SA96160586B1 - Ahighly polymerizable N - vinylcarboxylic acid amide and production method - Google Patents

Abstract

A highly polymerizable N-vinylcarboxylic acid amide having an N-1, 3-butadienylcarboxylic acid amide content of 30 ppm or less, a process for producing the same, and a process for producing a homopolymer of N-vinylcarboxylic acid amide or a copolymer thereof with another copolymerizable monomer using the same. Also, a highly polymerizable N-vinyl-carboxylic acid amide is produced by thermal cracking or catalytic cracking of N-(1-alkoxyethyl)carboxylic acid amide or ethylidenebiscarboxylic acid amide, wherein the N-vinyl-carboxylic acid amide content of the N-(1-alkoxyethyl)-carboxylic acid amide or ethylenebiscarboxylic acid amide is 10 wt% or less.

Description

Y

The highly polymerizable amide©-phenylcarboxylic acid and its production method

A highly polymerizable N-vinylcarboxylic acid amide Production of sual amide by weight Je polymer and a method for producing a polymer. Using the same compound, N-vinylcarboxylic acid amide, carboxylic acid 0, did oN, and with more specification; The present invention provides an amide compound with improved polymerizability and a carboxylic N-vinylcarboxylic acid amide method | to produce the same compound. N-vinylcarboxylic acid amide is used to produce a monomer in industry, distinguished as a monomer. Where this polymer is used. polymer by a method for producing the polymer Lad as a thickener. The present invention provides Nu vinyl carboxylic acid moreover + the present invention provides high quality N-vinylcarboxylic acid amide useful as a raw material for industrial chemicals N-vinylcarboxylic acid amide or medical products in various fields. So far, a large number of methods have been proposed for the production of Jag, N-vinylcarboxylic acid amide (ethyl carboxylic acid)-(Na) carboxylic acid is known, as it is synthesized as an intermediate compound produced from an amine N-)1-alkoxyethyl) carboxylic acid amide without v alcohol, acetaldehyde alcohol and carboxylic acid amide acetaldehyde, by cracking or catalytic cracking of the product. Phenylcarboxylic acid oN is another useful method. For the manufacture of an amide, including the manufacture of N-vinylcarboxylic acid amide acetaldehyde from a carboxylic acid ethylidene biscarboxylic acid ©, after that it is broken. carboxylic acid amide and an N-vinyl carboxylic acid amide produced into a carboxylic acid -carboxylic acid amide and an N-vinyl carboxylic acid amide in those methods; supply purification step; like distillation; extract and redo. The product is N-vinylcarboxylic acid amide N-Vethylcarboxylic acid crystallized amide 0 as (JP-A} means JP-A-61-286069 as an example; Japanese Patent No. Here [Untested Consulted Japanese Patent Application] Separation extraction method using aromatic hydrocarbon.This is because the distillation process fails to prevent formamide.Moreover did-87 miscibility of fumamide as unreacted raw material into

Gall that; JP No. 17-8-63-132868 describes cryogenic crystallization from ve extraction using mixed organic JP-A-2-188560; Japanese patent © aromatic hydrocarbon discloses an aqueous inorganic salt solution and aromatic hydrocarbon and US Patent No. 7 40 4 discloses hyperactive distillation of -polyhydric alcohol using polyhydric alcohol on the other hand; The amide 7<-vinylcarboxylic acid Ye vinyl —N polymerizing amide complex is obtained by polymerizing N-vinylcarboxylic acid amide alone or polymerizing N-vinylcarboxylic acid amide as a coagulant; or another polymer. The polymer monomer mixed with the monomer is used as a fluid absorbent or as a thickener; In any of these cases, the molecular weight must be high. polymer Yo sperm

¢ In any case; It is difficult to obtain “Nad-vinylcarboxylic acid amide” that shows consistent good polymerizability in any of the uses described above. General description of the invention: ° The object of the present invention is to supply a 7<-vinylcarboxylic acid amide, N-vinylcarboxylic acid, having a polymerizability of 50a and improved polymeriazbility. The objective of the present invention is to produce a high molecular weight polymer using Jind —N carboxylic acid amide N-vinylcarboxylic acid amide As a result of extensive research on the production process of Nad 0-vinylcarboxylic acid amide N-vinylcarboxylic acid amide, which has good polymerizability, the present inventors found It is possible to produce a high-molecular-weight polymer using N-vinylcarboxylic acid amide 87, which has an amide content of -1-7- buta oi 01 N-1,3-butadienyl carboxylic acid. amide 05 ppm or less ; most preferably 1 ppm or less; Thus achieving the present invention. customize more; The present invention provides a highly polymerizable N-vinylcarboxylic acid amide; Where the amide 1 - 38 Jb carboxylic acid N-vinylcarboxylic acid amide 0 has an amide content <- 1 » *- Buta chirophenyl carboxylic acid 51 N-13-butadienyl carboxylic acid amide part in million or less; And its production method “And a method for producing a high molecular weight polymer of ~N-vinylearboxylic acid amide using that same compound. Brief explanation of the drawings: Yo Figure (1) shows the relationship between viscosity and the content of 1-7 ?- BL Sa acetamide N-1,3-butadieny! acetamide amide from =N phenylacetamide crude Bala o The viscosity is (1) as measured after making Example No. vinylacetamide (NVA). Carboxylic acid 0 :) in the present 2 selector in general formula no

CH,=CH-NR'-COR'

J SU or a hydrogen group where each represents 21.82 hydrogen atoms to © atoms. 1 of carbon atoms contains a number of carbon atoms alkyl group ¢ N-vinylformamide Examples of this compound include the following : 77- Phenylformamide 01 11-formamild “N-methyl-N-vinylformamide ‎ -N -N « N-vinylpropion amide L-17-phylylpropionamide » N-methyl-N-vinylacetamide 71-phenylbutylamide » N-methyl-N-vinylacetamide phylylpropionamide “N- methyl among N-vinylisobutylamide 71-vinyl isobutylamide » N-vinylbutylamide 0 phenylacetamide -N ; Jay » N-vinylacetamide (I) β-diphenylcarboxylic acid with Formula ~ YON Amide Fa

CH,=CH-CH=CH-NR'-COR'? (ID) where both 21 and 62 have the same meaning as the previous 0 and include the two forms Ye nah which exist as geometric similarities of that and trans and the compound trans. vv

In the present invention, the highly polymerizable N-vinylcarboxylic acid amide did “Nad” is obtained by making the amide content of ALB Lr YON enyl carboxylic acid N-1,3-butadienylcarboxylic acid amide into an amide The -N-phenylcarboxylic acid 1 N-vinylcarboxylic acid amide © ppm or less; However, the higher polymerizability can be obtained by preferentially making the content Yo ppm or less; Most preferably, the content should be 1 ppm or less. If the content goes beyond the domain described above; It is difficult to obtain high polymerizability

TION checks this out; as an example; By the relationship between the content of 1 phenyl = ¥ » 1 -N of N-1,3-butadienylacetamide ALD buta crude and viscosity (degree of polymerization of N-vinylacetamide amicetamide). polymerizability There is no specific limit in the production process of the N-vinylcarboxylic acid amide Nad 0 used in that method to produce the highly polymerizable N-vinylcarboxylic acid amide of the present invention; As long as the raw N-vinylcarboxylic acid amide Nad that is obtained has an amide content of VN *- butadienylcarboxylic acid ,3-butadienylcarboxylic acid amide 000 1-1 in excess of “” 0 ppm and in some cases alc more than 10 ppm or 1 ppm In any case, and in one preferred example, N-vinylcarboxylic acid amide Nad is produced Through dealalcoholization of an amide <- ( -1-alkoxy (dd -alkoxyethyl) carboxylic acid amide Yo 1 is obtained as an intermediate compound of carboxylic acid amide and acetaldehyde ‎Sly Alkyl Ba Bala

acetaldehyde and dialkylacetal Ju in that case; The reaction of dealalcoholization is preferably related to thermal cracking or catalytic cracking. In favor of AT, N-vinylcarboxylic acid amide is produced by cracking ethylidene biscarboxylic acid amide or cracking or cracking ethylidene biscarboxylic acid The amide that is obtained as an intermediate compound resulting from acetaldehyde and carboxylic acid amide + in this case » ethylidene biscarboxylic acid breaks down into an amide 0 carboxylic acid amide and - -N-vinylcarboxylic acid amide in the present invention; Jd NEL can highly polymerizable N-vinylcarboxylic acid amide having an amide content vo VN — buta 0 Jay carboxylic acid N-1,3-butadienylcarboxylic acid amide Feo vo fragment in mlb or less by the diaphoretic method in which the amount of amide is reduced or eliminated by 10-17; - J,3-butadienylcarboxylic acid amide 1 from amide 7 <- Crude N-vinylcarboxylic acid amide » or by the diaphoretic method in which the amide 1-8 is reduced or removed ; * - Butadienyl carboxylic acid [N-] ,3-butadienylcarboxylic acid amide 0 or a lower compound thereof from the production raw material or the intermediate compound of Jud-N-carboxylic acid -N-vinylcarboxylic amide A method is described for reducing or eliminating Amed 1-17 »? - Di-butadienecarboxylic acid amide 1,3-butadienylcarboxylic acid amide 1 from 7<-N-vinylearboxylic acid amide Crude as follows: Yo The method includes purification to reduce or remove amide 1 -17 Vo - butadienylcarboxylic acid amide 1-1 from vvy amide

A

¢ raw As an example N-vinylcarboxylic acid amide Jad —N A physical purification method for treating the crude 7<-vinylcarboxylic acid amide or a solution thereof by repeated distillation; or N-vinylcarboxylic acid amide crystallization; or pressure crystallization; or treatment with an adsorbent such as sale) activated carbon VN method; And a purification treatment method using the chemical transformation of the amide 0 ¢ N-1,3-butadienylcarboxylic acid amide carboxylic acid Jui di-buta - ethyl carboxylic acid SB buta - FV oN similar to the amide treatment method using p-benzoquinone with barbenzoquinone N-1 ,3-butadienylcarboxylic acid amide Buta-diethylene - * 1 and a method for the treatment of the Diels-Alder group selectivity reaction. This hydrogenation can be accomplished using hydrogenation N-1,3-butadienyl | 0 Methods Either each method individually or in a group. Any method other than those described above may be used if it is possible to separate ; 1-butadienylcarboxylic acid 1 -<7 or the chemical transformation (amide) of the amide 77-vinylcarboxylic acid N-1,3-butadienylcarboxylic acid amide -N-vinylcarboxylic acid amide | 0 buta = Ve 1-17 is described for the method for removing or reducing the amount of amide from N-1,3-butadienylcarboxylic acid amide crude diphenylcarboxylic acid in preference to N-vinylcarboxylic acid amide ~N phenylcarboxylic acid More amides are as follows: In the method of the present invention; there is no specific limitation on the Ye distillation apparatus used for separation by re-distillation; a stratified column or column may be used. A 50-packet plate contains a theoretical number of plates In any case, it is preferable to use a re-distillation column, as it causes little loss in the Abd packet column, pressure and has excellent re-distillation ability, and includes using a uniform filling. It is preferable to conduct distillation at a temperature as low as Ye N-vinylcarboxylic acid amide phenylcarboxylic acid -N as possible because amide Bala q 0.10 decomposes easily due to heat. Therefore, the distillation is carried out under a reduced pressure of mm Hg.‎ 001 To the re-distillation can be connected either continuously or crosswise (with discontinuity); however, it is preferable to the continuous process from the point of view of productivity

ol, 0 in the process. The percentage of distillation is not precisely defined and can be determined according to the content of Nd (0) butadienylcarboxylic acid amide, N-1,3-butadienylcarboxylic acid amide type, 7<- phenylcarboxylic acid amide, and distillation column efficiencies. . And anyway; The distillation ratio is generally from 1.1 to Ye and it is preferable to be from 0# to .01.

b “In the process of the present invention; when Ay hah od all recrystallization involving quenching of the ON crude N-vinylcarboxylic acid amide » the amide of the 7 <- phenylcarboxylic acid N- vinylcarboxylic acid amide directly; or a recrystallization solvent that does not react with the 7<-phenylcarboxylic acid amide can be used.

