JPS5920311A - Production of cationic high-molecular weight acrylamide polymer - Google Patents

Abstract

PURPOSE:To facilitate the production of a high-MW acrylamide cationic polymer, by polymerizing a monomeric N-aminoalkyl-substituted (meth) acrylamide which is obtained by thermally decomposing a specified compound. CONSTITUTION:Monomeric N-aminoalkyl-substituted (meth)acrylamide of formula III which is prepared by thermally decomposing 5-alkyl-5-N-(N', N' -dialkylaminoalkyl)carboxamido-2-norbornene of formula I (wherein R1 is H or methyl, R2 is formula II, n is 2-4, and R3 and R4 are each H, or 1-2C alkyl is polymerized or this monomer is copolymerized with other vinyl monomers. The reason why it is possible to produce a high-MW polymer by the above process is not clear, and it is not possible to interpret this as the result of the purity of the N-aminoalkyl-substituted (meth) acrylamide. It is considered that the impurities formed during the production of the monomer have concern with it.

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 bathable polymers, polymer flocculants 1 oil recovery aids,! It has many uses such as textile and paper processing agents. The polymers used in 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 60,000 or more is usually required.

While it is desired to increase the molecular weight of acrylamide-based cationic polymers, a method for increasing the molecular weight of acrylamide-based cationic electropolymers using N-aminoalkyl-substituted (meth)acrylamide as a monomer has been developed using an initiator. Although methods by improving polymerization conditions such as combinations have been studied, the reality is that satisfactory high molecular weight has not been achieved by this method alone.

In this specification, (meth)acrylic...
``...'' means either or both of the following two compounds: acrylic and methacrylic.

The present inventors conducted intensive research on the polymerization of N-aminoalkyl-substituted (meth)acrylamide, and as a result, they came up with 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, rather than improving polymerization conditions by combining initiators, etc., the manufacturing method of N-aminoalkyl-substituted (meth)acrylamide, which is a raw material monomer, is improved. The present invention was completed by discovering that this has a large effect on molecular weight.

As a method for producing N-aminoalkyl-substituted (meth)acrylamide, in the presence of a tin-based catalyst, (meth)acrylic acid or (meth)acrylic acid ester and S A method for producing by 1ti-contact reaction with a ribatic or aromatic amine in a liquid phase (direct method). A method for producing β-aminopropionamide by thermal decomposition (β-aminopropionamide method), which is described in JP-A-57-50949, etc., and a method described in JP-A-49-66625. A method of producing 5-N-substituted carboxamide-2-norbornene by thermal decomposition (adduct method) is an industrially applicable production method. As a result of various studies on the polymerization properties of fcN-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 polymer, it is easier to produce a high-molecular-weight acrylamide-based cationic polymer compared to 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. 0 It can be seen from this table that the copolymer according to the present invention shows good results.

Table Polymerization conditions N,N-dimethylaminopropylacrylamide/acrylamide copolymerization molar ratio 1/8 Monomer concentration 18% aqueous solution Initiator Potassium persulfate, 0.5%/based on seven polymerization temperature 40°C 2 Polymerization time 1.5 hours The purity of N,N-dimethylaminopropylacrylamide was measured using a gas chromatograph.The reason why a high molecular weight polymer can be obtained by the method of the present invention is unknown, but the purity of N,N-dimethylaminopropylacrylamide is 1+1! Even if a similar experiment was conducted using N,N-dimethylaminopropylacrylamide with a purity of 97.4, a copolymer with a viscosity of 80 c, p, s was obtained, and compared with the comparative example. Still showing much higher values, the purity of N,N-dimethylaminopropylacrylamide alone cannot be explained. It is thought that the nature of impurities during monomer production may be involved.

As the vinyl monomer for copolymerization used in the present invention, two types can be selected depending on the application.For example, (meth)acrylamide, (meth)acrylamide,
A water-soluble vinyl monomer such as acrylic acid, dimethylacrylamide, diacetone acrylamide, etc. may be used as the eighth component within a range that does not affect the water solubility of the resulting copolymer.

