substituted carboxy A method of manufacturing by thermally decomposing amide-2-norbornene (adduct method) is an industrially applicable manufacturing method. As a result of various studies on the polymerization properties of N-aminoalkyl-substituted (meth)acrylamide produced by these production methods, we found that N- For unknown reasons, when aminoalkyl-substituted (meth)acrylamide is used as a monomer, it is easier to produce acrylamide-based cationic polymers with higher molecular weight than monomers produced by the other two methods. It is possible to do so. The following table shows an example of the viscosity characteristics of copolymers obtained by copolymerizing N,N-dimethylaminopropylacrylamide and acrylamide produced by the direct method, β-aminopropionamide method, and adduct method in an aqueous solution. . It can be seen from this table that the copolymer according to the invention shows good results.

[Table] Polymerization conditions N,N-dimethylaminopropylacrylamide/acrylamide copolymerization molar ratio 1/3 Monomer concentration 13% aqueous solution Initiator Potassium persulfate, 0.5%/to monomer Polymerization temperature 40°C, polymerization time 1.5 hours N,N - The purity of dimethylaminopropylacrylamide was measured by gas chromatography.The reason why a high molecular weight polymer can be obtained by the method of the present invention is unknown, but the purity of dimethylaminopropylacrylamide produced by the adduct method is unknown.
Even if a similar experiment was performed using 97.4% N,N-dimethylaminopropylacrylamide, the viscosity
A copolymer of 80 c.ps was obtained, which is still much higher than the comparative example and cannot be explained solely by the purity of N,N-dimethylaminopropylacrylamide. It is thought that the nature of impurities during monomer production may be involved. The vinyl monomer for copolymerization used in the present invention can be selected from various types depending on the application, and examples of fields where it is used as a water-soluble polymer include (meth)acrylamide, (meth)acrylic acid, dimethylacrylamide, and diacetone acrylamide. A part of the water-soluble vinyl monomer can be replaced with another vinyl monomer as a third component within a range that does not affect the water-solubility of the resulting copolymer. Examples of the vinyl monomer as the third component include methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, and (meth)acrylonitrile. Common hydrophobic vinyl monomers used as water-insoluble polymers include methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, styrene, vinyl chloride, vinylidene chloride, and vinyl acetate as monomers for copolymerization. It is used as. Conventional known polymerization methods can be used to polymerize the above monomer mixture to obtain a copolymer. Aqueous solution polymerization is generally used as a method for obtaining a water-soluble copolymer, but methods such as reverse phase emulsion polymerization and precipitation polymerization may also be used. Usually, the aqueous solution polymerization method used has a monomer concentration of 5 to 60% by weight.
Using an aqueous solution of
It is added in an amount of 0.05 to 5% by weight and polymerized at a temperature of 30 to 90°C for 1 to 8 hours. As a method for obtaining a water-insoluble copolymer, emulsion polymerization is generally used, but methods such as solution polymerization and bulk polymerization may also be used. As the polymerization initiator used in the method of the present invention, various conventionally known ones can be mentioned,
For example, azo compounds such as azobiscyanovaleric acid sodium salt, azobisaminopropane hydrochloride, azobismethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, etc. organic peroxides, potassium persulfate, ammonium persulfate, hydrogen peroxide,
Examples include inorganic peroxides such as sodium perbromate. In addition, in the case of redox polymerization, inorganic compounds such as sodium bisulfite, sodium metasulfite, sodium thiosulfate, nitrite, ferrous sulfate, ferrous chloride, dimethylaniline, 3-dimethylaminopropionitrile, etc. are used as reducing agents. Organic compounds such as diethylamine and phenylhydrazine can be added. The method of the present invention does not have any special features in the polymerization method and the polymerization initiator, and the present invention is fully applicable to the method that is widely and generally adopted as a vinyl monomer polymerization method and a polymerization initiator. It is something that can be achieved. That is, if the same polymerization recipe is employed, the molecular weight of the acrylamide-based cationic polymer produced by the method according to the present invention is always large. The method of the present invention is advantageous for producing acrylamide-based cationic polymers for use in applications requiring high molecular weight. The present invention will be explained below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited in any way by the description of these Examples, and can be applied in various ways. Example 1 As described in Example 1 of JP-A-49-66625, 172 g of methyl acrylate was placed in a reaction vessel, and the reaction temperature was raised to 40°C while stirring and cooling with water.