N-vinylcarboxylic acid amide '© has a suitable melting point for that compound. AB recrystallization solvent includes an aromatic hydrocarbon such as benzene ¢ and toluene ; And xylene or an aliphatic hydrocarbon such as pentane, cyclopentane, hexane ¢, cyclohexane, heptane, and alcohol

alcohol Y- such as methanol » ethanol » n-propyl alcohol » similar isopropyl alcohol Lu ll » n-butanol » isobutanol » secondary butanol sec-butanol «tert-butanol» and cyclohexanol ¢ hydrocarbon containing halogen Jie halogenated chloroform

¢ acetone Jie ketone ketone » chlorobenzene and chlorobenzene chloroform Yo ¢ cyclohexanone and cyclohexatone » methyl ethyl ketone and megel ethyl ketone

Except

.) an ester such as methyl acetate, ethyl acetate ¢, propyl acetate, and butyl acetate; Jie ether diethyl ether; Je amide 1031- Dimethylformamide “NN 1 N,N-dimethylformamide 2-methylacetamide N,N-dimethylacetamide ¢ and dimethylsulfoxide. Toluene and cyclohexane are preferred; methanol; and similar propyl alcohol. These solvents can also be used in formulation. The quenching temperature varies according to the type and quantity of N-vinylcarboxylic acid amide and the sa cf recrystallization solvent, but it is usually from 70 to fon; Preferably from 01 to 6 pm. Ve that the crystallization apparatus used in the present invention is not precisely defined with regard to its structural formula and it can be either a continuous system or a batch system. Also, the UW distillation method is used for heat exchange with a cooling medium; or concentration and cooling of the solvent upon evaporation. Load does not accurately specify the special device for separating crystals used in the invention JLo. A device using vacuum pressure or applying pressure may be used; Or a device that uses gravitational or centrifugal forces. In the present invention; A solid-liquid separator can also be used, which combines crystallization and separation in the same device. Device preference A AY includes 0 if the following crystallization solvent is not used; pressure crystallizer; Ye and a tower-type continuous crystallization purifier (eg 3140 or back-mixing column crystallizer). In the case of filtration of a highly concentrated micro-aqueous suspension; A Nutche filter is preferred to such a -Rosemund filter in the process of the present invention; When Nad prefers the crude N-vinylearboxylic acid amide by treatment with a Yo adsorption material such as activated carbon; The adsorbent does not accurately specify, Lalla, that it selectively adsorbs amide 1 SN » 7- buta-diethylcarboxylic acid VVV

Vy

EBs mY » 1 Nall Comparator N-1,3-butadienylcarboxylic acid amide

A Bd incl. 1-1 ,3-butadienylcarboxylic acid amide Carboxylic acid Ji; Among them; resin is preferred; zeolite resin, zeolite ¢ silica, and activated silica. carbon Vityl Nad in the adsorption process of the present invention; The crude can be put in direct contact with N-vinylcarboxylic acid amide, the carboxylic acid, the adsorption agent. Instead; The crude solution can be dissolved in a non-reactive solvent, where N-vinylcarboxylic acid amide, the carboxylic acid, Jud -<7, with an amide. have an appropriate solubility point; It is then brought into contact with the adsorbent 0 Examples of the solvent include water and those solvents mentioned above in relation to the activator as an adsorption agent; carbon by the recrystallization method; And when carbon is used, the ratio between the solvent to the amide of methanol is preferred, especially water and methanol. ¢ is not precisely defined. N-vinylcarboxylic acid amide phytyl carboxylic acid ~N as a solvent is preferred to be methanol. In any case; When using water or mechanol 0:1 to 0.1 (by weight); It is preferable that the ratio be from 1: 01 to 0 (by weight). to 7650 m. And if the adsorption temperature is from 0 to 1007 C, and the most preferable is from, then this hinders the diffusion process to the holes of the adsorbent material to the extent of “Ye - less than a certain one, which increases the adsorption time in an undesirable way. And if the degree of phenyl acid is oN M; It reduces the stability of the amide 001 at higher temperatures and at the same time significantly reduces the amount of N-vinylcarboxylic acid amide carboxylic adsorption.

VY

An adsorption method in the present invention does not specify precisely what its exact structural formula is received; But that method can be either a continuous system or a batch system. In the present invention; Bear ON amide content can reduce N-1,3-butadienylcarboxylic acid amide in 7<-phenylcarboxylic acid N-vinylcarboxylic acid amide to T+ fraction per million or less by chemical treatment of the crude N-vinylcarboxylic acid amide solution. There is no particular limitation of the chemical reaction used as long as it exploits the difference in activity between the N-vinylcarboxylic acid amide Nad and the amide —YO -N buta SB ethylcarboxylic acid N-1,3 -butadienylcarboxylic acid amide . For example, a reaction with a compound containing two double bonds is very active while a reaction with a compound containing one double bond is inactive. The method for treating the crude N-vinylcarboxylic acid amide © JN solution using the Diels-Alder reaction is described; The treatment process is performed by allowing the dienophilic compound ghd in the Diels-Alder reaction to exist in a 1<7-vinylearboxylic acid amide solution. The doubly hydrophilic compound is not precisely defined in the present invention since that compound Yo is commonly used as a double bonding compound in the Diels-Alder reaction; and more customization; That compound is selected from the unsaturated compounds in the a-place and substituted by de gana or more electron-attractive groups and does not interact with an amide—N-vinylcarboxylic acid amide + Examples of double bond loving compounds include the following: unsaturated carboxylic ester yo0 such as acrylic ester maleic ester, fumaric ester ji ¢ and ketone Bala

YY

Unsaturated such as methyl vinyl ketone, p-benzoquinone, unsaturated nitrile such as acrylonitrile, and saturated imide such as maleic acid imide. Among those vehicles; P-benzoquinone is preferred. The amount of 0 is not precisely defined as the double bond hydrophilic as long as it is equal to (or more than) the amount of 1-17”-N-1,3-butadienylcarboxylic acid amide in amide 7 <- Crude N-vinylcarboxylic acid amide. And anyway; The molar ratio of the hydrophilic compound of the double bonds to the amide of Byam oN diethyl 0,3-butadienylcarboxylic acid amide is 11-1 in a solution of the crude N-vinylcarboxylic acid amide general from 1 to 100 equiv ; Preferably from 017 to 01 equivalent. In the present invention “0” when a =N amide solution treats N-vinylcarboxylic acid amide by the Diels-Alder reaction » 11 can contact the amide 7<-N-vinylcarboxylic acid The crude acid amide directly with the hydrophilic compound of the two double bonds. Vary than that; The crude solution can be dissolved in a solvent that does not react with N-vinylcarboxylic acid amide and has a suitable solubility; Then, it is subjected to the Diels-Alder reaction. Examples of a solvent include those solvents described above in relation to the adsorption method in the present reaction. In addition 1 although no catalyst is required when the crude N-vinylcarboxylic acid amide is treated by the Diels-Alder reaction in the present invention; Those compounds known to have catalytic activity can be used in the Diels-Alder reaction and which do not react with the 137-did N-vinylcarboxylic acid amide treatment Yo. Examples of catalysts include Bala acids

B "Jie Lewis aluminum trichloride, boron trifluoride, and -lanthanide complex that 0 die from -JY; and most preferably from 0 to TA if the reaction temperature is less than 10"C; the reaction rate is very slow; while if the temperature exceeds 100"C fie This reduces the stability of the N-vinylcarboxylic acid amide 87 in an appropriate manner Je dae contains oN the N-vinylcarboxylic acid amide 0 treated by the Diels-Alder reaction in the invention lal on the Diels-Alder product produced by the Diels-Alder reaction, but this compound has almost no detrimental effect on the oN-vinylcarboxylic acid amide polymerization process. -Alder produced in the present invention has a lower vapor pressure value compared to Byam VV Nall Sle enyl carboxylic acid wy.

N-1,3-butadienylcarboxylic acid amide ely If the crude N-vinylcarboxylic acid amide Nad solution was purified by distillation after treatment with the Diels-Alder reaction in the present invention; Diels-Alder can be separated more easily than I Ge a TON amide, 3-butadienylcarboxylic acid amide | 0 1-1 which is separated by fractionation alone. That is, the compound can be separated using a simple distillation apparatus. Treatment of the crude N-vinylcarboxylic acid amide using the hydrogenation reaction of the present invention by contacting the crude N-vinylcarboxylic acid amide with the YO hydrogen hydrogen in the presence of a catalyst. The catalyst is not precisely determined as long as it has general activity in the selective hydrogenation reaction except

Vo catalyst In any case + it is preferable for the catalyst to have 1 olefins of SU levins, the double-bonded binary compounds at hydrogenation, with high selectivity for hydrogenation and the double-bonding compounds together. Monoolefins include the presence of monoolefins or cobalt series or pladium series catalyst catalyst ZB or a concentrate product of these metals equipped with NCo-Cr nickel-cobalt-chromium metals© activator or silica 911168 including carbon or carbon alumina over alumina asl and palladium-silver Pd-alumina compounds; Preferably palladium - alumina - and palladium » Pd-Pb-alumina Palladium - lead - alumina ¢ Pd-Ag-alumina Supplied as agents Pd-alumina and palladium - alumina Pd-Cr-alumina chrome alumina as a metallic component; It is preferable that the quantity of pladium when using the palladium catalyst catalyst be 0 to 0.01 to 78 of the weight, and it is more preferable that it be from 1.0010 carried, of which the rate of weight is 70.0009 of weight. If the quantity carried is less than 1 very slowly, while if the quantity exceeds 75 by weight, this increases the amount of Jeli amide hydrogenation resulting from the hydrogenation of N-ethylacetamide amide 7<- ethyl acetamide in an inappropriate way. N-vinylcarboxylic acid amide Carboxylic acid Jud [h-1 phenylcarboxylic acid Nad Laie treated in the present invention can be » hydrogenation by direct hydrogenation reaction N-vinylcarboxylic acid amide N-vinylcarboxylic acid amide ~N-vinylcarboxylic acid amide contacts or can be dissolved in a solvent; Where this hydrogen solvent does not interact with hydrogen, and where N-vinylearboxylic acid amide with amide 17- phenylcarboxylic acid 0 000 hydrogenation has a suitable melting point and then is subjected to an acid hydrogenation reaction that the acid has Examples of solvent include Those solvents described above regarding the adsorption method, preferably “alcohol” is among those solvents; Alcohol is preferred. Jal in the similar invention. The isopropyl alcohol and methanol propyl alcohol in particular the methanol of the present invention hydrogenation The appropriate reaction temperature for the hydrogenation reaction varies 0001 to -100 for the type of catalyst used; But preferably from a ba ba balla