It is also possible to replace a portion of the water-soluble vinyl monomer with vinyl monomer. Examples of the vinyl monomer as the third component include methyl (meth)acrylate, ethyl (meth)acrylate, and hydroxyethyl (meth)acrylate-(meth)acryloni). 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 a crop.

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 precipitated P# filtration may also be used.

Usually, the aqueous solution polymerization method used is to use an aqueous solution with a monomer concentration of 5 to 60 monomers, and blow an inert gas such as nitrogen gas into the water bath solution so that oxygen is present in the polymerization system.
7 and add water-soluble Togane initiator to the monomer.

Add in the range of 0.05 to 5.80 to 9.0
Polymerization is carried out in the range of 0°C for 1 to 8 hours.

Emulsion polymerization is a common method for obtaining water-insoluble copolymers, but bath liquid polymerization 1. Methods such as bulk polymerization may also be used.

As the polymerization initiator used in the method of the present invention.

Various conventionally known compounds can be mentioned, such as azo compounds such as azobiscyanovaleric acid sodium salt, azobisaminopropane hydrochloride, azobismethylvaleronitrile, azobisisobutyronitrile, and benzoyl peroxide. , organic peroxides such as lauroyl peroxide, tertiary butyphrenoid lobar oxide, potassium persulfate, ammonium persulfate, hydrogen peroxide,
Examples include inorganic peroxides such as perbromic acid and IJium. In addition, in the case of redox polymerization, sodium bisulfate and sodium metasulfite are used as reducing agents.

Inorganic compounds such as thiosulfate, nitrite, ferrous sulfate, and ferrous chloride, and organic compounds such as dimethylaniline, 3-dimethylaminopropionitrile, 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 can be carried out using a method that is widely and generally adopted as a vinyl monomer polymerization method and a polymerization initiator. This will be achieved.

That is, if the same polymerization recipe is employed, the molecular weight of the acrylamide-based cationic polymer produced by the two methods of the present invention is always larger. 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; however, the scope of the present invention is not limited in any way by the description of these Examples, and the present invention can be applied in two different ways.

Example 1 As described in Example 1 of JP-A-49-66625, 172f of methyl acrylate was added to a reaction vessel, and while stirring and keeping the reaction temperature below 40°C by cooling with water, cyclopentane was added. Jie 7182t was added dropwise. After the dropwise addition, the mixture was stirred for 5 hours and then distilled under reduced pressure to obtain 27 fl of 5-methylcarboxylate-2-norbornene. This 5-methylcarboxylate-2-norbornene 22
8f and N, N-dimethyl aminopro pylamine
16 (1) and sodium hydride (36?) were placed in a 1z reaction vessel equipped with a thermometer and a stirrer, and allowed to react at 70°C for 6 hours. After one reaction was completed, the reaction solution was placed under reduced pressure.

Distilled to give 5-N-(N',N',-dimethylaminopropyl)carboxamido-2-norbornene28
I got 02. This 5-N-(N',N'-dimethylaminopropyl)carboxamide-2-norbornene 2
00 tons was heated under reduced pressure of 5 kakudama to vaporize it, 45
Heated to 0°C. It was passed through a hard glass cracking tower filled with Raschig rings. The decomposition products were condensed and collected in a water-cooled condenser, and the decomposition products were distilled under reduced pressure, and
A fraction 105f of 110-115°C was obtained. The purity of N,N-dimethylaminopropylacrylamide thus obtained by the adduct method was 99.5% as determined by gas chromatography.

N,N-dimethylamine produced here, 8v of nobrovir acrylamide and 15f of acrylamide were mixed with 100f of water.
8 equipped with a stirrer, a jet cooler, and a nitrogen gas tube.
00-Person ft in separable flask.

After introducing elementary gas for 80 minutes, add a 10% by weight ammonium persulfate aqueous solution (lt) and a 5M amount of hydrogen sulfite (l).
) 1 r of Rum aqueous solution was added and polymerization was carried out at a temperature of 45"C for 2 hours. After the polymerization was completed, 9 polymerized products were poured into acetone,
The copolymer was precipitated, separated by F, washed with acetone, and dried under vacuum at room temperature. The polymerization yield was 95.8%.