132 g of cyclopentadiene was added dropwise while keeping the temperature below °C. After dropping and stirring for 5 hours, under reduced pressure,
Distillation yielded 276 g of 5-methylcarboxylate-2-norbornene. 228 g of this 5-methylcarboxylate-2-norbornene and N,N-
160 g of dimethylaminopropylamine and 3.6 g of sodium hydride were placed in a reaction vessel equipped with a thermometer and a stirrer, and reacted at 70°C for 6 hours. After the reaction was completed, the reaction solution was distilled under reduced pressure and 5-N
230 g of -(N',N'-dimethylaminopropyl)carboxamide-2-norbornene was obtained. 5mm of this 5-N-(N',N'-dimethylaminopropyl)carboxamide-2-norbornene
It was vaporized by heating under reduced pressure of Hg and passed through a hard glass decomposition column filled with Raschig rings heated to 450°C. The decomposition products were condensed and collected in a water-cooled condenser. This decomposition product was rectified under reduced pressure to obtain 105 g of a fraction having a temperature of 1 to 2 mmHg and 110 to 115°C. The purity of N,N-dimethylaminopropylacrylamide thus obtained by the adduct method was 99.5% as determined by gas chromatography. 8 g of the N,N-dimethylaminopropylacrylamide produced here and 15 g of acrylamide were added to water.
Place 100g of the liquid into a 300ml separable flask equipped with a stirrer, reflux condenser, and nitrogen inlet tube, introduce nitrogen gas for 30 minutes, and then add 1g of a 10% by weight aqueous ammonium persulfate solution and a 5% by weight aqueous sodium bisulfite solution. 1 g was added and polymerization was carried out at a temperature of 45° C. for 2 hours. After the polymerization was completed, the polymer was poured into acetone to precipitate the copolymer, which was separated, washed with acetone, and vacuum-dried at room temperature. The polymerization yield was 95.3%. This copolymer was dissolved in water to a concentration of 0.5% by weight, and the viscosity of this aqueous solution was measured at 20° C. using a B-type viscometer and found to be 150 c.ps. Comparative Example 1 As described in Example 8 of JP-A-56-100749, 300 g of ethyl acrylate was placed in a flask equipped with a thermometer and a 10-stage distillation column.
N,N-dimethylaminopropylamine 102.2g,
5 g of phenothiazine and 3 g of dibutyltin dimethoxide were added and heated until boiling. The azeotropic mixture of ethanol and ethyl acrylate to be distilled was reacted for 3 hours while being distilled at a tower top temperature of 77 to 80°C. The obtained reaction mixture was rectified under reduced pressure to give 1
97 g of a fraction of ~2 mmHg 110-115°C was obtained. The purity of N,N-dimethylaminopropylacrylamide thus obtained by the direct method was 99.4% as determined by gas chromatography. Also, as described in Example 1 of JP-A-57-50949, 135 g of methyl acrylate and 377 g of N,N-dimethylaminopropylamine were added in place of methyl methacrylate in a stainless steel autoclave of capacity 1, and 15 g of magnesium chloride was added. I put it in with. A nitrogen atmosphere was applied and the mixture was heated to 85°C and maintained at this temperature for 8 hours. After the reaction is completed, the reaction mixture is cooled, and 440 g of the reaction mixture is reduced to 402 g at 90°C under vacuum.
It evaporated to . 400 g of this product was placed in the dropping funnel of a 300 ml three-necked flask equipped with a magnetic stirrer, a thermometer, a Vigreux column with a distillation head, and a dropping funnel. Add N,N-diphenyl-p-phenylenediamine 3 to the flask.
g and 35 ml of the product in the dropping funnel,
The mixture was heated to 180° C. under reduced pressure and 1 to 2 mmHg. The decomposition products were quickly distilled and a replenisher was added through the dropping funnel to carry out the decomposition while maintaining the initial volume. The reaction temperature varied from 180 to 215 °C. After 4.5 hours of reaction, 400 ml of the feed liquid was added from the dropping funnel, and 293 g of decomposed products were distilled and condensed from the distillation head. The obtained decomposition product is rectified under reduced pressure,
84 g of a fraction having a temperature of 1 to 2 mmHg and 110 to 115°C was obtained. The purity of N,N-dimethylaminopropylacrylamide obtained by the β-aminopropionamide method in this way was 99.2% as determined by gas chromatography.