1 C 01 - If the reaction temperature is less than . aA to 0 and more preferably from, the reaction rate is very slow, while if it exceeds 0100m; This reduces 0 N-vinylcarboxylic acid amide phenylcarboxylic acid ~N amide stability suitable for the hydrogenation reaction The partial pressure of hydrogen is preferably 1 MS/MGC 001 to 1.01 Selectivity of the present invention hydrogenation © kg/cm? This causes the rate of reaction to be very slow; on Je it is from acetamide JAN kg / cm ", this increases the production of amide 001 if the acid Lay exceeds Jd -37 amide hydrogenation The resultant hydrogenation of N-ethylacetamide, and the device becomes more expensive. N-vinylcarboxylic acid amide carboxylate when charged and asked the catalyst; the appropriate conditions vary for speed Vs and temperature of vacuum hydrogen of the liquid depending on the partial pressures of hydrogen reaction and content amide-701-butadienylcarboxylic acid, but the stereovelocity is preferably 11-1,3-butadienylcarboxylic acid amide 1-butadienylcarboxylic acid 1-butadienylcarboxylic acid amide 1-1 CF-18, as this causes insufficient conversion of amide 0001 to the liquid Whereas, if “N-1,3-butadienylcarboxylic acid amide enyl carboxylic acid ve is less than 0.05, this reduces the reaction efficiency. The reaction method used in the present invention can perform continuously or In batches and the reaction vessel does not specify precisely in its structural form Any of the gas-solid contact, the gas-liquid-solid contact, and the solid-liquid contact can be used, however, it is preferable to a solid-liquid reactor that has the capacity - 0 » ’ . On the homogeneous contact of the raw material with the catalyst under relatively mild conditions, a stem is dissolved in hydrogen when performing the solid-liquid interaction » the hydrogen is N-vinylcarboxylic acid amide phenyl carboxylic acid -N amide solution Important for the reaction. Hydrogen is supplied with hydrogen, the reaction solution contains products » hydrogenation after the hydrogenation reaction Yo 0 hydrogenation Hydrogenation Jeli is undesirable accompanying the product produced by sperm

VV

Methods for selecting a reaction solution include; as an example; repeat distillation; recrystallization by cryogenic and pressure crystallization of the solution; These two methods can be used either alone or together. Change these two methods; Any method can be used without exact determination if the undesirable product and the amide can be easily separated. N-vinylcarboxylic acid amide Phenylcarboxylic acid -N©dd as described above; It contains a 7:1-37-bibuta cis in the form of cis N-1,3-butadienylcarboxylic acid amide the carboxylic acid ¢ and the activity of both of them is physical and due to a difference in the physical properties trans AT That the amount of separation differ in the current invention. in that case; A similar cis-trans reaction of the amide compound L-3,7-01”-butadienylearboxylic acid 0 can be performed under the appropriate reaction conditions N-1,3-butadienylearboxylic acid carboxylic acid in combination with the processes described above eg Chapter.‎ In any case; The 17-vinylcarboxylic acid amide causes solvent dissolution or hydrolysis when there is N-vinylcarboxylic acid amide 800 present. And on that; Additional facilities for use in the current VO are preferred; like a production device; a device for separating; and a tank for the raw material; Jeli or (nitrogen) and a tank for filtration under an atmosphere of inert gas (nitrogen 0) and a container for the product air dry. In addition, to prevent the hydrolysis reaction of the amide <-phenylamide, add a small amount ( Say « N-vinylcarboxylic acid amide carboxylic acid to the raw material. magnesium sulfate too from a drying agent such as magnesium sulfate Ye dimerization (dimerization when a base is present; produces a dimer reaction to form a dimer). Preferably, monomer means the union of two molecules of the monomer vinylcarboxylic acid -N - of an amide solution pH adjusting the pH value 01 before the distillation and adsorption processes to a value from ? to N-vinylearboxylic acid amide when the solution is 1. It is more preferable to be from * to 01 and preferably from 4 to Yo crude N-vinylcarboxylic acid amide phenylcarboxylic acid -N amide Bala

Ya

by adding a base compound. pH pH 1 adjust + acid value includes sodium carbonate Jia sodium salts Examples of a base compound include ¢ sodium hydrogencarbonate, ¢ sodium carbonate, and sodium phosphate hydroxede and sodium hydroxide salts ¢ sodium acetate and sodium (hydrogen)-phosphate © « potassium carbonate potassium potassium hydroxide ¢ potassium acetate a gr WS gl acetate « potassium (hydrogen) phosphate

Jie aromatic amines and amines and aromatics 00

N-phenyl-a-naphthylamine, 4,4"-bis(a,a-dimethylbenzyl)diphenylamine, N-phenyl-

N-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N"-isopropyl-p-phenylenediamine, N-phenyl-N’-(1-methylheptyl)-p-phenylenediamine, N-phenyl-

N'-cyclohexyl-p-phenylenediamine, N,N -diphenyl-p-phenylenediamine, N,N'-di-B- naphthyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p- phenylenediamine, Yo

N,N"-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N “-bis(1-methylheptyl)-p-phenylenediamine and N-phenyl-N "-(p-toluenesulfonyl)-p -phenylenediamine, compounds with sodium hydroxide Sh to be als where preferably -sodium hydroxide 00001 to 1 The added amount of the base compound is preferably from Ye . ppm 0001 to 01 ppm and it is preferable that it be from Ala salt other than ppm » in 00001 if the added amount exceeds extra il organic; This leads to the complete quantity not being dissolved and there is no expected excess quantity. in the case of an aromatic amine; It is difficult to completely remove this in the purification step; the aromatic amine Yo 0 N-vinylcarboxylic acid amide polymerizability is reduced ppm; 1 effect will not be obtained if the amount added is less than approximately stable. Moisturizes

When the crude N-vinylcarboxylic acid amide solution oN is basic, the adjustment process is performed by adding an acidic compound. Examples of an acidic compound include inorganic acidic compounds such as hydrochloric acid ©, sulfuric acid, nitric acid ¢, and salts ody phosphoric acid among them 1 And acidic organic compounds that include carboxylic acids such as acetic acid, phthalic acid ¢, citric acid + fis carbolic acids, phenol “hydroquinone” and catechol |0 ; and salts of 5 thereof. Among the methods used in the present invention is a method for reducing or removing the amide YON 3-butadienylcarboxylic acid amide 1-1, or A precursor compound thereof that is contained in the productive raw material or intermediate of Nad N-vinylcarboxylic acid amide © as described below The content of the precursor compound is expressed in terms of content =F + 1 - Nad buta SLB Ethyl carboxylic acid N-1,3-butadienylcarboxylic acid when all the precursor compounds are converted to amide YON butadienyl carboxylic acid -N-1,3-butadienylcarboxylic acid 9. In a method of the present invention 0 The production raw material or intermediate for the 7<-N-vinylcarboxylic acid amide includes the N-(-)-alkoxy amide (J) carboxylic acid amide (N-(I-alkoxyethyljcarboxylic acid amide ¢) and the di-alkyl Dialkylacetal acetal and ethylidenebiscarboxylic acid amide. The alkoxyl group ~~ Yo in the amide-1-(oN alkoxyethyl) amide includes a carboxylic acid N-(1-alkoxyethyl)carboxylic acid amide and dialkylacetal vvy

Y.

Aliphatic alkoxy group such as methoxy, ethoxy, n-propyl ¢, the similar iS0propoxy ©, n-butoxy and sec-butoxy. Examples of the carboxylic acid amide group include 8. R-1-(Nd alkoxyethyl) Sy SU a eal N-(1-alkoxyethyl)carboxylic acid amide ethylidene dicarboxylic acid formamide ethylidene biscarboxylic acid amide formamide » N-methylformamide » acetamide ¢ and N-methylacetamide 11-1; propionamide; butyramide 0 and butyramide 16000070200106. WAY) includes the corresponding compound: as 1-(AN alkoxyethyl) carboxylic acid amide oS sie -1 ) -N ¢ N-(1-alkoxyethyl) carboxylic acid amide Eichl)-1-acetamide - N-methoxyethyl)formamide-1(-N « N-(1-methoxyethyl) acetamide alkoxyethyl)-acetamide -1(-N « N-(1-methoxyethyl) formamide alkoxy (Ji 0 formamide) -1(-11 ¢ N-(l-ethoxyethyl) acetamide propoxyethyl analogue) N-(1-isopropoxyethyl) acetamide and 1<- 1-(alcoxyethyl)formamide Jia N-(1- isopropoxyethyl) formamide — alkyl acetal dialklacetal “dimethylacetal” tafsi J3) diethylacetal ¢ and the cognate “di isopropylacetal” as amide J WORRY Fc chain 0 carboxylic acid ethylidenebiscarboxylic acid amide » ethylidenebiscarboxylic acid amide » adi 013110001588006 » ethylidenebisformamide » ethylidenebis (N-methylformamide) ethylidenebis (N-methylformamide) and ethylene Sb propionamide

.ethylidenebispropionamide a Saal (J eS 1) Nad Oe re SLE lay or N-(1-alkoxyethyl) carboxylic acid amide

unless

The carboxylic ethylidenebiscarboxylic acid amide was converted to N-vinylcarboxylic acid amide by a known method such as thermal cracking or catalytic cracking. The reaction conditions are; as an example; Use the gas phase or the liquid form. The reaction temperature is from 0 to 0000 C; The reaction time is from 1 sec to 2 hours, and the atmospheric pressure is calm. Amalgamation of the catalyst used in the case of catalytic cracking includes an alkali metal salt of a carboxylic acid such as potassium acetate and alkali metal oxide 6 or an alkaline earth metal such as magnesium oxide Ve amide TON butadienylcarboxylic acid (N-1,3-butadienylcarboxylic acid) is produced by removal of two alcohols induced by thermal cracking or catalytic cracking (Nal (Nal(dialkoxybutyl)) induced by thermal cracking or catalytic cracking (F CV) ,3-dialkoxybutyl) carboxylic acid amide 1-1 or by removing Jy aS and a carboxylic acid amide 05 that is induced by thermal cracking or catalytic cracking of the amide =F alkoxybutylidene carboxylic acid 3- alkoxybutylidene biscarboxylic acid amide . The N-(1,3-dialkoxybutyl) carboxylic acid amide ON *- dialkoxybutyl) carboxylic acid amide is produced by the reaction of =e) » 1 0 alkoxybutane 1,1,3-trialkoxybutane with carboxylic acid amide 7 and so on; And in the present invention; Examples of amide subarrays =F} - 7-butadienylcarboxylic acid FO 1 1,1,3-trialkoxybutane amide (17 GB -1) N-(1,3-dialkoxybutyl) carboxylic acid amide and *- alkoxybutylidene iE carboxylic acid amide Yo Examples include alkoxy group and amide groups of the carboxylic acid ‎carboxylic acid amide group is at Ba Bala

