CN1193959A - Highly polymerizable n-vinylcarboxylic acid mide and production process thereof - Google Patents

Highly polymerizable n-vinylcarboxylic acid mide and production process thereof Download PDF

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CN1193959A
CN1193959A CN95197828A CN95197828A CN1193959A CN 1193959 A CN1193959 A CN 1193959A CN 95197828 A CN95197828 A CN 95197828A CN 95197828 A CN95197828 A CN 95197828A CN 1193959 A CN1193959 A CN 1193959A
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carboxylic acid
acid amide
vinyl
acid amides
amide
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CN1082943C (en
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相泽利行
中村仁至
若林邦俊
工藤哲雄
岛村顕治
长松俊一
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Resonac Holdings Corp
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Showa Denko KK
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Priority claimed from PCT/JP1995/002757 external-priority patent/WO1997024315A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/03—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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-vinylcarboxylic acid amide is produced by thermal cracking or catalytic cracking of N-(1-alkoxyethyl) carboxylic acid amide or ethylidenebiscarboxylic acid amide, wherein the N-vinylcarboxylic acid amide content of the N-(1-alkoxyethyl)-carboxylic acid amide or ethylenbiscarboxylic acid amide is 10 wt.% or less.

Description

Can height polymeric N-vinyl carboxylic acid acid amides and preparation method thereof
Invention field
The present invention relates to can height polymeric N-vinyl carboxylic acid acid amides, its preparation method and with the method for the high-molecular weight polymer of its preparation N-vinyl carboxylic acid acid amides.Particularly, the invention provides the N-vinyl carboxylic acid acid amides and preparation method thereof of polymerizability with improvement.N-vinyl carboxylic acid acid amides advantageously is used as the monomer of producing N-vinyl carboxylic acid amide polymer in industry, and this polymkeric substance is used as setting accelerator, liquid-absorbant or thickening material.The present invention also provides the method for producing polymkeric substance.And, the invention provides high-quality N-vinyl carboxylic acid acid amides, this product is used as the raw material of chemical industry or pharmaceutical prod in a lot of fields.
Background of invention
People have proposed the method for many production N-vinyl carboxylic acid acid amides up to now.For example, be known from carboxylic acid amide, acetaldehyde and alcohol production as N-(1-the alkoxyethyl)-carboxylic acid amide of intermediate with by the cracking of product or the method for the synthetic N-vinyl carboxylic acid acid amides of catalytic pyrolysis.The method of the synthetic N-vinyl carboxylic acid acid amides that another is useful comprises from acetaldehyde and the synthetic ethylene carboxylic acid amide of carboxylic acid amide.Then this product is cracked into carboxylic acid amide and N-vinyl carboxylic acid acid amides.
In these methods, the purification step of the N-vinyl carboxylic acid acid amides that obtains is provided, as distillation, extraction and re-crystallization step.For example, JP-A-61-286069 (term used herein " JP-A " refers to " disclosed unexamined Japanese patent application ") has disclosed the extracting and separating that makes water and aromatic hydrocarbon.This is because distillation can not be avoided mixing in the N-vinyl formamide as the methane amide of unreacting material.And JP-A-63-132868 has disclosed crystallisation by cooling from mixed organic solvents, and JP-A-2-188560 has disclosed the extraction and the US4401516 that use inorganic salt solution and aromatic hydrocarbon and disclosed the extractive distillation of using polyvalent alcohol.
On the other hand, N-vinyl carboxylic acid amide polymer is by obtaining with the independent polymerization of N-vinyl carboxylic acid acid amides or with another monomer copolymerization.This polymkeric substance is used as setting accelerator, liquid-absorbant or thickening material and under any circumstance this polymkeric substance must have high molecular.But the N-vinyl carboxylic acid acid amides that obtains demonstrating all the time good polymerizability in any above-described application is difficult.
Summary of the invention
The purpose of this invention is to provide and have highly polymeric N-vinyl carboxylic acid the acid amides good and polymerizability of improving.
Another object of the present invention is to produce high-molecular weight N-vinyl carboxylic acid amide polymer.
