JPS6360732B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to a method for producing an α,β-unsaturated N-substituted carboxylic acid amide, a novel α,β-unsaturated N-substituted carboxylic acid amide, a polymer of α,β-unsaturated N-substituted carboxylic acid amide, and the like. Concerning use as a sedimentation agent, flocculant, dehydration agent and retention aid. N-substituted acrylamides have been known for a long time. This is the reaction between acrylonitrile and 1-olefin (Journal of American.
Chemical Society Vol. 73 (1951) 4076) or by the reaction of a primary or secondary amine with an addition compound of maleic anhydride and triphenylphosphine (Japanese Patent Publication No. 20083/1983). According to British Patent No. 746,747, N-substituted acrylamides are obtained by dehydrohalogenation of β-chloropropionic acid amides, and according to West German Patent No. 2344070, β-methoxypropionic acid Obtained by thermal decomposition of amides. moreover,
N-substituted acrylamides can be prepared by the catalytic addition of functionalized amines to acetylene under a CO atmosphere (U.S. Pat. No.
2773063), ring element amination of diacetone acrylamide (Journal of Polymers)
Science Vol. 10 (1972) 595), and further by thermal decomposition of norbornene derivatives (West German Patent Publication No. 2354602). Furthermore, this compound is prepared according to DE 2502247 and DE 2656682 and US Pat. No. 3,878,247 by adding an amine to an acrylic or methacrylic ester in a simultaneous aminolysis reaction to form an N-substituted aminopropionic acid amide. and then thermally decompose it into the corresponding α, β−
It can also be obtained by using an unsaturated N-substituted carboxylic acid amide. The earlier, unpublished West German patent applications P2819735 and P2836520 describe the reaction of β-hydroxy or β-alkoxy acid amides with amines with elimination of ammonia, resulting in N-substituted hydroxy or alkoxy acid amides. A process is described for preparing the corresponding α,β-unsaturated N-substituted acid amides by heating in the liquid phase in the presence of a catalyst to carry out a dehydration or alcohol elimination reaction. The present inventors have proposed that α,
We have discovered a method for producing β-unsaturated N-substituted acid amides. The method involves the transamidation reaction of a β-hydroxy or β-alkoxycarboxylic acid amide with an amine.
This is a method for producing a desired N-substituted α,β-unsaturated N-substituted carboxylic acid amide by dehydrating or dealcoholizing a hydroxy or β-alkoxycarboxylic acid amide in a gas phase. This invention is based on the general formula (Here, R ¹ and R ² are hydrogen or methyl groups,
Y is a linear or branched divalent organic group having 2 to 30 carbon atoms, preferably 2 to 18 carbon atoms, preferably of the formula -(Y ₁ )m-(Y ₂ )n-(Y ₃ )t
- (where Y ₁ , Y ₂ and Y ₃ are an alkylene group or a cyclic group having 5 or 6 carbon atoms, and the sum of m, n and t is 2 or 3), and is hydrogen or the formula -N(R ⁴ ),
(R ⁵ ) (wherein R ⁴ and R ⁵ are alkyl groups having 1 to 4 carbon atoms) an α,β-unsaturated N-substituted carboxylic acid, A β-substituted carboxylic acid amide is subjected to an amide substitution reaction with elimination of ammonia to form a compound of the formula H ₂ N-(Y)-(X) (where Y and X are as described above). A method for producing a starting β-substituted carboxylic acid amide by reacting it with a primary amine and converting the resulting N-substituted carboxylic acid amide into an α,β-unsaturated N-substituted carboxylic acid amide. general formula as (Here, R ¹ and R ² are hydrogen or methyl groups,
and Z is a hydroxy group or an alcohol residue of the formula R ⁸ O- and R ⁸ is a β-
The desired α,β-unsaturated N -substituted carboxylic acid amide. In this invention, N-substituted β-hydroxy or β-
α,β-unsaturated N alkoxycarboxylic acid amide
- The step of conversion to substituted carboxylic acid amides is not carried out in the liquid phase, but rather the β-hydroxy or β-
The alkoxycarboxylic acid amide is preferably vaporized in a gentle manner and this gas is introduced onto a solid catalyst which is preferably housed in a heatable reaction tube. It is advantageous to use a vacuum evaporator to carry out the vaporization mentioned above. Furthermore, in order to perform the process more gently, vaporization is performed by vacuuming as desired. Unlike thermal decomposition in the liquid phase, which requires long-term heating, in this invention, the residence time in the thermal reaction tube is very short, so side reactions that cannot be avoided with high-temperature liquid-phase heating, such as N- The risk that the substituted β-hydroxycarboxylic acid amide will polymerize or self-react with elimination of the amine to form a polyester is reduced. The transamidation reaction is preferably carried out at a temperature of 100 to 200°C, optionally with the addition of a catalytic amount of acid. Particularly when β-alkoxycarboxylic acid amide is used, it is preferable to add 0.5 to 1.0 mol % of acetic acid as a catalyst. Acid amides and amines can be reacted by simply heating without adding a solvent, with the reaction equilibrium changing to the desired product (N) by removing the ammonia formed.