YY

Those ancestral enantiomers are the examples described above for the precursor compounds of Jud -N-vinylcarboxylic acid amide. And for that - include 1 2 0,7-trimethoxybutane 1 1,1,3-trialkoxybutane L 7-trimethoxybutane Db -010 1 Y «1,1 3-trimethoxybutane ETOXY 0 1-010-Butane » 1,1,3-triethoxybutane Tripropoxybutane analogue 0 1,1,3-triisopropoxybutane amide includes (1-<[ ; SET alkoxybutyl) carboxylic acid — Y <1) -N « N-(1,3-dialkoxybutyl) carboxylic acid amide ,3-dimethoxybutyl) acetamide L =V ¢ V)-N dimethoxybutyl)formamide formamide (Anzanata(:1,3-01016010)-17 » amide -N ~N ¢ N-(1,3-diethoxybutyl) acetamide diethyloxybutyl)acetamide -” ay) L 1 N -(1,3-diethoxybutyl) formamide (ethoxybutyl)-formamide (SBT)

N-(1,3-diisopropoxybutyl) acetamide propoxybutyl conjugate (SBF +1) propoxybutyl conjugate (propoxybutyl conjugate) formamide ET CY) -8 f alkoxybutylidine dist = v or including amide 1 , 3-diisopropoxybutyl) formamide 10 carboxylic acid = F 3-alkoxybutylidene biscarboxylic acid amide 3-methoxybutylidene bisacetamide ; f=Y methoxybutylidenebisacetamide 3-methoxybutylidenebisacetamide ali¢, F=methoxybutylidenebisacetamide + methoxybutylidenebisacetamide ali 7-ethoxybutylidenebisacetamide ali-1-ethoxy butylidene ali formamide ethoxybutylidenebisformamide and ?-propoxy al ie butylidenebisformamide ED acetamide 3-isopropoxybutylidenebisacetamide and ?- propoxy-like butylidenebisformamide ?-3-1sopropoxy butylidenebisformamide includes example for reduction of amide components (01-17-7) Buta AE ethylcarboxylic acid 1,3-butadienylcarboxylic acid 10-1 or its lower compound in ve production raw material or intermediate compound of N-vinylcarboxylic acid amide to 01 ppm or less; as an example; method b except

repeat instillation; And the method of recrystallization by cooling the solution of the lower compound of N-vinylearboxylic acid amide (where the lower compound means the parent compound from which the amide (N-vinylcarboxylic acid amide) is derived pressure crystallization method for the bottom 0 compound n, the physical adsorption method by treating the substrate with an adsorbent such as activated carbon, and a method for the chemical treatment of the bottom compound These methods can be used either individually or in combination Other methods can be used without exact limitation as long as they can be easily separated The amide, TON, buta-diethylcarboxylic acid, N-1,3-butadienylcarboxylic acid, for 0 of the production material, Jad, or for the intermediate compound of the amide <- did the carboxylic acid -N-vinylcarboxylic acid amide In addition, as a result of extensive research in the process of producing N-vinylcarboxylic acid amide which has good polymerization ability, the inventors of the present invention found that N-vinylcarboxylic acid amide is produced Novinylearboxylic acid amide is used in the manufacture of a high molecular weight polymer baie (in the case of producing N-vinylcarboxylic acid amide by thermal cracking or catalytic cracking of 1-(N-alkoxyethyl) amide ) N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide « 00 The amide content of -N-vinylcarboxylic acid amide is less than - 1 (Nad alkoxyethyl) carboxylic acid N-(I-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide to 701 by weight or less and the pH value is adjusted of an aqueous solution of 277 (hereinafter simply referred to as the vo value pH (PHT) of amide 7<--1(Ji)carboxylic acid 'AA'

Y¢

N-(1-alkoxyethyl) carboxylic acid amide or SLE

The carboxylic acid ethylidenebiscarboxylic acid amide from © to .01 and more specifically; The present invention provides a method for producing an N-vinylcarboxylic acid amide having good polymerizability; where ¢ © when N-vinylcarboxylic acid amide is produced by thermal cracking or catalytic cracking of N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide of “Na (- alkoxyethyl) carboxylic acid amide N-(1-alkoxyethyl) carboxylic acid amide 0 or amide cpa ly dicarboxylic acid ethylidenebiscarboxylic acid amide to 701 by weight or less; preferably 75 weight or less and most preferably 77 weight or less; The pH value of N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide is adjusted to 15 ge to 01 It is preferable to adjust from 3 to CA and most preferably to adjust from 6,7 to 7,8; it is still preferable that the Nad content reduces the N-vinylcarboxylic acid amide to AY of weight or less and at the same time

time; The pH value is set by Vio (HUY) There are many reasons why amide may contain 7<-1(alcoxyethyl)Ye carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide or ethylidene amide The ethylidenebiscarboxylic acid amide is generally more than 0:701 by weight of the N-vinylcarboxylic acid amide. One of the reasons is that when purifying and separating a reaction solution containing an amide -1(-N-alkoxyethyl) carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide or © ALS cpa dad carboxylic acid amide ethylidenebiscarboxylic acid amide were obtained by the above mentioned manufacturing method by Distillation process b only

Yo (1-alkoxyethyl) -<7 or any similar process; a portion of the carbamide or ethylidene amide N-(1-alkoxyethyl) carboxylic acid amide breaks down to ethylidenebiscarboxylic acid amide carboxylic acid ALD

N-vinylcarboxylic acid amide phenylcarboxylic acid -N phenylcarboxylic acid Nad Another reason is that when ° is made by thermal cracking or catalytic cracking of N-vinylcarboxylic acid amide or N-(L-alkoxyethyl ) carboxylic acid amide (alkoxyethyl) carboxylic acid -1) -N ethylidenebiscarboxylic acid amide SUE carboxylic acid ¢ N-vinylcarboxylic acid amide carboxylic ia asl phenyl -N and the 1-alkoxyethyl) carboxylic acid ( NY ) Ve acid is recycled SUB or N-(1-alkoxyethyl) carboxylic acid amide which contains the carboxylic acid ethylidenebiscarboxylic amide for cracking. N-vinylcarboxylic acid amide N-vinylcarboxylic acid Nad A method is described to reduce the N-1-alkoxyethyl (N-) acid content of the amide N-vinylcarboxylic acid amide 0 or N-(1-alkoxyethyl) carboxylic acid amide carboxylate by weight or 0 to ethylidenebiscarboxylic acid amide carboxylic acid is less as follows: The method is not precisely defined as long as it is a method to reduce the content of N-amide of N-vinylcarboxylic acid amide

N-(1-alkoxyethyl) carboxylic acid amide (Ji alkoxy =) ethylidenebiscarboxylic acid amide or ethylidenebiscarboxylic acid amide by weight or less. This method includes; as an example; Example processing Amide 701 to or N-(1-alkoxyethyl) carboxylic acid amide 1-(Ji-alkoxyethyl) -N or ethylidenebiscarboxylic acid amide Yo solution of them by the method of repeated distillation, or the method of distillation

VVYV

Isotropic) which is a specific method of distillation that depends on adding some materials to the material to be distilled, where these materials unite with existing materials for distillation and change their boiling points by decrease or increase, which makes the distillation process easier. or recrystallization method; Or the pressure recrystallization method, and these methods can be used either on the © dora combined with each other. other than those ways; Any other method may be used without specific limitation if it is possible to separate N(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide and N-vinylcarboxylic acid amide 1. An example of reducing the Nad content of N-vinylcarboxylic acid amide from 1-(N-alkoxyethyl) amide is described. N-(1-alkoxyethyl) carboxylic acid amide ply) ethylidenebiscarboxylic acid amide is reduced to 0 or less in more detail as follows: vo in the process of the present invention; The distillation used in the separation by the method of repeat distillation is not determined precisely and a layer column or a bundle column is used with a theoretical number of layers from 1 to 0, but it is better to use a re-distillation column as it causes very little pressure loss and has excellent re-distillation capabilities, for example Jota Re-distillation column This is a packet column using uniform filling The compounds are N-(-N 0-alkoxyethyl) carboxylic acid amide or pala Carboxylate ethylidenebiscarboxylic acid amide and N-vinylcarboxylic acid amide are compounds that decompose easily due to heat. And on that; It is preferred that the distillation process take place at a low temperature as possible. And on that; The distillation process is performed under reduced pressure YO. from 0.10 to 0.100 mm Hg. Vvyv

The present invention can be performed either continuously or in batches; And anyway; As a productivity and process security point of view; Prefer continuous operation. The percentage of distillation is not precisely defined and can be determined depending on the content and type of “Naa phenylcarboxylic acid amide” and the capabilities of the distillation column 0. However, 0; The distillation ratio is generally from 11 to 71 preferably from 0 to Aa in the process of the present invention; When separation is carried out according to the method of recrystallization by quenching of the N-(1-alkoxyethyl) carboxylic acid amide or ST 0 ethylidenebiscarboxylic acid solution amide Use of recrystallization solvent, apparatus and method described above Lad is related to the method of recrystallization of 17-N-vinylcarboxylic acid amide al-N-vinylcarboxylic acid amide A method for adjusting the pH value of ethylidenebiscarboxylic acid amide is described © to 01 as follows. The pH value of N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide becomes less than © due to the presence of a carboxylic acid Jia carboxylic acid has acetic acid in it. Although it is not clear why the carboxylic acid is present in 0 in that location ald, it is assumed that the acid results from the oxidation of the acetaldehyde used in the manufacture of the 1-(-N-alkoxy) amide N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide or carboxylic acid amide production by solvent hydrolysis. Yo that the method of adjusting the pH value 11M for the 7<- (-1) alkoxy amide (J) carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide or Pf amide

Ya

When ethylidenebiscarboxylic acid amide is not precisely defined. The method includes + as an example; Treatment of amide 10 of © to or N-(1-alkoxyethyl) carboxylic acid amide 1-(N-ethylidenebiscarboxylic acid amide HD Cpa ly) amide or solution of them by the method of re-distillation; or the azeotropic method 5 or the recrystallization method all or the azeotropic method 0 by using a physical barometric treatment or a physical crystallization method or with an acid base neutralization with an acid chemical adsorption or chemical method sale by These methods can be used either separately or in groups. Including physical among those methods; It can carry out the physical method Ve treatment by re-distillation method; Or the method of isotropic distillation, the recrystallization method, Lill, or the method | iq) sale) or the method of “azeotropic vinyl acid N” by pressing the same method as described above with regard to amide removal, including the method of using an adsorbent. N-vinylcarboxylic acid amide carboxylate adsorption. 32S anion method where an anion exchange resin is used ve Examples of a basic compound used in an acid neutralization method include such as sodium carbonate chemical method chemical 6 sodium hydrogencarbonate; sodium carbonate sodium hydroxide sodium hydroxide salt potassium ¢ sodium acetate sodium (hydrogen) phosphate 0 potassium carbonate Jia potassium salt and potassium hydroxide ¢ potassium hydrogencarbonate PPR potassium (hydrogen) and potassium (hydrogen) phosphate ¢ potassium hydroxide -potassium acetate and potassium acetate phosphate alkoxyethyl)-1-carboxylic acid ( Nad) when the Yo solution is diacid Orlin or N-(1-alkoxyethyl) carboxylic acid amide solution

The carboxylic ethylidenebiscarboxylic acid amide is basic ¢ The pH value of 11 M is adjusted for that solution by adding an acidic compound 20. BY on acidic compounds includes acidic inorganic compounds. inorganic such as hydrochloric acid, sulfuric acid, nitric acid ¢, phosphoric acid and salts thereof, and acidic compounds including carboxylic acids such as acetic acid organic, phthalic acid, citric acid, and carbolic acids such as phenol and hydroquinone

Catechol and salts 5 thereof.