By the production method of N-vinyl carboxylic acid acid amides with good polymerizability being carried out the result of broad research, the inventor has been found that high-molecular weight polymer can have the 30ppm of being equal to or less than by use, preferably be equal to or less than 10ppm, more preferably be equal to or less than the N-1 of 1ppm, the N-vinyl carboxylic acid acid amides of 3-butadienyl carboxylic acid amide content is produced, and has finished the present invention thus.
Particularly, the invention provides can height polymeric N-vinyl carboxylic acid acid amides, its production method and produce the method for N-vinyl carboxylic acid acid amides high-molecular weight polymer with it, wherein N-vinyl carboxylic acid acid amides has the N-1 that is equal to or less than 30ppm, 3-butadienyl carboxylic acid amide content.
Brief description of the drawings
Fig. 1 shows according to the viscosity of the method mensuration of embodiment 1 and the N-1 in the thick N-vinyl acetamide (NVA), the relation between the 3-butadienyl ethanamide content.Viscosity is measuring of the polymerization degree.
Detailed Description Of The Invention
The below explains the present invention.
The N-vinyl carboxylic acid acid amides that the present invention uses represents with formula (I):
CH 2＝CH-NR 1-COR 2    (I)
(R wherein1And R2Represent respectively hydrogen atom or have the alkyl of 1-5 carbon atom). The example comprises the N-vinyl formamide, N-methyl-N-vinyl formamide, N-vinyl acetamide, N-methyl-N-vinyl acetamide, N-vinyl propionamide, N-methyl-N-vinyl propionamide, N-vinyl butyramide and N-vinyl isobutyramide. Wherein, preferred N-vinyl formamide and N-vinyl acetamide, more preferably N-vinyl acetamide.
N-1,3-divinyl carboxylic acid amide is represented with formula (II):
CH 2＝CH-CH＝CH-NR 1-COR 2????(II)
(R wherein 1And R 2Have respectively and identical implication as defined above) and comprise cis and the trans forms that it exists as geometrical isomer.
In the present invention, can pass through to regulate N-1 by height polymeric N-vinyl carboxylic acid acid amides, the content of 3-butadienyl carboxylic acid amide in thick N-vinyl carboxylic acid acid amides obtains to being equal to or less than 30ppm, but required high polymerizability can be by regulating this content preferably to being equal to or less than 10ppm and more preferably obtaining to being equal to or less than 1ppm.If this content surpasses above-described scope, high polymerizability just is difficult to obtain.
This can pass through, for example, N-1,3-butadienyl ethanamide in thick N-vinyl acetamide content and the relation (accompanying drawing 1) between the viscosity (polymerization degree) be verified.
The present invention has no particular limits the method for producing N-vinyl carboxylic acid acid amides, this N-vinyl carboxylic acid acid amides is used to produce highly polymeric N-vinyl carboxylic acid acid amides of the present invention, as long as the N-1 that the thick N-vinyl carboxylic acid acid amides that obtains thus has, 3-butadienyl carboxylic acid amide content surpasses 30ppm, in some cases, surpass 10ppm or 1ppm.But, in an embodiment preferred, the dealcoholization of N-vinyl carboxylic acid acid amides by N-(1-alkoxyethyl) carboxylic acid amide, or the dealcoholization production by N-(1-alkoxyethyl) carboxylic acid amide that obtains by carboxylic acid amide, acetaldehyde and alcohol or by carboxylic acid amide and acetaldehyde dialkyl group acetal as intermediate.In this case, dealcoholization is preferably undertaken by thermo-cracking or catalytic pyrolysis.In another embodiment preferred, the cracking of N-vinyl carboxylic acid acid amides by the ethylene carboxylic acid amide, or the cracking production by the ethylene carboxylic acid amide that obtains by acetaldehyde and carboxylic acid amide as intermediate.In this case, the ethylene carboxylic acid amide is cracked into carboxylic acid amide and N-vinyl carboxylic acid acid amides.