-substituted β-hydroxy or β-alkoxy acid amides). The transamidation reaction can also be carried out at normal pressure without the addition of a catalyst, using amines with a boiling point above 110° C. in order to limit the reaction time (approximately 6 hours). In addition to this, preference is given to amines which form a homogeneous phase with the melt of the acid amide or are partially soluble in the melt of the acid amide or are themselves partially soluble in the melt of the acid amide. Although the initial reaction is inhibited by low mutual solubility, the generated N-substituted β-
Since the hydroxy or β-alkoxycarboxylic acid amide acts as a solubilizing agent and forms a homogeneous phase, the reaction rate increases as the exchange reaction progresses. In order to speed up this initial reaction induction time, it is preferred to add 5 to 10% of the respective N-substituted .beta.-hydroxy or .beta.-alkoxycarboxylic acid amide. Each amine is added in excess relative to the hydroxy or alkoxyamide. The dehydration or alcohol withdrawal reaction is preferably
It is carried out at a temperature of 200 to 400°C. In the case of amino group-containing β-hydroxy or β-alkoxycarboxylic acid amides, temperatures up to 250°C are sufficient. Metal oxides, such as aluminum oxide, are particularly suitable as dehydration catalysts. Alongside that,
Mixtures of oxides, such as mixtures of aluminum oxide and silicon dioxide, or impregnated supports, such as acidic aluminum oxide or phosphoric acid impregnated pumice, as well as salts, such as aluminum phosphate or boron phosphate, are also useful. Solid catalysts for the alcohol elimination reaction include acidic or basic inorganic oxides such as aluminum oxide, as well as silicon oxide and barium oxide (which can be impregnated with an acid such as phosphoric acid or a base such as sodium hydroxide). ) is particularly suitable. For the purpose of this invention, β-hydroxycarboxylic acid amide is preferably β-hydroxypropionic acid amide or β-hydroxybutyric acid amide. Suitable examples of amines represented by the general formula H ₂ N-(Y)-(X) () include 2-dimethylaminoethylamine, 2-diethylaminoethylamine, 3-dimethylaminopropylamine, benzylamine, and cyclohexylamine. , dodecylamine and stearylamine. General formula for amine (Here, R ⁶ and R ⁷ are an alkyl group, preferably a lower alkyl group having 1 to 4 carbon atoms, especially a methyl group or an aryl group, or jointly constitute an aliphatic cyclic group, especially a cyclohexyl group or a cyclopentyl group. You can do it. n is 0 or
^{10 , _ _} cycloalkyl groups) are preferred. The divalent organic group Y is a straight or branched alkylene group which may be substituted. When Y is a group represented by the formula -(Y ₁ )m-(Y ₂ )n-(Y ₃ )t-, each group of Y ₁ , Y ₂ and Y ₃ is a straight chain or branched chain. is an alkylene group or an organic ring group having 5 or 6 carbon atoms, which may be substituted by . In that case, the cycloalkyl group may be substituted, for example by an alkyl group. When X represents an amine residue represented by the formula -N(R ⁴ ) or (R ⁵ ), these R ⁴ and R ⁵ are the same or different linear or branched alkyl groups, such as methyl group, ethyl group, propyl group. isopropyl or n-butyl, or a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, when Z in formula () is an alcohol residue of the formula R ⁸ O-, R ⁸ is a straight or branched alkyl group such as a methyl group, ethyl group, isopropyl group or n-butyl group. A preferred amine is N',N',2,2-tetramethylpropylenediamine-1,3 (dimethylaminoneopentylamine (formula', n=1, ^R6 = ^R7
=CH ₃ ), and in particular: 3-dimethylamino-2,2-dimethylpropylamine 3-diethylamino-2,2-dimethylpropylamine 3-dibutylamino-2,2-dimethylpropylamine 4-dimethylamino-3,3-dimethylbutylamine-1 5-dimethylamino-4,4-dimethylpentylamine-1 5-diethylamino-4,4-dimethylpentylamine-1 3-dimethylamino-2-ethyl-2-methylpropylamine 3-dimethylamino-2-methyl-2-phenylpropylamine 3-dimethylamino-2-ethyl-2-butyl-