This copolymer was dissolved in water to a weight ratio of 0.5,
The viscosity of this aqueous solution was measured at 20°C using a B-type viscometer and found to be 150 c, p, s.

Comparative Example l Ethyl acrylate 80 (1,N,N-
Add dimethylamine propylamine 102.2F, phenothiazine 5 and dibutyltin dimethoxide 89,
Heat to boiling point +4. The azeotropic mixture of ethanol and ethyl acrylate produced in 4 was reacted for 8 hours while being distilled at a tower top temperature of 77 to 80°C. The obtained reaction mixture was distilled under reduced pressure into #I column, and 1 to 2 columns Hy l l O~1
A 15"C fraction, 971, was obtained. The purity of N,N-dimethylaminopropylacrylamide obtained by the direct method was 99°4.
As described in Example 1 of Father 2% Publication No. 57-50949, methyl acrylate 185r and N,N-dimethylaminopropylamine 377v were added to a stainless steel plate with a capacity of 1z instead of methyl methacrylate. It was placed in an autoclave together with 15f of magnesium chloride. A nitrogen atmosphere was applied and the mixture was heated to 85"C and maintained at this temperature for 8 hours. After the reaction was completed.

Cool the reaction mixture and add 2 reaction mixtures 44. 4. At 90℃ in an empty room. (It evaporated to 12? This product 4
00t as magnetic stargy. thermometer.

It was placed in a Vigreux column equipped with a distillation head and a dropping funnel of an Lfc800-Mitsuro flask with a dropping funnel e.

N,N-diphenyl-p-phenylenediamine 8 and the product 85 in the dropping funnel were added to a flask, and heated under reduced pressure to a temperature of 180°C for 1 to 2 hours to rapidly distill the decomposed product. Replenishment was added using a dropping funnel, and the initial volume was maintained while disassembly was carried out. The reaction temperature is 180
The temperature changed to ~215°C. After 4.5 hours of reaction, 4,00 mg of supplied R+ was added from the 9 dropping funnel, and the decomposition product 2982 was distilled from the distillation head and condensed.
The obtained decomposition product is rectified under reduced pressure to 1 to 2 mmH?
.

110~], fraction 84 at 15°C? The purity of the N,N-dimethylaminopropylacrylamide thus obtained by the β-aminopropionamide method was 99.2% as determined by gas chromatography. The N,N-dimethylaminepropylacrylamide obtained by the ffi contact method and the β-aminopropionamide method was removed and subjected to polymerization under the same polymerization conditions as in Example 1.

The polymerization yields were 94.2%+94.8%, respectively. In addition, the viscosity of the 05w'lth% water bath solution of these copolymers at 20°C is 25C, μs, 20c, respectively.
Example 2 Using the method of Example 1, methyl methacrylate and methyl methacrylate were used instead of methyl acrylate in the method of Example 1. 15.62 tons of N,N-dimethylaminoethylmethacrylamide and 9.9t of N,N-dimethylacrylamide were prepared by an adduct method using N,N-dimethylaminoethylamine instead of propylamine. It was placed in a 200 m Mitsuro flask equipped with a stirrer, a thermometer and a reflux condenser containing 60 tons of water, and after purging with nitrogen, it was placed in a 1.82% aqueous solution of ammonium persulfate of 10% by weight and a sodium bisulfite water bath of 5% by weight. Add 1°8f of liquid and conduct polymerization for 2 hours with 45"C. After the end of fC0 electrolysis, the polymer was poured into acetone to precipitate the copolymer. After separating from F, it was washed with acetone. .

The copolymer yield after drying at room temperature was 95.8%. This copolymer was dissolved in water to a concentration of 0.5% i.
When the viscosity of this aqueous solution was measured at 21)"C using a B-type viscometer, it was 150c, βS, and fc.