In the present invention, has N-1, the content of 3-butadienyl carboxylic acid amide be equal to or less than 30ppm can height polymeric N-vinyl carboxylic acid acid amides can be by purification processing method production, this method reduces from thick N-vinyl carboxylic acid acid amides or removes N-1,3-butadienyl carboxylic acid amide; Perhaps can be by purification processing method production, this method reduces from the raw materials for production of N-vinyl carboxylic acid acid amides or intermediate or removes N-1,3-butadienyl carboxylic acid amide or its precursor.
Reduce from thick N-vinyl carboxylic acid acid amides or remove N-1, the method for 3-butadienyl carboxylic acid amide is described below.
From thick N-vinyl carboxylic acid acid amides, reduce or remove N-1, the purification processing method of 3-butadienyl carboxylic acid amide comprises, for example, by rectifying, recrystallization method, piezocrystallization or with the physical purification treatment process of the processing of sorbent material such as activated carbon treatment thick N-vinyl carboxylic acid acid amides or its solution, with use N-1, the purification processing method of the chemical conversion of 3-butadienyl carboxylic acid amide, as use diels-Alder reaction to handle N-1 with right-benzoquinones, the method of 3-butadienyl carboxylic acid amide and use selective hydration are handled the method for 1,3-butadiene base.These methods can be used separately or be used in combination.Except aforesaid method, everyly can make N-1,3-butadienyl carboxylic acid amide separates from N-vinyl carboxylic acid acid amides easily or easily by any method of chemical conversion, all can use.
Be described in more detail below and from thick N-vinyl carboxylic acid acid amides, remove or reduce N-1, the method for the quantity of 3-butadienyl carboxylic acid amide.
The inventive method has no particular limits the water distilling apparatus that uses in the rectifying separation, can use column plate post or packed column with 1 to 50 theoretical plate number.But, preferably use rectifying column, its build-up of pressure loss hardly, and have good rectifiable property, the example comprises the packed column that uses conventional fillers.Distillation is preferably carried out under alap temperature, because N-vinyl carboxylic acid acid amides is heated apt to deteriorate.Therefore, distillation is being to carry out under 0.01 to 100mmHg the decompression from pressure.
Rectifying can be continuously or off and on intermittently, still, considers preferred operate continuously from throughput and safety operation.Reflux ratio is not particularly limited, can be according to N-1, and the content of 3-butadienyl carboxylic acid amide, the kind of N-vinyl carboxylic acid acid amides and the property regulation of distillation column.But, reflux ratio normally from 0.1 to 20, preferably from 0.5 to 10.
In the inventive method, when separation is when comprising the recrystallization method that cools off thick N-vinyl carboxylic acid acid amides and carry out, can directly cool off N-vinyl carboxylic acid acid amides, perhaps can use and N-vinyl carboxylic acid acid amides recrystallization solvent reaction and that have suitable solubleness.The example of recrystallization solvent comprises aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; Aliphatic hydrocarbon such as pentane, pentamethylene, hexane, hexanaphthene and heptane; Pure as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol and hexalin; Halohydrocarbon such as chloroform and chlorobenzene; Ketone such as acetone, methylethylketone and pimelinketone; Ester such as methyl acetate, ethyl acetate, propyl acetate and butylacetate; Ether such as ether; Acid amides such as N, dinethylformamide and N,N-dimethylacetamide; And methyl-sulphoxide.Preferred toluene, hexanaphthene, methyl alcohol and Virahol.These solvents also can be used in combination.Cooling temperature changes according to the kind of N-vinyl carboxylic acid acid amides and quantity and recrystallization solvent, but normally at-20 to 50 ℃, preferred-10 to 40 ℃.
The structure formation of the crystallization apparatus that uses among the present invention is not particularly limited, and can be continuous system or batch system.Crystallization method also can use the heat exchange that utilizes heat-eliminating medium, perhaps the evaporation concentration of solvent and cooling.
The device of the fractional crystallization that uses among the present invention also is not particularly limited.Can use the device that utilizes vacuum pressure or exert pressure, or utilize the device of gravity or centrifugal force.
Among the present invention, also can use in same device in conjunction with crystallization and isolating solid-liquid separator.The preferred embodiment of this device comprises, under the situation of not using recrystallisation solvent, and pressure crystallizer, falling-film crystallizer (for example, fractional crystallization device) and tower continuous crystallisation purifier (for example, BMC or backmixing post mould assembly).Under the situation of filtering the high density slurries, preferably use automatic Nutsche filter such as Rosemund filter.