propylamine 1-(aminomethylene)-1-(dimethylaminomethylene)-cyclohexene In these amines, hydrogen is not present at the carbon atom located at the β-position with respect to the tertiary amino group, and an alkyl group is substituted instead. Amines of the general formula () that do not have a hydrogen atom at the carbon atom located at the β position with respect to such tertiary nitrogen are preferred for this invention. This is because reaction products prepared using such amines do not involve temperature-limited β-elimination of the amine. This amine elimination creates a terminally located double bond in addition to the α,β double bond for the α,β-unsaturated N-substituted carboxylic acid amide of the monomer; The use of monomeric acid amides in the preparation of water-soluble polymers is entirely disadvantageous, since it causes undesired crosslinking reactions. By selecting the β-substituents, the hydrophilicity or lipophilicity of the monomers and the polymers prepared therefrom can be modified depending on the intended use. Furthermore, the purpose of this invention is to (Here, R ₁ and R ₂ are hydrogen or methyl groups,
R ₆ and R ₇ are an alkyl group, preferably a lower alkyl group having 1 to 4 carbon atoms, especially a methyl group or an aryl group, or R ₆ and R ₇ are jointly a part of an alicyclic ring, especially a cyclopentyl ring or a cyclohexyl ring. n is an integer from 0 to 10,
X is an amine residue of the formula -N(R ₄ ), (R ₅ ), R ₄ and
R ₅ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms). There is also. The α,β-unsaturated N-substituted carboxylic acid amides of this invention can be formed into homopolymers, copolymers or other interpolymers by themselves or together with other polymerizable monomers according to known methods. Can be easily polymerized. These polymers are excellent flocculants and dewatering agents for wastewater treatment and are useful in increasing the dry and wet strength of paper and as retention aids. In these polymers, elimination of the amine reduces the specific activity and in extreme cases leads to complete inactivity. Furthermore, the object of the present invention is to provide a polymer of the compound obtained by the above method, which has the formula (Here, R ¹ , R ² , R ⁶ , R ⁷ , X and n are
(1)), which method comprises polymerizing the starting compound alone or with other polymerizable monomers by a method known per se; Another object of the present invention is to provide a polymer obtained by this method. The above polymerization follows a known method. The polymerization can thus be carried out thermally, photochemically, by radiation or by means of conventional radical initiators. Moreover, this polymerization can be carried out in a solution, suspension or emulsion state. Suitable initiators are in particular inorganic peroxides (for example hydrogen peroxide) or organic hydroperoxides or peroxides (for example tert-butyl hydroperoxide, cumene hydroperoxide or dibenzoyl peroxide), radically cleavable azo compounds (for example 2, 2'-Azo-bis-isobutyric acid nitrile),
Oxidation ring base catalyst systems (for example systems of persulfates or chlorates and disulfites or iron() salts), as well as chelates of transition metals known as radical formers. These initiators are generally used in an amount of 0.001 to 1% by weight based on the monomer amount. Optimal amounts and initiators can be easily determined by experiment. The above polymerization is preferably carried out in the presence of a solvent or diluent. Suspension, solution or emulsion polymerization techniques customary for other monomers are also suitable for the polymers of this invention. Depending on the case, auxiliary agents such as buffers, dispersants, and protective colloids may be used. The copolymerizable monomer has a polymerizable double bond, and the following are particularly preferred. Vinyl aromatic compounds (e.g. styrene, α-
methylstyrene, vinylpyridine) acrylonitriles (e.g. acrylonitrile and methacrylonitrile) acrylamides (e.g. acrylamide,
(Methacrylamide, N-mono- or N-disubstituted acrylamide or methacrylamide) Acrylic and methacrylic esters Acrylic acid and methacrylic acid Vinyl esters and vinyl ethers Fumaric acid and maleic acid or derivatives thereof; Compounds having heavy bonds (eg divinylbenzene, methylene bisacrylamide and acrylallyl ester) Among these, acrylamide is particularly preferred. The composition of the copolymers of this invention can vary within a wide range. The copolymers of this invention may have a composition in which the monomers of this invention are present in a small amount, for example 5% by weight, and the remainder, for example 95% by weight, are other copolymerizable monomers. On the other hand, copolymers in which the monomer of this invention is present in a larger amount, for example 50 to 95% by weight, and other copolymerizable monomers are present in an amount of 50 to 5% by weight also belong to the scope of this invention. Needless to say, homopolymers of the monomers of this invention also fall within the scope of this invention.