Comparative Example 2 Using the method of Comparative Example 1, using methyl methacrylate instead of ethyl acrylate and N,N-dimethylaminoethylamine instead of N,N-dimethylaminepropylamine, N,N-dimethylaminoethyl was prepared by a direct method. Acrylamide was produced. Also, methyl methacrylate was used instead of methyl acrylate, and N,N-dimethylaminoethylamine was used instead of N,N-dimethylaminopropylamine.

Example 2 Using the 0 direct method in which N,N-dimethylaminoethyl acrylamide was produced by the β-aminopropionamide method and the N,N-dimethylaminoethyl acrylamide produced in the β-aminopropionamide method, respectively.
The zero polymerization yield when polymerization was carried out under the same conditions as
．． 6%, 0.5 of these copolymers with 941%
The viscosity of the wt% aqueous solution is 15 c at 20”C, respectively.
p, s, : l 8c, p, s, which is a very low value compared to the method of the present invention.

It showed that the molecular weight of the copolymer was low.

Examples N,N-diethylaminepropylacrylamide 82 and methacrylamide 22 produced by the adduct method using the method of Example 1, using N,N-diethylaminepropylamine instead of N,N-dimethylaminopropylamine, and Methyl acrylate 57 was placed in a 200 rrt glass autoclave containing acetone Bof.
After purging with nitrogen, a solution of 0.83% benzoyl oxide dissolved in 52% acetone was added, and polymerization was carried out at a temperature of 60°C for 8 hours. After the polymerization was completed, a precipitate was formed, and the copolymer was taken from door to door. It was washed with acetone and vacuum dried at room temperature. The polymerization yield was 96.7%.

This mixture was mixed with water so that it became (1, Fl fN %), and the viscosity of this aqueous solution was measured with a one-type viscometer to be 2.
When measured at 0''C, it was (S5c,p,S).

Comparative Example 3 Using the method of Comparative Example 1, N,N-diethylaminopropyl acrylamide was prepared using N,N-dimethylaminopropylamine by two methods: the direct method and the β-aminopropionamide method. 7jN,N-diethylaminepropyl aqueous I7 7
Polymerization was carried out under the same conditions as in Example 3 using -amide, respectively. The fcO electrolyte kneading yields were 94.7% and 9-(
■It was. The viscosity of the 0.5 liter volume of these copolymers is 78. The viscosity of the fermentation solution is 20"C.
．． , 1 8q sieve. This 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 Using the method of Example 1, using methyl methacrylate instead of methyl acrylate and N,N-dimethylaminobutylamine instead of N,N-dimethylaminopropylamine, 1! was obtained by the adduct method. ! N left behind.

20 t of N-diethylaminoprolylacrylamide to 1 t of water
Joined the 200 Me Mitsuro flask equipped with a stirrer, thermometer and reflux condenser containing 00 tons.

After replacing with nitrogen. 0.4f of 2,2-azobis-(2-amidinopropane) hydrochloride was added, and the mixture was incubated at 60"C for 8 hours. After the polymerization was completed, the subcompound was added to acetone, and the polymer was precipitated. After P'411, it was washed with acetone and vacuum dried at room temperature. The polymerization yield was 93.7.
He was in charge.

Dissolve this polymer in water to a weight ratio of 0.5 l,
When the viscosity of this aqueous solution was crushed at 20°C using a B-type viscometer, the result was +40 c. llLs. Met.

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-') methyl was prepared by a direct method. Aminobutyl methacrylamide was produced. father.

Methyl methacrylate instead of methyl acrylate using N,N-dimethylaminobutylamine.

N,N-dimethylaminobutylacrylamide was produced by the β-aminopropionamide method.

N produced by direct method and β-aminopropionamide method
Polymerization was carried out under the same conditions as in Example 4 using n and N-dimethylaminobutylmethacrylamide. The polymerization yields were 90.2% and 92.8%, respectively.
The viscosity of a 0.5% aqueous solution of these copolymers is 20°
C, +7 C9p, S-+10 c, respectively
, p, s, which are very low values compared to the method of the present invention, indicating that the molecular weight of the water-copolymer is low.