In the inventive method, when when separating thick N-vinyl carboxylic acid acid amides with sorbent material such as activated carbon treatment, the sorbent material that uses among the present invention is not particularly limited, as long as it optionally adsorbs N-1,3-butadienyl carboxylic acid amide with the comparison of N-vinyl carboxylic acid acid amides.The example of sorbent material comprises gac, clay, aluminum oxide, silicon-dioxide, zeolite and adsorptive resin, wherein preferred gac.
In the adsorption operations of the present invention, thick N-vinyl carboxylic acid acid amides can be put into directly and contacted with sorbent material.On the other hand, crude product solution can be dissolved in the reaction of N-vinyl carboxylic acid acid amides and have in the solvent of suitable solubleness, put into then with sorbent material and contact.The example of solvent comprises water and those solvents about recrystallization of describing in the above, when using gac as sorbent material, especially preferably makes water and methyl alcohol.Solvent is not particularly limited with the ratio of thick N-vinyl carboxylic acid acid amides, and still, when making water or methyl alcohol as solvent, this ratio is 0 to 10: 1 (by weight) preferably, is more preferably 0.1 to 3: 1 (by weight).
Be fit to carry out of the kind variation of the adsorption temp of adsorption operations of the present invention, but be preferably-20 to 100 ℃, more preferably 0 to 80 ℃ according to sorbent material.If adsorption temp is lower than-20 ℃, the diffusion in the sorbent material hole is seriously slowed down so that has been prolonged adsorption time unfriendly.If temperature is higher than 100 ℃, then the stability of N-vinyl carboxylic acid acid amides is lowered, and equilibrium adsorption capacity is greatly reduced simultaneously.
Adsorption method of the present invention is not particularly limited with regard to its structure formation, but can be continuous system or batch system.
Among the present invention, N-1, the content of 3-butadienyl carboxylic acid amide in N-vinyl carboxylic acid acid amides can be reduced to 30ppm or lower by the thick N-vinyl carboxylic acid of chemical treatment amide solution.The present invention is not particularly limited the chemical reaction that uses, as long as this reaction has utilized N-vinyl carboxylic acid acid amides and N-1, the difference between the 3-butadienyl carboxylic acid amide on reactivity.For example, with the reaction of diene be highly active and with the reaction of monoene be non-activity.
The method of using diels-Alder reaction to handle thick N-vinyl carboxylic acid amide solution is described below and uses selective hydration to handle the method for this solution.
Among the present invention, when using diels-Alder reaction to handle thick N-vinyl carboxylic acid amide solution, this processing is by allowing nucleophilie diene compound (dienophile) be present in diels-Alder reaction in the thick N-vinyl carboxylic acid amide solution.Nucleophilie diene compound of the present invention is not particularly limited, as long as it is the compound that is often used as nucleophilie diene compound in diels-Alder reaction, particularly, be be selected from replaced by one or more electron withdrawing groups and not with the α of N-vinyl carboxylic acid acid amides reaction, the compound of β-unsaturated compound.The example of nucleophilie diene compound comprises esters of unsaturated carboxylic acids, as acrylate, and maleic acid ester and fumarate; Beta-unsaturated ketone such as methyl vinyl ketone and right-benzoquinones; Unsaturated nitrile such as vinyl cyanide; With unsaturated acyl imines such as toxilic acid imide.Wherein, preferably right-benzoquinones.The quantity of nucleophilie diene compound is not particularly limited, if its equivalent in or greater than contained N-1 in thick N-vinyl carboxylic acid acid amides, the quantity of 3-butadienyl carboxylic acid amide.But, nucleophilie diene compound and the N-1 that in thick N-vinyl carboxylic acid acid amides, comprises, the mol ratio of 3-butadienyl carboxylic acid amide is 1 to 100 equivalent normally, preferred 1.2 to 10 equivalents.