A preferred copolymer is a monomer of the present invention, that is, an unsaturated carboxylic acid amide represented by the formula (') having 5 to
60% by weight, especially 10-50% by weight, and other copolymerizable monomers account for 95-40% by weight, especially 90-50% by weight. In this case, as the other copolymerizable monomer, an acrylic or methacrylic acid derivative (for example, acrylamide, methacrylamide, acrylic ester or methacrylic acid amide) is preferably used. The obtained α,β-unsaturated N-substituted carboxylic acid amide polymer has the formula (Here, R ₁ , R ₂ , R ₆ and R ₇ are expressed by the formula (′)
Another object of the present invention is to provide a product characterized by having the minimum repeating unit shown in (as described above). The monomer products of this invention can be neutralized and/or quaternized. Polymers obtained from this cationic monomer are useful as excellent flocculation and dewatering aids for wastewater treatment, and as aids or retention aids to improve the dry and wet strength of paper. Moreover, based on its temperature stability, it can also be added to lubricants as viscosity regulators and dispersants. Anion exchange resins can also be produced by polymerization in the presence of limited amounts of crosslinking agents. When used as a flocculation aid and a dehydration aid, the polymers of this invention preferably contain 5 to 10 Mio
(1,000,000), preferably has a molecular weight of the order of 1 to 5 Mio when used as a paper additive, and for other applications
Preferably it has a molecular weight on the order of less than 1 Mio. The present invention will be explained in detail below using Examples and Reference Examples. Reference example A N-(N',N',2',2'-tetramethylaminopropyl)acrylamide (TEMAPA) β-hydroxypropionamide (471g) and N,N,2,2-tetramethylpropylenediamine-1 , 3 (722 g) were heated at a temperature of 140°C to 160°C for 7 hours until ammonia evolution ceased. β-hydroxy-N-(N′,
1058 g of N',2',2'-tetramethylaminopropyl)propionic acid amide was obtained. Boiling point 206°C/10 torr. NMR: (COCl ₃ ) δ = 0.9 (s, 6); 2.25 (s,
2); 2.3 (s, 6); 2.45 (t, 2); 3.2
(d, 2); 3.9 (t, 2) 917 g of the above product were successively evaporated in a thin-layer evaporator, and the vapor was introduced into a reaction tube filled with 700 g of aluminum oxide and heated to 220°C. After 3.5 hours, 727 g of N-(N',N',2',2'-tetramethylaminopropyl)acrylamide was obtained.
Boiling point 137℃/10mb. NMR: (CDCl ₃ ) δ = 0.9 (s, 6); 2.3 (m,
8); 3.25 (d, 2); 5.4-6.2 (m,
3); (See Figure 1) Reference example B N-(N',N',2,2-tetramethyl-3-aminopropyl)-3-methoxypropionamide 3-methoxypropionamide (412.5g, 4.0
mol) was heated with N,N,2,2-tetramethylpropanediamine-1,3 (547 g, 4.2 mol) and 4 ml of glacial acetic acid at a temperature of 145 DEG C. to 170 DEG C. for 8 hours until ammonia evolution ceased. Colorless desired liquid with boiling point _0,2 105-108 ° C by distillation under high vacuum
820 g (3.8 mol, yield 95%) was obtained. NMR (in CCl ₄ ): δ = 0.9 (s, 6); 2.0-2.5 (m,
10); 3.05 (d, 2); 3.3 (s, 3);
3.55 (t, 2); 7.40 (m, 1) N-(N',N',2',2'-tetramethyl-3-aminopropyl)-acrylamide All in a distillation flask heated to 170-180°C in
802 g (3.8 mol) of N-(N',N',2,2-tetramethyl-3-aminopropyl)-3-methoxypropionamide were introduced and the resulting vapor was
Under a vacuum of m bar, it was introduced into a reaction tube (length 100 cm, diameter 3 cm) filled with gelled aluminum oxide impregnated with 10% sodium hydroxide and heated from the outside to 300° C. with a band heater. 150℃
Approximately 475 g of a yellow oil was obtained in the course of 2 hours at a head temperature of -220 DEG C., which was again distilled under high vacuum for further purification. Thus, the boiling point
383 _g (2.1 mol, 3-
Yield 52 based on methoxypropionamide
%) was obtained. NMR (in CCl ₄ ): δ = 0.9 (s, 6); 2.1 (s,
2); 2.3 (s, 6); 31.5 (d, 2); 5.3
~6.5 (m, 3); 8.0 (m, 1) (see Figure 1) Example 1 N-(N', N', 2,2-tetramethyl-3-aminopropyl)-2-methyl-3 -Methoxypropionamide 857 g ( _3.7 mol, yield