01 A 7<-1(ty) alkoxy amide N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide is converted to oN phenyl amide The carboxylic acid, N-vinylcarboxylic acid amide, was formed by thermal cracking or catalytic cracking described above.

Vo in the present invention; N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide causes solvent degradation or hydrolysis in the presence of an acid . And on that; It is preferable to put additional helices for use in the present invention; Like a production device and device

YL chapter; a tank for the material stamper; and a product vessel and filtrate tank in the presence of an inert gas (nitrogen) or a Gla vessel additionally – to prevent the hydrolysis reaction of the (1oN) alkoxy amide (J) N-(1) carboxylic acid -alkoxyethyl) carboxylic acid amide or 0 ethylidenebiscarboxylic acid amide A small amount of Yo drying agent such as magnesium sulfate can be added to the raw material.

Ye.

In the present invention; When an amide N-phenylcarboxylic acid is produced

N-vinglcarboxylic acid amide by thermal cracking or catalytic cracking of the amide

-1(-N alkoxyethyl) carboxylic acid N-(l-alkoxyethyl) carboxylic acid amide or

pa AN ethylidenebiscarboxylic acid amide « 0 The N-vinylcarboxylic acid amide content reduces the N-(N-alcoxyethyl)amide amide -(l-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide to 701 by weight or less; Most preferred

reduce to 77 pounds or less; The pH value of the amide is adjusted

-1( < 7 0 alkoxyethyl) carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide or pa ali ethylidenebiscarboxylic acid amide

To from * to 101, preferably from 1 to 8; It is more preferable to set from 1,7

to 7.0; It is still preferable to reduce the content of N-vinylcarboxylic acid amide to AY by weight or less and at the same time.

re time; The pH value of 11M was adjusted to from 6.9 to 0.5, by which the 17-did N-vinylcarboxylic acid amide, which has the required polymerization potential, was obtained. if the amide content—N-vinylearboxylic acid amide—exceeds the range described above; There will be a tendency to have difficulty obtaining MD

Jus oN Ye The carboxylic acid N-vinylcarboxylic acid amide is highly polymerizable by thermal cracking or catalytic cracking of the amide 77- (-1-alkoxyethyl) carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide. Also ¢ if the pH value exceeds AM of the range described above; vo there will be a tendency to difficulty in obtaining the amide 83 Nevinylearboxylic acid amide by thermal cracking or catalytic cracking of the amide

Dr

N-(-1-alkoxyethyl) carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide or -ethylidenebiscarboxylic acid amide The present invention provides a method for producing a homopolymer or a polymer Mixed ha Sp SU N-vinylcarboxylic acid amide© using the N-vinylcarboxylic acid amide described above. By using N-vinylcarboxylic acid amide is highly polymerizable as the crude N-vinylcarboxylic acid amide has an AR amide content of 1-1 N-1,3-butadienylccarboxylic acid amide © ppm or less; A high molecular weight homopolymer consisting of N-vinylcarboxylic acid amide or a copolymer mixed with another copolymerizable monomer can be obtained. as used here; The term "highly polymerizable" means that 0 the amount of viscosity as measured after completing Example No. (1) is *0 centimeters per second or more; preferably 10 centimeters per second or more; it also means that Peak time to completion as measured after completion of Example No. (VF) is 11 hours or less and preferably 10 hours or less The term "all weight factor" means mean molecular weight of 000000 or greater; Preferably 000001 or greater.Ye Particular examples of typical monomers copolymerizable with the N-vinylcarboxylic acid amide of the present invention include the following: alkali metal salt Jia alkali metal salt sodium salt or potassium salt of acrylic acid or methacrylic acid 0 « and the alkyl ester of the alkali metal salt © Methyl ester methyl ester, ethyl ester, and propyl ester

propyl ester and butyl ester; pentyl ester » and hexyl ¢ octyl ester ul; octyl heptyl ester, heptyl ester, hexyl ester, decyl ester, nonyl ester, and nonyl stearyl ester; and palmityl ester “hydroxy lower alkyl ester © molecular weight of the alkali metal salt” such as hydroxyethyl ester; Hydroxypropyl ester and hydroxybutyl ester 0 hydroxybutyl ester Low alkyl ester The molecular weight is derived from a low alkyl amino group The molecular weight of the alkali metal salt « 0 as Jira dimethylaminomethyl ester jiu) « dimethylamino Jl esscher dimethylaminoethyl ester ¢ dimethyl ind) propyl ester ¢ dimethylaminobutyl ester sid dimethylaminobutyl ester » dimethylaminopropyl ester precautionary michel amino » diethylaminomethyl ester (fi dimethylamino; Dimethylaminobutyl dimethylaminopropyl ester 0 Molecular Weight (preferably lower alkyl ester halide

Ac gana substituted by bromide or chloride halide bromide the halide is ¢ alkali metal salt ammonium group al ¢ trimethylammonioethyl ester halide fu) trimethylammonium halide Ethylamide amide ¢ trimethylammoniopropy! ester halide iu) trimethylammoniopropyl XY. The molecular weight of the salt lower alkyl amino group reduced sid substituted with an alkyl group such as chaimethylaminomethylamide 0 alkali metal salt (5 sal! metallic aud Ja) amino J fie Shaqshasi « dimethylaminomethylamide female michel aminopropylamide « dimethylaminoethylamide 1 dimethylaminoproylamide 8 chai mefsyl smd butylamicid dimethylaminobutylamide « Qafsai ethylaminomethylamide ¢ diethylaminomethylamide ¢ (Ji) diethylaminoethylamide © diethylaminopropyl diethylaminopropyamide » Chai Ethylamino Butyl Bala

0 dithylaminobutylamide an alkyl amide of lower molecular weight substituted with a quaternary ammonium group of the alkali metal salt

alkali metal salt » alkali halide J fe ammonio Gi trimethylammonioethylamide halide » halide 26 ethylpropylamide

© triethylammoniopropylamide halide » triethylammoniopropylamide halide « low alkyl amide Tower alkylamide Jad a with sulfonic acid alkali metal sulfonic acid for alkali metal salt Je ¢ alkali metal salt 0'' sulfomethylamide sulfoethylamide sulfoethylamide

0 propylamide sulfopropylamide + sulfobutylamide ; sodium sulfomethylamide; sly potassium sulfobutylamide ¢ and potassium sulfomethylamide ; and potassium sulfoethylamide © and sulfopropylamide 0 and sulfobutylamide

0 Potassium sulfobutylamide » acrylonitrile » vinyl ether such as methyl vinyl ether and ethyl vinyl ether

ethyl vinyl ether + propyl vinyl ether; and butyl vinyl ether

butyl vinyl ether » vinyl ketone methyl vinyl ketone » and ethyl vinyl detone; vinyl carboxylate

vinyl acetate Jia molecular weight lower vinyl carboxylate low Y. acid + maleic anhydride maleic anhydride » vinyl propionate, vinyl propionate, potassium maleate ¢ sodium maleate; Sodium maleate, maleic acid

Potassium maleate

Among these compounds, the following compounds are preferred: (meth)acrylic acid

‎ell, (Lua) 5 ¢ (meth) acrylate Ye sodium (meth) acrylate; methyl (meth) acrylate » ethyl (meth) acrylate © and propyl (meth) acrylate » and butyl (meth) acrylate

bye bye

Yi (meth) acrylate Jn hydroxy —Y ; butyl (meth) acrylate, 7-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butyl (meth) acrylate S32, ?-2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate « 2-hydroxybutyl (meth) acrylate » dimethylaminoethyl (meth) acrylate © ¢ acrylamide and acrylamide 0 » trimethyl aminoethyl (meth) acrylate chloride and sulfiobutyl » sodium sulfopropylacrylamide ¢ acrylonitrile and acrylonitrile ¢ sodium sulfobutylacrylamide sodium acrylamide; And methyl ethyl vinyl ether “methyl vinyl ether J) and methyl vinyl and methyl ¢ ethyl vinyl ether and ethyl vinyl ketone 0” ethyl vinyl ketone Kitson Jud And ethyl « methyl vinyl ketone

Sb, (meth) acid “Lia as used N-vinyl-2-pyrrolidone or acrylic acid” maleic anhydride .methacrylic acid 0 in the present invention; A crosslinking monomer or a crosslinking agent can be used, which is a single crosslinking monomer; It can be used eal on two or more unsaturated groups in mixed with an amide 17-vinyl acid polymerization as a monomer as a carboxylic acid -N-vinylcarboxylic acid amide 0 is necessarily defined and polymerization can be used Polymerization processes are not the traditional methods. Usually it is preferred to use solution polymerization or the reverse phase suspension polymerization method or the reverse phase 00 polymerization method. Solution; The components of polymerization are melted, for example; In the method of polymerization of Yo and cross-linking agent uniformly in water; Or in a monomer solvent, sperm

The dissolved oxygen in the system is removed from the system by removing the air in a vacuum or replacing it with an inactive gas dhe nitrogen gas or carbon dioxide gas and then after that ; A polymerization initiator is added to the system to initiate the reaction. The 0 degree polymerization initiation temperature is usually from 0 - Js a to about ale and the reaction time is from about 1 to about 10 hours. The determination of the amide compound Be YON di-enylcarboxylic acid N-1,3-butadienylcarboxylic acid of the present invention is investigated by mass spectrometry (electron shock method and chemical ionization method) and 0 infrared absorption and ultraviolet absorption spectra. Violet. as an example; Compound 1 - 18 is defined » *- Buta-Dienylacetamide -N-1,3-butadienylacetamide acid Physical properties of compound dd LBs -* 1 - N-acetamide -1,3-! ‎:butadienylacetamide acid ‎do ‎Mass spectrum (electronic shock method): Nl 03194 ‎EV cof ¢Mass spectrum (chemical ionization method): 11" ida infrared absorption (Tan) by 4 s read VEVY UV-Vis Absorption Spectrum (nm) 777 6 7776 nm In the present invention; the quantitative analysis of YON amide 0-butadienylcarboxylic acid N-1,3-butadienylcarboxylic acid is preferably performed by Cr-Mo High-speed liquid column chromatography can be performed, but the present invention does not specify that method.For example, the following operating conditions are preferred for high-speed liquid column chromatography.Unless another method is indicated, quantitative analysis was performed under the following conditions in ample CURRENT INVENTION.Yo Column: SHODEX* SIL5B (Showa Denko k.k.) Separation Material: NOR Hexane / Identical Propyl Alcohol (4) 1 10 10 mL/min except

ra UV4 709 nm detector. The present invention will be described below in more detail with reference to the following BY and comparative examples; And anyway; The present invention is not to be construed as limiting these examples.