It was hot. N,N-dimethylaminopropylacrylamide obtained by the direct method and the β-aminopropionamide method was polymerized under the same polymerization conditions as in Example 1, respectively. The polymerization yields were 94.2% and 94.8%, respectively. Furthermore, the viscosity of a 0.5% aqueous solution of these copolymers at 20°C is 25 c.ps and 20 c.ps, respectively, which are very low values compared to the method of the present invention, indicating that the molecular weight of these copolymers is low. suggested. Example 2 N,N-dimethylamino produced by the adduct method according to the method of Example 1, using methyl methacrylate instead of methyl acrylate and N,N-dimethylaminoethylamine instead of N,N-dimethylaminopropylamine. ethyl methacrylamide
15.6g and N,N-dimethylacrylamide 9.9g
was placed in a 200ml three-necked flask equipped with a stirrer, thermometer and reflux condenser containing 60g of water, and after purging with nitrogen, a 10% by weight ammonium persulfate aqueous solution was added.
1.3g and 5% by weight sodium bisulfite aqueous solution
1.3g was added and polymerization was carried out at a temperature of 45°C for 2 hours.
After the polymerization is completed, the polymerized product is poured into acetone to precipitate the copolymer, separated, and washed with acetone.
Vacuum drying was performed at room temperature. The polymerization yield was 95.3%. This copolymer was dissolved in water to a concentration of 0.5% by weight, and the viscosity of this aqueous solution was measured at 20° C. using a B-type viscometer and found to be 150 c.ps. Comparative Example 2 Using the method of Example 1, using methyl methacrylate instead of ethyl acrylate and N,N-dimethylaminoethylamine instead of N,N-dimethylaminopropylamine, N,N-dimethylaminoethyl was prepared by a direct method. Acrylamide was produced.
Also, using methyl methacrylate instead of methyl acrylate and N,N-dimethylaminoethylamine instead of N,N-dimethylaminopropylamine, N,
N-dimethylaminoethyl acrylamide was produced. Polymerization was carried out under the same conditions as in Example 2 using N,N-dimethylaminoethyl acrylamide produced by the direct method and the β-aminopropionamide method, respectively. Polymerization yields were 93.6% and 94.1%, respectively.
It was %. The viscosities of 0.5% aqueous solutions of these copolymers at 20°C were 15 c.ps and 18 c.ps, respectively, which were very low values compared to the method of the present invention, indicating that the molecular weight of the copolymers was low. Ta. Example 3 8 g of N,N-diethylaminopropylacrylamide, 22 g of methacrylamide and 5 g of methyl acrylate was placed in a 200 ml glass autoclave containing 80 g of acetone, the autoclave was purged with nitrogen, a solution of 0.33 g of benzoyl peroxide dissolved in 5 g of acetone was added, and polymerization was carried out at a temperature of 60° C. for 3 hours. After the polymerization was completed, the precipitated copolymer was separated, washed with acetone, and vacuum-dried at room temperature. The polymerization yield was 96.7%. This copolymer was dissolved in water to a concentration of 0.5% by weight, and the viscosity of this aqueous solution was measured at 20° C. using a B-type viscometer and found to be 65 c.ps. Comparative Example 3 Using the method of Comparative Example 1, N,N-diethylaminopropylamine was used instead of N,N-dimethylaminopropylamine, and N,N was prepared by two methods: the direct method and the β-aminopropionamide method. - Diethylaminopropylacrylamide was produced. Polymerization was carried out under the same conditions as in Example 3 using N,N-diethylaminopropylacrylamide produced by the direct method and the β-aminopropionamide method, respectively. Polymerization yields were 94.7% and 94.7%, respectively.
It was 94.0%. 0.5% by weight of these copolymers
The viscosity of the aqueous solution is 10c.ps and 13c.ps at 20℃, respectively.
shows a very low value compared to the method of the present invention,
It showed that the molecular weight of the copolymer was low. Example 4 N,N-dimethyl produced by the adduct method according to the method of Example 1, using methyl methacrylate instead of methyl acrylate and N,N-dimethylaminobutylamine instead of N,N-dimethylaminopropylamine. Put 20 g of aminobutyl methacrylamide into a 200 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser containing 100 g of water.
After purging with nitrogen, 0.4 g of 2,2-azobis-(2-amidinopropane) hydrochloride was added, and polymerization was carried out at a temperature of 60° C. for 3 hours. After the polymerization was completed, the polymer was added to acetone to precipitate the polymer, which was separated, washed with acetone, and vacuum-dried at room temperature. The polymerization yield was 93.7%. This copolymer was dissolved in water to a concentration of 0.5% by weight, and the viscosity of this aqueous solution was measured at 20°C using a B-type viscometer and found to be 40 c.ps. Comparative Example 4 Using the method of Comparative Example 1, using methyl methacrylate instead of ethyl acrylate and N,N-dimethylaminobutylamine instead of N,N-dimethylaminopropylamine, N,N-dimethylaminobutyl was prepared by a direct method. Methacrylamide was produced. In addition, N,N-dimethylaminobutylacrylamide was produced by the β-aminopropionamide method using methyl methacrylate instead of methyl acrylate and N,N-dimethylaminobutylamine instead of N,N-dimethylaminopropylamine. . Polymerization was carried out under the same conditions as in Example 4 using N,N-dimethylaminobutyl methacrylamide produced by the direct method and the β-aminopropionamide method, respectively. Polymerization yields were 90.2% and 90.2%, respectively.