93%). NMR (in CCl ₄ ): δ = 0.9 (s, 6); 1.05 (d,
3); 2.0-2.7 (m, 9); 3.05 (d,
2); 3.2-3.6 (m, 5); 7.3 (m, 1) N-(N', N', 2,2-tetramethyl-3-aminopropyl)-methacrylamide (TEMAPMA) According to Reference Example B, 857 g (3.7 mol) of the product
510 g of the desired product were obtained. 420 g (2.1 mol, 2-methyl-3
-Yield 53 based on methoxypropionamide
%) was obtained. Boiling point _0.2 = 92-94℃). NMR (in CCl ₄ ): δ = 0.9 (s, 6): 1.9 (d,
3);2.2(s,2);2.3(s,6);3.1
(d, 2); 5.1-5.7 (m, 2); 8.0 (m,
1) (See Figure 2) Example 2 N-(N',N',2,2-tetramethylaminopropyl)crotonic acid amide β-hydroxybutyric acid amide (412 g) and N,
N,2,2-tetramethylpropylenediamine-
1,3 (546 g) was heated at 148-160°C for 16 hours. 829g of this reaction product was transferred to a thin layer evaporator (250℃/
This vapor was introduced into a reaction tube filled with 700 g of aluminum oxide and heated to 220°C. N-(N′, N′,
543 g of 2',2'-tetramethylaminopropyl)crotonic acid amide was obtained. Lip102℃/0.035mb. NMR: (CDCl ₃ ) δ=0.9 (s, 6); 1.9 (dd,
3); 2.15-2.6 (m, 8); 3.35 (m,
2) 5.6 to 7.0 (m, 2) (see Figure 3) Example 3 N-(N',N',2,2-tetramethyl-3-aminopropyl)-3-methquinbutyric acid amide of Reference Example B According to the procedure, 800 g (3.5 mol, yield 87%) of a pale yellow liquid with a boiling point of _0.2 112 DEG -114 DEG C. was obtained from 468.6 g (4.0 mol) of 3-methoxybutyric acid amide. NMR (in CDCl ₃ ): δ = 0.9 (s, 6); 1.15 (d,
3); 2.0-2.5 (m, 10); 3.1 (d,
2); 3.35 (s, 3); 3.7 (q, 1); 7.7
(m.1) N-(N',N',2,2-tetramethyl-3-aminopropyl)-crotonic acid amide 587 g of the desired product from 800 g (3.5 mol) of the above product according to Reference Example B This was distilled under high vacuum to give 516 g (2.6 mol, 65% yield based on 3-methoxybutyric acid amide) of a pale yellow viscous oil. Boiling point _0.2 = 104-108℃ NMR (in CCl ₄ ): δ = 0.9 (s, 6); 1.8 (dd,
3); 2.1 (s, 2); 2.3 (s, 6); 5.6
~7.0 (m, 2); 7.6 (m, 1) Each amine was reacted with each β-hydroxy or β-methoxycarboxylic acid in an equimolar amount in the same manner as in Reference Examples A and B and Examples 1 to 3. The following compounds were manufactured. Example 4 N-(3-diethylamino.2,2-dimethylpropyl)acrylamide. Boiling point 110℃/0.1mb. NMR (CCl ₄ ) is shown in Figure 4. Example 5 N-(3-diethylamino-2,2-dimethylpropyl)methacrylamide. Boiling point 117℃/
0.1mb. NMR (CCl ₄ ) is shown in Figure 5. Example 6 N-(3-diethylamino-2,2-dimethylpropyl)crotonamide. Boiling point 113℃/
0.035mb. NMR (CDCl ₃ ) is shown in Figure 6. Example 7 N-(3-dibutylamino-2,2-dimethylpropyl)acrylamide. Boiling point 155℃/0.09mb. NMR (CCl ₄ ) is shown in Figure 7. Example 8 N-(3-dibutylamino-2,2-dimethylpropyl)methacrylamide. Boiling point 125℃/
0.032mb. NMR (CCl ₄ ) is shown in Figure 8. Example 9 N-(3-dibutylamino-2,2-dimethylpropyl)crotonamide. Boiling point 129℃/0.03mb. NMR (CCl ₄ ) is shown in Figure 9. Example 10 N-(4-dimethylamino-3,3-dimethylbutyl)acrylamide. Boiling point 107℃/0.08mb. NMR (CCl ₄ ) is shown in Figure 10. Example 11 N-(4-dimethylamino-3,3-dimethylbutyl)methacrylamide. Boiling point 113℃/0.14mb. NMR (CCl ₄ ) is shown in Figure 11. Example 12 N-(4-dimethylamino-3,3-dimethylbutyl)crotonamide. Boiling point 120℃/0.03mb. NMR (CCl ₄ ) is shown in Figure 12. Example 13 N-(5-dimethylamino-4,4-dimethylpentyl)acrylamide. Boiling point 127℃/0.03mb. NMR (CCl ₄ ) is shown in Figure 13. Example 14 N-(5-dimethylamino-4,4-dimethylpentyl)methacrylamide. Boiling point 127℃/
0.04mb. NMR (CCl ₄ ) is shown in Figure 14. Example 15 N-(5-dimethylamino-4,4-dimethylpentyl)crotonamide. Boiling point 134/0.03mb. NMR (CCl ₄ ) is shown in Figure 15. Example 16 N-(5-diethylamino-4,4-dimethylpentyl)acrylamide. Boiling point 130℃/0.06mb. NMR (CCl ₄ ) is shown in Figure 16. Example 17 N-(5-diethylamino-4,4-dimethylpentyl)methacrylamide. Boiling point 132℃/0.035mb.NMR (CCl ₄ ) is shown in Figure 17. Example 18 N-(3-dimethylamino-2-ethyl-2-
Methylpropyl) acrylamide. Boiling point 98℃/0.03mb.NMR (CCl ₄ ) Figure 18. Example 19 N-(3-dimethylamino-2-ethyl-2-