° Example 1 to a three-neck flask (Ja Yor) with a thermometer and stopcock on dry ice - ethanol ; Added 5.4 g (Use 1) of acetamide + g (No 3 + (Use) of cognate propyl alcohol 1.11 ¢isopropyl alcohol g (0 mmol) of ethylenediaminetetraacetamide 11.06 ethylidenebisacetamide g (eV) 0 mol) acetaldehyde Hd isopropyl acetate acetaldehyde diisopropylacetal Then the mixture was stirred and melted at a temperature from £0 to 8 C until it became homogeneous. A solution containing 1, 47 grams (1.1 by weight based on the residue) of concentrated sulfuric acid dissolved in ¥ grams (Joelle) of isopropyl alcohol (as done in the following examples) Jud 0 after stirring, then 17.1 grams (8. + mol) of acetaldehyde was added to it through a drip funnel and within a period of ? minutes. After adding the drops, the mixture was allowed to react at 0 #"m. for ¥ hours to neutralize the catalyst, and then Glad the reaction mixture by gas chromatography 8h to find that the conversion rate of acetamide was JAA; Ethyl)acetamide (N-(1-propoxyethyl) acetamide) was 744, and the selectivity of ethylidenebisacetamide as an undesirable product was 78.7. From the resulting J cli solution; <-(-1-propoxyethyl)acetamide N-(1-propoxyethyl) acetamide was obtained by distillation under low pressure. This is the thermal cracking of that compound into 17-vinylacetamide N-vinylacetamide and a similar yo-propyl alcohol isopropyl alcohol at 0” m with a residence time of 1 sec. The crushed solution was cooled to 10 °C and the basic solution was separated from it at AL kg Yau 1077 °C in an apparatus.

with exception

b High pressure crystallizer. as a result; 7+-N-vinylacetamide was obtained with a purity of 799.9 and has a bear YO -N dicyclic content of 1,3- butadienyl Jui ppm. To evaluate the polymerizability of Jd NS all N-vinylacetamide acetamide » ©5000 ppm of oo 7-50 ( 1017 - azoshai - (7-amidineopropane) (N) dihydrochloride was added , N-azobis-(2-amidinopropane) dihydrochloride 7-50 to that solution, then immerse the container in the system bath by 74 by weight of an aqueous solution 71 of hydroquinone, the degree of viscosity is measured at 17 m and the number of turns Ve revolutions per minute by using a viscometer of type BL (rotary) and it was found that the amount of viscosity is 0 001 sttimeter per second Comparative example 1 Presentation of thermally cracked solution obtained in Example No. (1) to simple distillation at a pressure of +0 mm Hg to provide JN N-vinylacetamide of purity 799.0 and containing a content of L- ?-1-buta-chae 0-enylacetamide 7001 N-1,3- butadienylacetamide ppm The process of evaluating the polymerizability was performed in the same way as in Example No. 1 and it was found that the viscosity was 01 cm per second or less. Introducing methanol containing 70.5 by weight of sulfuric acid to the fifth stage from the top of a repetitive distillation column made of glass and Oldershaw type having a Yo stage where the introduction is done in the amount of VAL grams per hour; and to the fifteenth stage from the top of the shaft; Jay acetaldehyde at an amount of TY grams per hour g was placed at the bottom of the repeat distillation column » and in a 500 ml flask Yo was placed in that place 100 grams of water was supplied and heated to 1000 °C to extract the content of The flask is 749 grams per hour. The solution that was released did not contain a vacuum

Ya

The decanter was actually extracted on any organic material. From the top of the column » grams / hour of a mixture of diacetalmethyl - methanol (YY) was extracted at the rate of distillation? . The dropper did not actually contain dimethylacetal-methanol

ZY “+ acetaldehyde was the conversion rate for acetaldehyde. aldehyde Water or aldehyde 7001 dimethylacetal methyl acetal El and the product was 0 (Separation of acetal) Separation of the acetal type lal to the first stage of the top of the repeat distillation column Regular place in the amount of 576 grams Jay stage Ye contains Oldershaw per hour to the tenth stage of condyle; Starchy methyl acetal was evaporated per gram per VY with an amount of methanol by weight. Methanol AYA containing dimethylacetal 0 m 0 h. The column was heated so that the column top temperature was maintained at the bottom of the repeat distillation column and in a volumetric flask. 1 At the rate of distillation, 001 g dimethyl acetal, placed in that place, was supplied with 0 s 1011, and then heated by immersing that flask in an oily bath at dimethylacetal extraction, thus the content of the vessel by 1; grams per hour. Solution 1 was and did not contain dimethylacetal SD extracted from the flask actually from . methanol containing 750.7 n-hexane n-hexane - g per hour mixture of dimethylacetal Av column top; The dropper was not included. dimethylaceatal-methanol-n-hexane 0 acetaldehyde or bottom product real on water or 0 acetaldehyde (Synthesis of N-(1-methoxyethyl) acetamide: Synthesis 7<- (1-methoxyethyl) High purity acetamide, which dimethylacetal was mixed Dimethyl acetal and dimethyl acetal obtained in the acetal separation process obtained in the methanol process containing dry dimethylacetal methanol in that mixture acetamide, then the acetamide ¢ methanol was dissolved to recover the methanol Yo doe to prepare a raw material solution for the reaction consisting of acetamide / di-ally pf

Acetal | acetamide/dimethylacetal/methanol J sie with a molar ratio of 3/7/1. That solution was introduced from the Jiu portion of a reaction tube having an inner diameter of 0 mm 0 Aga dey mL acid ion exchange resin [Amberlist]5 « in the amount of µl per hour. and in the reaction tube casing; Hot water was circulated at Joo oo to control the reaction temperature at 2700 . The reaction solution obtained from the outlet of the upper part of the reaction vessel was subjected to quantitative analysis; As a result ; The reaction solution was found to have an approximate molar composition of acetamide/dimethylacetal/methanol/ acetamide/dimethylacetal/methanol 171-(1-methoxyethyl)acetamide », 1/4/19/00 (MEA); The conversion rate for acetamide was 7/9548 0 and the product was N-(1-methoxyethyl)acetamide (MEA).

JA

Recovery of acetal The reaction solution obtained in the step of manufacturing N-(1-methoxyethyl) acetamide was fed to a continuous evaporator 1 from Membrane type with a shell having a heating area o,f m? under reduced pressure 100 millimeters of mercury; 7069 grams per hour. and in the cover; The heating medium was cycled. A precipitate was obtained upon evaporation containing the fact 17-(1-methoxyethyl)-methoxyethyl) acetamide 1 in an amount of 11 grams per del. A solution containing dimethylacetal containing Yo 27 by weight methanol with stoichiometric volatile components was obtained in the amount of OAT grams per hour. Recovery of methanol: To phase es ile) Top of an Oldershaw glass repeat distillation column containing Yo phase; The dimethylacetal | 0 produced from the dropper containing IV by weight methanol, which was obtained in the acetal recovery step at an amount of 100 grams per hour. Bye bye

Preheat the column such that the temperature of the TOA stick top was maintained at a distillation ratio + . At the bottom of the hil repetition column a 550 ml flask was supplied and heated by immersion in an oil bath at 1100°C to extract the contents of the flask at VAS grams per hour. The solution extracted from the beaker was 00 dimethylacetal, containing 5.6 volumes by weight of Michael; from the top of the column; An azeotropic de-acetal-methanol mixture (methanol: ; 77 by weight) was extracted at a rate of 0 grams per hour. manufacturing bid N | ASPETAMIDE: Synthesis of N-vinylacetamide 01 fed J, lad) containing the fact (JA iscothym-1(~N) N-(1-methoxyethyl) acetamide obtained in a recovery step J acetal: A stainless steel acetal reaction tube with an inner diameter of 01 millimeter and a total length of 1 meter, where it was under low pressure 100 millimeters of mercury and heated to the mouth at a rate of 71 ml per minute. The mixture of wale J Jaen N-vinylacetamide 05 and methanol produced by thermal cracking reaction was condensed in a condenser located at the outlet of the reaction tube and then recovered. -(1-methoxyethyl) acetamide 7 concentration 7<-vinylacetamide: N-vinylacetamide to the tenth stage of the top of an Oldershaw Ye glass repetition column containing 01 stages; the reaction solution that was prepared was introduced Obtained in the step of manufacturing [-N-vinylacetamide] at an amount of 100 grams per hour. The pressure was millimeters hg and the column was heated so that it maintains the temperature at its top at 40 °C at a distillation rate? A flask was supplied volume of 0 ml at the bottom of the repeat distillation column and that vo flask was heated by immersion in an oil bath at 80 m to extract the content of the flask in the amount of 100 | grams per hour. The solution extracted from the beaker was Bala's solution

1 ore containing 7494 by weight 17-phenyl N-vinylacetamide 77-phenylacetamide methano J sill from the top of the column; extracted. N-vinylacetamide, raw N-vinylacetamide, grams per hour. The 17-phylylacetamide fo in diphenylacetamide Gr VON ppm of Ve contained N-1,3-butadienylacetamide ~~ °: N-vinylacetamide Purification of H-phenylacetamide The raw N-vinylacetamide solution [2-vinylacetamide] was introduced to the phase N-vinylacetamide obtained in the concentration step 7<-phenylacetamide

Oldershaw fifth column from the top of the glass repeat distillation column of the type, and the repeat distillation process was performed under dale depression 01, which contains 0 mm Hg and at a distillation rate of ? . as a result; 000+ was obtained with a purity of 7948 and contains; N-vinylacetamide to 17-phenylacetamide. N-1,3-butadienylacetamide diethylacetamide bs VA -N ppm butadienelacetamide OF - N The polymerization ability of a compound was evaluated and it was found that 1 yielded by the same method as in the example No. N-1,3-butadienylacetamide Vo centimeter per second. 001 Amount of viscosity was + shawl No. of the raw material containing N-vinylacetamide acetamide Jd No ya The degree of enylacetamide Ge has been set. TON on 01 ppm of which was obtained in the step of concentrating 17-phenyl N-1,3-butadienylacetamide 0 M and the original solution was separated ov in Example No. ? At N-vinylacetamide acetamide. kg/cm? And 09 m in a high-pressure VA crystallizer, which has a pressure value of one million degrees, N-vinylacetamide, and as a result; The resulting A1-phenylacetamide was obtained with the same or less N-vinylacetamide. The polymerizability of 17-phenylacetamide was evaluated; It was found that the amount of viscosity is 1500 cm per second. JUS No. 1 method as in Ye b Bala

The methatol solution of 17-phenylacetamide N-vinylacetamide containing Ve ppm Ger TON enylacetamide N-1,3-butadienylacetamide obtained in the manufacturing step of A1-0-phenyl-0acetamide N -vinylacetamide in Example No. to a column charged with activated carbon at the value of the liquid's vacuum velocity in hours? hour' and at room temperature. The resulting solution contained 4 parts per million Boar PON di(Ji)acetamide N-1,3-butadienylacetamide. The resulting solution was subjected to simple distillation under reduced pressure. The polymerizability of distilled 7+-phenylacetamide 0 was evaluated by the same method as in Example 1; It was found that the magnitude of the viscosity is 700 cm per second. The number e

to 0 parts by weight of N-vinylacetamide 77-vinylacetamide containing Yee ppm of MEL Se ar TON vinylacetamide N-1,3-butadienylacetamide 0 | obtained in comparative example no. 1; 50 parts by weight of toluene were added and dissolved at 46 °C in a nitrogen atmosphere, after cooling the mixture to mm, separating the precipitated crystals by filtration and drying under low pressure. The resulting J dN N-vinylacetamide acetamide contained an A ppm of 1 - 77; =F butadienylacetamide N-1,3-butadienylacetamide 0 . ALE was evaluated for the polymerization of that product by the same method as in

JB No. 1; It was found that the viscosity is .8 cm per second.