It was 92.3%. 0.5% by weight of these copolymers
The viscosity of the aqueous solution at 20℃ is 7c.ps and 10c.ps, respectively.
ps and the method of the present invention, it showed a very low value, indicating that the molecular weight of the copolymer was low. Example 5 6 g of N,N-dimethylaminopropyl methacrylamide and 40 g of diacetone acrylamide were produced by the adduct method according to the method of Example 1, using methyl methacrylate instead of methyl acrylate.
was placed in a 300 ml three-necked flask equipped with a stirrer, thermometer, and reflux condenser containing 155 g of water, and after purging with nitrogen, 2 g of a 10% by weight ammonium persulfate aqueous solution was added, and polymerization was carried out at a temperature of 50°C for 2.5 hours. .
After the polymerization was completed, the polymerization rate was determined by iodometry (determination of unreacted double bonds) and found to be 97.4%. The copolymer concentration of this aqueous solution polymer was set to 0.5% by weight.
Dilute with water until the viscosity is 20% using a B-type viscometer.
When measured at °C, it was 95 c.ps. Comparative Example 5 Direct method using the method of Comparative Example 1, using methyl methacrylate instead of ethyl acrylate;
N,N-dimethylaminopropyl methacrylamide was produced by the β-aminopropionamide method using methyl methacrylate in place of methyl acrylate. Polymerization was carried out under the same conditions as in Example 5 using N,N-dimethylaminopropyl methacrylamide produced by the direct method and the β-aminopropionamide method, respectively. The polymerization yields were 96.7% and 96.1%, respectively, by iodometry. When the copolymer concentration of these aqueous solution polymers was diluted with water to 0.5% by weight and the viscosity was measured at 20°C with a B-type viscometer, the viscosity was 22 c.ps and 30 c.ps, respectively. It shows a very low value compared to the method of the invention,
It showed that the molecular weight of the copolymer was low. Example 6 6 g of N,N-dimethylaminopropylacrylamide produced by the adduct method in Example 1 and 84 g of ethyl acrylate were placed in a nitrogen inlet tube containing 4.5 g of polyoxyethylene nonyl phenyl ether and 200 g of water, a reflux condenser, 500 with stirrer and thermometer
ml in a four-necked flask, and after passing nitrogen through it for 30 minutes while stirring, add 1 g of a 10 wt% potassium persulfate aqueous solution and 1 g of a 5 wt% sodium bisulfite aqueous solution, and emulsify at a temperature of 40°C for 2 hours. Polymerization was carried out. The emulsion obtained was a mechanically stable emulsion. This emulsion was poured into methanol to precipitate the copolymer, and after separation,
It was washed with methanol and vacuum dried at room temperature.
The polymerization yield was 97.3%. This copolymer was insoluble in water, and its viscosity was measured as a 0.5% by weight acetone solution at 20° C. using a B-type viscometer and found to be 30 c.ps. Comparative Example 6 Emulsion polymerization was carried out under the same conditions as in Example 6 using the N,N-dimethylaminopropylacrylamide produced by the direct method and the β-aminopropionamide method in Comparative Example 1, respectively. The resulting emulsion had good mechanical stability. The polymerization yields were 96.8% and 97.0%, respectively. These copolymers are also insoluble in water and have a viscosity of 20% using a B-type viscometer as a 0.5% acetone solution.
Measured at °C, 19c.ps and 22c.p., respectively.
s., and the difference in viscosity was smaller compared to the aqueous solution polymerization method, etc., but it showed a lower value than the method of the present invention.

Claims (1)

[Claims] 1. General formula (However, R ₁ represents hydrogen or a methyl group. R ₂ represents
It is represented by CnH ₂ n, and n represents an integer of 2 to 4.
R ₃ and R ₄ represent hydrogen or an alkyl group having 1 to 2 carbon atoms. ) 5-alkyl-5-N-(N',N'-dialkylaminoalkyl)carboxamide-2
-General formula obtained by thermally decomposing norbornene Production of a high molecular weight acrylamide-based cationic polymer characterized by polymerizing the monomer N-aminoalkyl-substituted (meth)acrylamide represented by or copolymerizing the monomer with another vinyl monomer. Method.