Methylpropyl) methacrylamide. Boiling point 98℃/0.06mb.NMR (CCl ₄ ) is shown in Figure 19. Example 20 N-(3-dimethylamino-2-methyl-2-
phenylpropyl) acrylamide. Boiling point 128℃/0.06mb.NMR (CCl ₄ ) is shown in Figure 20. Example 21 1-(acrylamidomethylene)-1-dimethylaminomethylene-cyclohexene. Boiling point 122℃/0.04mb.NMR (CCl ₄ ) is shown in Figure 27. Example 22 1-(methacrylamidomethylene)-1-dimethylaminomethylene-cyclohexene. Boiling point 122℃/0.05mb.NMR (CCl ₄ ) is shown in Figure 28. The amino compounds obtained by the above method can be converted into the corresponding amine salts by reaction with a suitable acid (for example sulfuric acid) or can be quaternized with a suitable alkyl halide or alkyl sulfate.
These matters will be explained in the following examples. Example 23 Trimethyl-3-(1-acrylamide-2,
2-dimethyl-propyl)-ammonium methosulfate N-(N',N',2',2'-tetramethylaminopropyl)acrylamide 289.5g was dissolved in 317g of water, and the solution was stirred and ice-cooled. dimethyl sulfate
185.4g was administered over 2.5 hours. The reaction was continued for an additional 3 hours to obtain a 60% solution of the desired quaternized product. Example 24 (3-acrylamido-2,2-dimethylpropyl)-trimethylammonium chloride N-(3-dimethylamino-2,2-dimethylpropyl)acrylamide (of Example 1)
TEMAPA) 376g dissolved in 320g of water,
While stirring vigorously, 103 g of methyl chloride was added at 80° C. over 3.5 hours. The operating pressure was 0.4 bar.
In this way, an aqueous solution of the desired quaternized product was obtained. The acrylamide compound of the present invention can be used alone or by polymerization with other comonomers to form homopolymers, copolymers, or other interpolymers. This will be explained below using examples. Reference example 1 Homopolymer of TEMAPA・1/2H ₂ SO ₄ Dissolve 160 g of N-(N', N', 2', 2'-tetramethylaminopropyl) acrylamide in 85 g of water,
Acidified with 199.5 g of 20% sulfuric acid. This solution was heated to 55°C.
Polymerization was carried out by heating the mixture to 80 mg and adding 80 mg of azobisisobutyronitrile. After 2 hours, the resulting gel-like polymerization reaction product was crushed, dried,
It was further finely ground. Residual monomer content 0.72%.
Viscosity (1% aqueous solution) 184 m.Pa.s.o NMR ( _D2O ) and IR (dissolved in _H2O and dried with KBr) are shown in Figures 21 and 22, respectively. Reference example 2 TEMAPA・1/2H ₂ SO ₄ /acrylamide copolymer Dissolve 80 g of N-(N', N', 2', 2'-tetramethylaminopropyl) acrylamide in 386 g of water,
Acidified with 100 g of 20% sulfuric acid. Acrylamide 100
The solution was heated to 55° C. and polymerization was initiated with 80 mg of azobisisobutyronitrile. 3
After a reaction time, the resulting gel-like copolymerization product was crushed, dried, and further finely ground. Residual monomer content 0.7%. Viscosity (1% aqueous solution) 1200 m.Pa.s. Reference example 3 TEMAPA・CH ₃ Cl homopolymer Dissolve 200 g of TEMAPA・CH ₃ Cl in 380 g of water,
Adjusted to PH4. After nitrogen blowing, 3 mg of potassium peroxide sulfate, 2 mg of sodium disulfite, 0.2 mg of iron sulfate () and 30 mg of 2,2'-azobis-(2-amidinopropane) dihydrochloride (AIBA) were added to initiate polymerization. It started. The resulting gel-like product was dried to a moisture content of 10% and crushed. Intrinsic viscosity (10% saline solution) 387.5ml/g. Reference example 4 Acrylamide (78% by weight)/TEMAPA・1/
2H ₂ SO ₄ (22% by weight) copolymer acrylamide 234g and TEMAPA・1/2
Mix 66 g of H ₂ SO ₄ with 30 mg of AIBA in 700 g of water,
After nitrogen was introduced, it was irradiated with a lamp (OSRAM HWL 250 watts) for 30 minutes. The resulting gel-like product was dried to a moisture content of 11% and crushed. Intrinsic viscosity (10
% saline solution) 1640ml/g. NMR (D ₂ O) and IR (dissolved in H ₂ O and dried with KBr) were each
Figures 3 and 24. Reference Example 5 Homopolymer of N-(3-dimethylamino-2,2-dimethylpropyl)methacrylamide/1/2H ₂ SO ₄ (TEMAPA/1/2H ₂ SO ₄ ) Disperse 80 g of TEMAPAMA in 40 g of water, %