Examples N, N produced by the adduct method according to the method of Example 1, using methyl methacrylate instead of methyl acrylate.
- 800me Mitsuro 7 with a stirrer, a meter and a reflux condenser containing 6f of dimethylamine propylmethacrylamide and 402 diacetone acrylamide with 155f of water
After joining Lasco, the air was replaced with nitrogen, 100% by weight ammonium persulfate aqueous solution Q2v was added, and the mixture was incubated at a temperature of 50°C for 2.5 hours. After the completion of the 0-polymerization, iodometry (quantification of unreacted two-point bonds) When I calculated the union rate, it was 97.4.

The copolymer concentration of this aqueous solution polymer was diluted with water to 1.5% by weight, and the viscosity was measured at 20°C using a B-type viscometer and found to be 95 c, p, s.

Comparative Example 5 A direct method using the method of Comparative Example 1 but using methyl methacrylate instead of ethyl acrylate.

f')B by the β-aminopropionamide method using methyl methacrylate instead of methyl acrylate;
N,N-dimethylamine propylmethacrylamide was produced.

N produced by direct method and β-aminopropionamide method
Polymerization was carried out under the same conditions as in Example 5 using n and N-dimethylaminopropyl methacrylamide. The polymerization yields were 96.7% and 96.7% for IJ- and IJ-, respectively.
It was 961%. The polymer concentration of these hydroxyl liquid polymers was diluted with water to give a concentration of 5% by weight, and the viscosity was determined using a B-type viscometer at 20"C. The results were +22, respectively. c, p-5-+ 80 c, ps.

9 shows a very low value compared to the method of the present invention, indicating that the molecular weight of the coelectrolyte is low. ,Ta.

Example 6 6t of N,N-dimethylaminoglopylacrylamide produced by the adduct method in Example 1 and 84% of ethyl acrylate
．． 9e Polyoxyethylene nonyl phenyl ether 4.
5f and 200t of water were placed in a 500ml four-eye flask equipped with a nitrogen inlet tube, a magnetic condenser, a stirrer, and a thermometer, and while stirring, nitrogen was passed through it for 30 minutes.
@ti-% potassium persulfate 1, shim aqueous solution 1f and 5% by weight
Average value of oxyhydrogen) IJum aqueous solution l? was added, and emulsification was carried out at a temperature of 40° C. for 2 hours. The resulting emulsion was made into a mechanically stable emulsion. This emulsion was poured into methanol to precipitate the copolymer.

After each house, it was washed with methanol and vacuum dried at room temperature. The false positive yield 4A was 97.8%.

This copolymer is 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 3 Q c, p, s.

Comparative Example 6 Emulsion polymerization was carried out under the same conditions as in Example 6 using N,N-dimethylaminoglopylacrylamide produced by the direct method and the β-aminopropionamide method in Comparative Example 1, respectively. The mechanical stability of the prepared emulsion was good. The polymerization yields were 96.8% and 97%, respectively.
．． It was 0%.

These copolymers are also unbathable in water (when the viscosity was measured at 20°C with a B-type viscometer as an acetone solution with a concentration of 1.5 mi, the viscosity was +19 c, S, 22 c, p, respectively).
, s, and the difference in viscosity was small compared to the aqueous solution polymerization method, etc., but it showed a lower viscosity than the method of the present invention.

Patent applicant: Kojin Co., Ltd.

Claims (1)

[Claims] General formula (where It represents hydrogen or a methyl group. R, 5H
It is represented by CnH,n, and n represents an integer of 2 to 4. 1
4. , R, represents hydrogen or an alkyl group having 1-2 carbon atoms. ) is obtained by thermally decomposing 5-alkyl-5-N-(N', N'-dialkylaminoalkyl)carboxamido-2-norbornene. ) A method for producing a high molecular weight acrylamide-based cationic polymer, which comprises polymerizing acrylamide or copolymerizing the monomer with another monomer.