The number “ to a methanol solution of 77-Vylacetamide N-vinylacetamide contains Ve ppm 1 - 17 ; =F biota SLB enylacetamide N-1,3-butadienylacetamide | Yo obtained in the synthesis step of N-vinylacetamide 7-phenylacetamide in Example Y ; Para-benzoquinone was added to ey p-benzoquinone to give an AY ppm concentration (equivalent to 0.5 for N-1; *- Buta-Dienylacetamide 0106E11-1,3-0018016071861) It was stirred at room temperature for one hour. The reaction solution contains 1 parts per million (FO) SN butadienylacetamide (N-13-butadienylacetamide ~~ © ). Presentation of the solution for a simple distillation process under reduced pressure. The polymerizability of distilled N-vinylacetamide 7<-vinylacetamide was evaluated using the same method as in Example 1; It was found that the value of the viscosity, Ve, is cm per second. Laying © grams of catalyst for steel containing 70.8 of 560 carrier and alumina loaded on palladium alumina palladium weight 0 parts per Ve ore containing Nevinglacetamide 77 grams -phenylacetamide ¢ N-1,3-butadienylacetamide buta-dienylacetamide =F ; 1 - N millionth of -1 < by weight Vo N-vinylacetamide acetamide Jud N by weight 8 ) 1-methoxyethyl) acetamide (AYO 1 -methoxyethyl) acetamide from acetamide; and 0.7700 by weight methanol were placed in a flask of 700 ml, where they reacted in a hydrogen atmosphere at room temperature for 1 minute with stirring. After completing the reaction, the catalyst was separated by filtration from the reaction solution, and the filtrate was analyzed. 18-)=-butadienylacetamide (N-1,3-butadienylacetamide) was analyzed by high-performance liquid chromatography and gas chromatography. Other components were analyzed by Ganz chromatography.

Bali butadienyl (F) - N The reaction solution had a content of 71.4 ppm or less and contained 1 N-1,3-butadienylacetamide by weight N-Egelacetamide -N-ethylacetamide after removing methanol by distillation under low pressure » Yo 7-vinylacetamide, N-vinylacetamide, crystallized in a high-pressure crystallizer under kg pressure | cm" and the original solution was separated at 0 °C. Did N acetamide in solution tt -' 1 oN had a purity of 744.7 by weight and a da content of the resulting crude N-vinylacetamide. ppm or less 1 N -13-butadienylacetamide buta-dienylacetamide; it was found that 1 number Jl The polymerizability was evaluated in the same way as in cm per second. 061 The degree of viscosity was of 701.09 Solid (58 g) including catalyst catalyst oa was carried as a carrier to an alumina hydrogenation reactor on alumina palladium weight ¢ nitrogen in a nitrogen atmosphere of 0. Under an atmosphere of crude nitrogen hydrogenation Contains N-vinylacetamide Recycled 45 grams of 7-phenylacetamide Buta-chai ethyl acetamide 1-9-N ppm 46000 ¢” N-vinylacetamide and 5 by weight L<-phenylacetamide + N-1,3-butadienylacetamide « N-(1-methoxyethyl) acetamide by weight A<- (1-methoxyethyl) acetamide 858 in a reaction vessel at liquid velocity methanol by weight methanol 0 for a period Hours sub vdeo (LHSV) enylacetamide JB buta-1 reaction solution had a content of 7 - 3;0

Oa le YL ppm or less and contained 1 N-1,3-butadienylacetamide -N-ethylacetamide acetamide JN Weight after removing methanol by distillation under low pressure from the resulting reaction solution - the solution was separated Al-Masali in a high-pressure crystallizer at ° C. As a result ; Obtained 17-phenyl 1 kg/name "and VAY with a purity of 794.5 by weight; it contains N-vinylacetamide acetamide part in 1 N-1,3-butadienylacetamide ?- Buta-dienylacetamide 1 - 7 million or less. The yield is the same as N-vinylacetamide. The polymerization ability of 17-vinylacetamide cm per We was evaluated and it was found that the viscosity was 1 1 in the method as in Example No. vo sec. Sperm

Do you shawl a number? A solid (g) Yo catalyst (comprising 70.59 by weight palladium on alumina Lise NV) was charged as a carrier in a reaction vessel under nitrogen atmosphere and crude N-vinylacetamide 77. Containing 50601 ppm [+1 - 3] oo ?-buta Ji (1,3-butadienylacetamide) and 00 pounds by weight! 7-phenylacetamide 0 + N-vinylacetamide by weight 7<- (1-methoxyethyl) acetamide No (I-methoxyethyl) acetamide « 77 by weight acetamide » 0 by weight methanol were circulated in that vessel. The reaction solution had a content of - 1 7-butadiene (Ji)acetamide 1 N-1,3-butadienylacetamide 0 ppm or less and contained 70.5 by weight JBN -N-acetamide ethylacetamide from the resulting reaction solution; The methanol was removed after the methanol removal

BRAT You / original solution in a high-pressure crystallizer at 1,800 kg in N-vinylacetamide °C. and as a result; 87-phenylacetamide 05 was obtained with a purity of 744.5 by weight and having a SN content of 0 (0) 0-butadienylacetamide 1 N-1,3-butadienylacetamide ppm or less. The ability to polymerize: <-N-vinylacetamide obtained by the same method as in Example No. © and it was found that the viscosity was 1171 cm per Al No. 01 Y. This was performed The example is in the same style as in Example No. 7; Except that a catalyst comprising 70.06 by weight palladium and 70.07 by weight silver carried on alumina as a carrier was used. The reaction time was changed to one hour. The reaction solution contained 1 » 10-3-butadienylacet Lot ppm or less and contained 1 N-1,3-butadienylacetamide acetamide Yo Linef-1 acetamide 11-00318662006 . The polymerizability of JAN was evaluated by weight from the resulting N-vinylacetamide Bala i acetamide obtained by the same method as in Example No. © and it was found that the viscosity was 170 cm/sec. 11 ad ) Example: Dimethylacetal compound containing VO was reconstituted from © weight methanol “which was obtained in the acetal recovery step in Example No. ? To the acetal separation step, methanol was separated from the acetal. sl acetal = You contained ppm of 1 + 1 ; (DEY) is 1,1,3-trimethoxybutane. This acetylation was distilled using a stack column containing an isotopic segment number of Yo at a ratio of

TONY ppm of 11 distillate * to obtain an acetal containing 0,3-trimethoxybutane 1 . Display the acetylation resulting from the processes following the step of manufacturing 1-methoxyethylacetamide as described in Article 9. anyway ; In this example; Simple distillation Yu was performed from repeated distillation in a purified step with B-vinylacetamide 0 N-vinylacetamide “VON ppm of 01 on N-vinylacetamide [7-vinylacetamide sma) De Polymerizability was evaluated. 1-1 ,3-butadienylacetamide Buta-Dienylacetamide ; It was found that the value of the viscosity of the product produced by the same method as in the example No. cm per second. 71 JL was comparative? 9 The compound 7+-phenylacetamide, N-vinylacetamide, was produced by the same method as in Example No. 1 except for the omission of the repeated acetal distillation. The resulting Jobo N-vinylacetamide contained ppm of [-701-butadienylacetamide N-1,3-butadienylacetamide + then evaluated the polymerizability by the same method as in Example No. © and it was found that the viscosity value It was 01 cm per second or less. VY Example No. Yo To a glass reaction vessel Vio g of water and Yoo g of JEN N-vinylacetamide obtained in Example No. ? And bye bye

and GM of 7037-(chai-acetyl); NN phenyl) - el) SE) ef (Jicyclohexane N,N'-(deacetyl) -N,N"-(divinyl) -,4-bis (aminomethyl) cyclohexane as a cross-linking agent After removing the dissolved oxygen by nitrogen gas, 0.075 gm of 7-7-azodi-71-(7-imidazolin) (d=propane oe-dihydrochloride 2,2"-azobis 2-(2-imidazolin-) was added. 2-yl) propane dihydrochloride dissolved in ¾ mL dehydrated water; the mixture was isolated from heat and allowed to stand. After 'hours the internal temperature reached IVY due to the heat of polymerization and after that ¢ the internal temperature gradually decreased due to Heat loss The period of time that passes from the addition of the polymerization initiator 00170062800 to the time the internal temperature of the reaction vessel reaches its maximum point is called the “peak time.” In that example, the peak time was “hours.” Comparative example no. polymerization using the same method as in example VY » except that Jud-N acetamide N-vinylacetamide obtained in comparative example No. 1 was used instead of JN acetamide N-vinylacetamide obtained in example Y, no increase in internal temperature associated with polymerization was observed even 48 hours after the addition of the polymerization initiator example VE 0 to a glass reaction vessel to which vio was added and dissolved gm of water »and #?? gram A7-phenylacetamide obtained in Example 7; YY, g sodium acrylate. After removal of the dissolved 0 oxygen by gas nitrogen » 016 g of SY azothiene “-(“-imidazolin-7-yl)dihydroxypropane 2-(2-imidazolin-2-) was added yl) propane dihydrochloride dissolved Yo 5 220- 2.2 dissolved in ml vy