The mixture was neutralized with 100 g of sulfuric acid, bubbled to remove oxygen, and 100 mg of AIBA was added, followed by irradiation for 1 hour (OSRAM HWL 250 watts). Bruckfield viscosity of dry polymer (1% aqueous solution)
240 mPas. NMR (D ₂ O) is shown in Figure 25. Reference example 6 Acrylamide (75% by weight)/TEMAPMA・
1/2H ₂ SO ₄ (25% by weight) copolymer Dissolve 150g of acrylamide in 470g of water,
40 g of TEMAPMA was added and neutralized with 50 g of 20% sulfuric acid. After adding 25 mg of AIBA, oxygen was removed by bubbling and irradiation was performed for 30 minutes (OSRAM HWL 250 Watts). The resulting gel-like product was dried and ground. Burtskfield viscosity (1% aqueous solution)
3800 mPas. NMR (D ₂ O) is shown in Figure 26. Reference Example 7 A product prepared according to the invention was tested as a sedimentation agent in a flocculation test. The flocculation state after adding the aqueous solution of the copolymer of Example 26 or 28 to a suspension of kaolin suspended in water and adjusted to pH approximately 4.8 with an Al ₂ (SO ₄ ) solution is the sedimentation rate. It was tested by measuring . The results are shown in the table.

[Table] (Table: Solid content 20g/( _Al2SO4 added, _product 0.1% solution) concentration 2ppm, experimental method by H. Akyel/
Chemie−Ing.−technik 39 by M.Neven
(1967) 172) The product was further tested for dewatering of sacrificial mud. The solid content was 3.7%. The results are shown in the table below.

[Table] Reference Example 8 The copolymers of Examples 26 and 28 were tested for applicability as dehydration aids and retention aids for papermaking. a. Dehydration test device and test method A Schopper Leeglar freeness tester (SR-device) was used as the test device. In order to measure the dewatering time of the suspension, the overflow was put into the graduated cylinder of the apparatus together with the nozzle outlet, and the dewatering time (t _E , seconds) of 600 ml of the filtrate was measured. The freeness of the material was kept as low as possible below 55°SR. The suspension used was 2g under standard conditions for SR゜ measurement.
(absolutely dry) Fibrin Suspension In the above test, 400g of funnel paper was beaten in 20% of water and 55g was beaten for 2 hours in a Vouret beater under a small load.
It was fractured to ~57°SR. Test results

[Table] b Yield test method Filler yield: RK - in sheet forming machine SR - in equipment Test sheet for sheet forming machine weighs 100g/m ²
The paper material in the SR-equipment was limited to 2.0g (absolutely dry). The retention effect in the sheet forming machine was evaluated by the amount of ash remaining based on the addition of filler. To test the yield in the SR-apparatus, the turbidity of 600 ml of wastewater was measured with a Lange colorimeter. 3 Test results 3.1 Yield in sheet forming machine Charge amount: 0.02% yield improver/filler

【table】 3.2 Yield in SR-equipment Charge amount: 0.02% retention improver/filler

[Table] Reference example 9 TEMAPA (90% by weight)/dodecyl methacrylate (10% by weight) copolymer 23.33 g of TEMAPA and 210 g of dodecyl methacrylate were mixed with 0.1167 g of dodecyl mercaptan in neutral oil (BP-ENERTHENE 1269).
Polymerization was carried out in 116.67g by heating to 80°C and adding 1.2g of AINB to the total over 5 hours.
The obtained high viscosity reaction product (2 parts) was further BP
- Mixed with ENERTHENE 1269 (98 parts) and used in the following tests. Reference Example 10 TEMAPMA (10% by weight)/dodecyl methacrylate (90% by weight) copolymer In the same manner as in Example 33, TEMAPMA
(10% by weight) / Dodecyl methacrylate (90% by weight)
A mixture of copolymer and neutral oil was prepared. The influence of the above two types of copolymers on the viscosity of the above neutral oil was investigated by measuring the viscosity index according to ASTM D-2270-77. Also,
The dispersibility of these copolymers was tested based on their inhibition of sedimentation of suspensions of charcoal powder in neutral oil.

[Table] Reference example 11 Propylene-bis [(3-acrylamide-2,
Homopolymer of 2-dimethyl)propyldimethylammonium dibromide 73.7 g of TEMAPA and 40.4 g of 1,3-dibromopropane were stirred in 50 g of water at 90°C for 6 hours, then cooled to 40°C, and potassium peroxydisulfate was added. Polymerization was carried out by adding 0.5 g. The resulting crosslinked polymer was dried to a water content of 10%, crushed, and its ion exchange properties were tested. Ion exchange capacity: 3.1mval/g (Br ^- body)

[Brief explanation of drawings]

Figures 1 to 28 are NMR or IR spectral diagrams of products obtained according to the invention.

Claims (1)

[Claims] 1. A β-substituted carboxylic acid amide represented by the following general formula, β of an N-substituted carboxylic acid amide obtained by reacting with a primary amine represented by the following general formula and an amidation exchange reaction between the two accompanied by elimination of H ₂ N-(Y)-(X) ammonium. - An α,β-unsaturated N-substituted carboxylic acid characterized in that a compound represented by the following general formula is obtained by heating the substituted product in a gas phase in the presence of a catalyst to perform a HZ removal reaction. Method for producing amides. In addition, in the above, R ¹ and R ² represent hydrogen or a methyl group, R ⁶ and R ⁷ are an alkyl group or phenyl group having 1 to 4 carbon atoms, or together constitute a cyclohexenyl group, and n is represents ^an integer ^from 1 ^{to 3} ; or jointly 3 to 8
cycloalkyl group with carbon atoms) or formula (Here, R ³ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are as described above, and A is a salt-forming anion.) is the expression Z represents a hydroxy group or an alcohol residue represented by the formula R ⁸ O- (wherein R ⁸ is an alkylene group having 1 to 4 carbon atoms). However, R ₁ and R ² are both hydrogen, n=1, R ⁶
and R ⁷ are all methyl groups, and X is -N
( _CH3 ) Except for ₂ . 2. The manufacturing method according to claim 1, wherein the N-substituted β-hydroxy or β-alkoxycarboxylic acid amide is gently vaporized. 3. A patent characterized in that the N-substituted β-hydroxy or β-alkoxycarboxylic acid amide is converted into the corresponding α,β-unsaturated N-substituted carboxylic acid amide by conducting the vapor over a solid catalyst. The manufacturing method according to claim 1 or 2. 4 Claim 1, characterized in that the amidation exchange reaction is carried out at a temperature range of 100 to 200°C.
The manufacturing method according to any one of Items 1 to 3. 5. The production method according to claim 4, wherein the amidation exchange reaction is carried out in the presence of a catalytic amount of acid. 6. The production method according to claim 5, wherein the amidation exchange reaction is carried out using 0.5 to 1 mol% acetic acid as a catalyst. 7 Metal oxides, oxide mixtures, impregnated carrier catalysts or salts are used as solid catalysts for dehydration of β-hydroxycarboxylic acid amides, and acidic or basic inorganic oxides are used as alcohol elimination catalysts for β-alkoxycarboxylic acids. 7. The manufacturing method according to any one of claims 1 to 6, characterized in that: 8 The metal oxide is aluminum oxide, the mixture of oxides is a mixture of aluminum oxide and silicon dioxide, the impregnated carrier catalyst is acidic aluminum oxide or phosphoric acid impregnated pumice, and the salt is aluminum phosphate or boron phosphate. The manufacturing method according to claim 7, wherein the inorganic oxide is aluminum oxide, silicon dioxide, or barium oxide. 9. The manufacturing method according to claim 7 or 8, characterized in that the material is impregnated with an inorganic oxide. 10 Claims 1 to 9, characterized in that dehydration of β-hydroxycarboxylic acid amide or alcohol elimination of β-alkoxycarboxylic acid amide is carried out at a temperature of 200 to 400°C. manufacturing method. 11 α,β-unsaturated N represented by the following general formula
-Substituted carboxylic acid amide. In the above, R ¹ and R ² represent hydrogen or a methyl group, R ⁶ and R ⁷ are an alkyl group or phenyl group having 1 to 4 carbon atoms, or together constitute a cyclohexenyl group, and n is 1 represents an integer ^{from 3 to 3} ; 3 to 8 jointly
cycloalkyl group with carbon atoms) or formula (Here, R ³ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ are as described above, and A is a salt-forming anion). However, R ¹ and R ² are both hydrogen, n=1, R ⁶
and R ⁷ are all methyl groups, and X is -N
( _CH3 ) Except for ₂ .