£A of deaerated water; The mixture was removed from heat and allowed to stand. The peak time was 7 hours. ° ad) Comparative example In the same way as in the example, polymerization was performed from A17-vinyl Ya, N-vinylacetamide acetamide Jind-N except Using the lad ;11 digit oo obtained in the example of a number ? . No nevinylacetamide acetamide observed an increase in internal temperature associated with the polymerization process even after 4 weeks; An hour of adding a polymerization initiator. Example No. (Determined with a solution of 1.0 pH A solution with a pH value of 01 aqueous “777) was fed and contains 798 by weight <-7- (1-methoxy ethyl)acetamide acetamide (J iscothym-1() =N and 77 by weight N-(1-methoxyethyl) acetamide in an amount of © ?g per minute to a stainless N-(1-methoxyethyl) acetamide reaction tube Meter .1 mm was heated and a total length of 71 has an inner diameter of stainless steel Ascel .Ga) 001 mm was condensed; the pressure was reduced to pee reaction tube to ve. The thermal cracking mixture was in a condenser supplied at the outlet of the reaction tube and “YON ppm of YA was recovered on N-vinylacetamide containing <7-phenylacetamide and the conversion rate was “N-1,3-butadienylacetamide” Buta-diethylacetamide 7/8 N-(1-methoxyethyl) acetamide ethyl)iscothym-1(-N) reaction solution yielded to the tenth stage of the value of Jad; ¢ 01 stages were done It contains an Oldershaw glass repeat distillation column of the type grams per hour The column was heated so that it retained a peak temperature of 000 at an amount of 1 millimeter (30) and at the Yoo distillation ratio the column was at 56 m at low pressure A flask was provided at the bottom of the repeat distillation column and heated to 100 to extract the content of the flask in the amount of SSA the flask was immersed in an oily bath at Ye acetamide JN g per hour. The solution extracted from the beaker was dissolved

VARY

£9 N-vinylacetamide . from the top of the column; The micelles were extracted at an amount of gram per hour. A solution of 7<-vinylacetamide, N-vinylacetamide, was introduced to the fifth stage from the top of a type 7 glass distillation repeat column containing ©01 stages and a display of the distillation repeat at a low pressure value of 1©, stelle hg and at a distillation ratio ? . as a result; JN Acetamide N-vinylacetamide was obtained with a purity of 7948 and the content of cD By YON Ji) Acetamide 70106A1-1,3-0018010718 was 4.4 ppm. The polymerizability of the resulting N-vinylacetamide b-vinylacetamide was estimated by the same method as in 0 Example No. 1; It was found that the viscosity was 100 cm per second. Example revision 1 methanol was removed from a solution of 77-vinylacetamide N-vinylacetamide methanol containing YA ppm Loar VON di(Ji)acetamide N-1,3-butadienylacetamide obtained in the article Ve.Vo number by distillation. After the concentration of the Jus-N acetamide, N-vinylacetamide, the temperature was set at 0 * “C, and the original solution was separated in a high-pressure crystallizer at 1,800 kg Yau and 16 C. As a result, it was obtained L<-N-vinylacetamide N-vinylacetamide with a purity of 799.9 and containing ?ppm-0,7-butia-Jd-acetamide N-1,3-butadienylacetamide OY susceptibility was estimated. The resulting N-vinylacetamide 77 polymerization using the same method as in example No. © and it was found that the viscosity value was 80 cm per second Examples 11 to 11 and examples from “to +” The reaction was performed in the same way as in Example No. Lad [Ve except using N-(1-methoxyethyl) acetamide containing 17-phenylYo-Nevinylacetamide in different concentrations as raw material. Reaction and contents of Gs ar YO -N dienylacetamide N-1,3-butadienylacetamide after BA solution

° The purification and polymerizability of 7<-N-vinylacetamide are listed together in Table 1 below. Table 1 a1-phenyl exponential value transformation 7 N-buta-dienyl polymerizability acetamide-7 | pH 777 Acetamide (ppm) | cm per second ee l noa the Te TT Ta l a a Ce Te TT Tee eae yen y y y y y y y y y y y y y yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy can! ; For example ¢ 1 by dealalcoholization of the 1-(-N-alkoxyethyl) amide (Ji) carboxylic acid Y 1 N-(1-alkoxyethyl) carboxylic acid amide by removal of an amide group <7 - 1-(alkoxyethyl) carboxylic acid N-(1-alkoxyethyl) carboxylic acid amide produced as an intermediate compound from the reaction of 0-carboxylic acid amide with acetaldehyde and alcohol “R from the reaction of carboxylic acid amide; and dialkylacetal acetaldehyde” or © by cracking ethylidene biscarboxylic acid amide or by cracking oD ethylidene biscarboxylic acid acid amide, which was then obtained as an intermediate compound of acetaldehyde and a carboxylic acid amide.The crude 14-vinylacetamide N-vinylacetamide obtained by these known production methods does not have a good polymerization ability. VVV

0. polymerizability, however, when the amide content of =F -N-butadienylcarboxylic acid, N-1,3-butadienylcarboxylic acid in the 17-vityl carboxylic acid amide, is reduced to a T+ fraction in million or less ¢ preferably reduced to 10 ppm or less; most preferably to be reduced to 1 ppm 0 or less; Then, the crude vinylearboxylic acid amide is subjected to a purification process. N-vinylcarboxylic acid amide Jud N-vinylcarboxylic acid amide is obtained with a high degree of polymerizability, as its polymerizability is improved in addition to that; The amide =TO-N buta SB can reduce N-1,3-butadienylcarboxylic acid to the content range described above by exposing the JN N-vinylcarboxylic acid amide Crude or a solution thereof to flee purification process A method of repeated distillation + or a method of re-crystallization ,— Lal » or a method of pressure recrystallization » or a method of physical adsorption using activated carbon 0 as an adsorption material + or a method Diels-Alder; or by the method of the selective hydrogenation reaction of the Gaur Yo) di-1,3-butadienyl group in addition; According to the present invention; in Production of N-vinylearboxylic acid amide dN by Thermal Cracking or Catalytic Cracking of N-(1-alkoxyethyl) carboxylic acid amide | 00 or SUE ethylidenebiscarboxylic acid amide did N-vinylcarboxylic acid amide, which is highly polymerizable. In addition, a high molecular weight N-vinylcarboxylic acid amide polymer can be produced using a highly polymerizable Yo monomer. B with a solution oY ¢ While the invention has been described in detail and with reference to certain examples thereof it will be obvious to a person skilled in the art that various variations and modifications can be made without deviating from the spirit and scope of | To choose a.. bala

Claims (1)

oy Alaa) alc N-vinylcarboxylic acid amide A process to produce an amide of L-8-vinylcarboxylic acid 1-1 to a high degree; Which includes reducing the polymerizable amide content “N-vinylcarboxylic acid amide” Jaud-N carboxylic acid contained in an amide of 7 ppm or less. 70;- Crude to N-vinylcarboxylic acid amide A process for the production of 1-vinylcarboxylic acid amide - 1 to a high degree as mentioned in Claim No. 0) where the polymerizable for polymerization JG N-vinylcarboxylic acid amide N-vinylcarboxylic acid Jd N amide is produced Alkoxyethyl (1-)-14 by removing an alcohol group from the cf amide obtained N-(1-alkoxyethyl) carboxylic acid amide carboxylic acid and acetaldehyde carboxylic acid amide as an intermediate compound From carboxylic acid amide or from carboxylic acid amide alcohol and alcohol acetaldehyde 1 -acetaldehyde dialkylacetal and dialkyl acetaldehyde + N-vinylcarboxylic acid amide to produce 77-vinylcarboxylic acid amide Ale -* 1 Where 1, as mentioned in claim No. Ale, is polymerizable to the degree of polymerizable Y by N-vinylcarboxylic acid amide producing an amide 11-vinylcarboxylic acid - “ethylidene biscarboxylic acid amide” dicarboxylic acid ¢ acetaldehyde obtained as an intermediate compound of acetaldehyde 0 -carboxylic acid amide carboxylic acid 1 N-vinylcarboxylic acid amide carboxylic acid Jad N ;- process to produce amide 1; Where it includes 1 highly polymerizable as mentioned in claim No. “The aforementioned reduction step is to purify the crude 17-vinylcarboxylic acid amide or a solution thereof using the N-vinylcarboxylic acid amide 4 replication method or the polyserase method.” Distillation recrystallization or re-beggler method oo by physical dl or adsorption method 0 barometric recrystallization 1 pa ot or Diels-Alder method or reaction method 0 activated as adsorption carbon js SHY ethyl (SD Ber) selective group hydrogenation includes hydrogenation A -1,3-butadienyl group q N-vinylearboxylic acid amide to produce 17-phenylcarboxylic acid amide 4 lee —0 1 as mentioned in claim No. 4; -N-1,3-butadienylcarboxylic acid amide ° N-vinylcarboxylic acid amide Juid-N carboxylic acid A process for the production of amide 1 1 ; including cracking 1 for high polymerization as mentioned in the thermal EY protectant or catalytic cracking amide 7<-(1-alkoxyethyl)carboxylic acid- » or N-(1-alkoxyethyl) carboxylic acid amide ¢ to produce ethylidene biscarboxylic acid amide | © carboxylic acid Jd N where the amide content is N-vinylcarboxylic acid amide 7 ethyl) cycloa-1 -N from N-vinylearboxylic acid amide v HB or ethylidene amide No(1 -alkoxyethyl) carboxylic acid amide A by weight or less. 701 ethylidene biscarboxylic acid amide 3 N-vinylcarboxylic acid amide to produce amide 71-vinylcarboxylic acid (ide = v) for high degree polymerization; These include thermal cracking or catalytic cracking the amide GY N-(1-atkoxyethyl) carboxylic acid amide (1-alkoxyethyl)-carboxylic acid (-N YF) where © ethylidene biscarboxylic acid amide or ethylidene biscarboxylic acid amide 4 A 7" aqueous solution by weight of amide 7 <- (1-alkoxyethyl) acid 0 or N-(1-alkoxyethyl) carboxylic acid amide 3 used to produce ethylidene biscarboxylic acid is adjusted. amide carboxylic acid so that the exponent value is N-vinylcarboxylic acid amide 7-vinylcarboxylic acid + .01 pH11m from © to a Babla oo N-vinylcarboxylic acid amide Process to produce an amide [-vitylcarboxylic acid-1-8]; It includes 1 highly polymerizable 6M as mentioned in the protection element amide 7 <- (1-alkoxyethyl) catalytic thermal cracking or catalytic cracking or ethylene amide N-(1-alkoxyethyl) carboxylic acid amide LS gp SI; The acid is 17-vinylcarboxylic acid amide zs ethylidene biscarboxylic acid amide oo where the amide content of 17-vinylcarboxylic acid amide is N-vinylcarboxylic acid + (Jd -1-alcoxy) -N of N-vinylcarboxylic acid amide ass Y or N-(1-alkoxyethyl) carboxylic acid amide carboxylic acid A by weight or 701 ethylidene biscarboxylic acid amide 9 alkoxy ethylidene (-1) less;” and a 777 aqueous solution by weight of amide L<-0 or ethylidene amide N-(1-alkoxyethyl) carboxylic acid amide 11 used to produce ethylidene biscarboxylic acid amide Carboxylic acid SLD 1" to have value N-vinylcarboxylic acid amide pomopolymer A process for the production of a polymer 4-1 mixed with a pomopolymer or a polymer N-vinylcarboxylic acid carboxylic acid and includes another copolymerizable monomer N-vinylcarboxylic acid; Lar Te) -1- di--vitylamide amide is of high degree and has a polymerizable amide content ° p1 N-1,3-butadienylcarboxylic acid amide carboxylic acid did 1 million or less. Nad-vinyl acid; Claim 4 process; Where it includes the production of 1-01 of any La, by polymerization, N-vinyl carboxylic acid amide carboxylate ¥ AY protective elements from ¥ Ba La