Among the present invention, when handling thick N-vinyl carboxylic acid amide solution by diels-Alder reaction, thick N-vinyl carboxylic acid acid amides can directly contact with nucleophilie diene compound.On the other hand, crude product solution can be dissolved in not with the reaction of N-vinyl carboxylic acid acid amides and have in the solvent of suitable solubleness, carries out diels-Alder reaction then.The example of solvent comprises above-described solvent about adsorption method of the present invention.And, though when the present invention handles thick N-vinyl carboxylic acid amide solution by diels-Alder reaction, do not need catalyzer, can use those known in diels-Alder reaction, have catalytic activity and not with N-vinyl carboxylic acid acid amides catalyst for reaction.The example of catalyzer comprises Lewis acid such as aluminum chloride, boron trifluoride and lanthanide complex.
Be suitable for of the kind variation of the temperature of reaction of diels-Alder reaction of the present invention, but temperature of reaction is more preferably 0 to 80 ℃ preferably-20 to 100 ℃ according to the nucleophilie diene compound that uses.If temperature of reaction is lower than-20 ℃, then speed of reaction is too slow, if but temperature of reaction surpasses 100 ℃, and then the stability of N-vinyl carboxylic acid acid amides is lowered unfriendly.
The N-vinyl carboxylic acid amide solution of handling by diels-Alder reaction of the present invention contains the Diels-Alder adduct that produces by diels-Alder reaction, but this compound does not almost have injurious effects to the polymerization of N-vinyl carboxylic acid acid amides.Diels-Alder adduct of Chan Shenging and N-1 in the present invention, 3-butadienyl carboxylic acid amide is compared has low vapour pressure.Therefore, if N-vinyl carboxylic acid acid amides is purified by distillation after handling through diels-Alder reaction of the present invention, Di Ersi Alder affixture is than N-1, and 3-butadienyl carboxylic acid amide is easier to be separated, and the latter only just is removed by distillation.In other words, this compound can use simple distillation plant to separate.
Using hydrogenation of the present invention to handle N-vinyl carboxylic acid acid amides is undertaken by thick N-vinyl carboxylic acid acid amides is contacted in the presence of catalyzer with hydrogen.The present invention is not particularly limited this catalyzer, as long as it has the general activity of the selective hydrogenation of alkene, still, catalyzer preferably has Senior Two olefin hydrogenation selectivity when having monoolefine and diolefine simultaneously.The example of catalyzer comprises and loads on aluminum oxide, Pd series on gac or the silicon-dioxide, the improvement product of Co series or Ni-Co-Cr series metal or these metals, wherein, preferred Pd-aluminum oxide, the Pd-Ag-aluminum oxide, the Pd-Pb-aluminum oxide, Pd-Cr-aluminum oxide and Pd-aluminum oxide-catalyst based.When using Pd as metal component, its charge capacity is preferably 0.001 to 5wt%, and more preferably 0.01 to 1wt%.If its charge capacity is lower than 0.001wt%, then speed of reaction is quite slow, if but its charge capacity surpasses 5wt%, and the N-ethyl acetamide that obtains from the hydrogenation of N-vinyl carboxylic acid acid amides increases unfriendly.
Among the present invention, when handling N-vinyl carboxylic acid acid amides by hydrogenation, N-vinyl carboxylic acid acid amides can directly contact with hydrogen, maybe can be dissolved in the solvent, this solvent is not with the reaction of N-vinyl carboxylic acid acid amides and have suitable solubleness, carries out hydrogenation then.The example of solvent is included in above-described solvent about adsorption method of the present invention.Wherein, preferred alcohols, special particular methanol and Virahol.The temperature of reaction that is suitable for hydrogenation of the present invention changes according to the kind of the catalyzer that uses, but preferred-20 to 100 ℃ of temperature of reaction, more preferably 0 to 80 ℃.If temperature of reaction is lower than-20 ℃, then speed of reaction is quite slow, if but temperature of reaction surpasses 100 ℃, and then the stability of N-vinyl carboxylic acid acid amides is lowered.
The hydrogen partial pressure that is suitable for selective hydrogenation of the present invention is 0.01 to 100kg/cm 2, preferred 0.5 to 50kg/cm 2If hydrogen partial pressure is lower than 0.01kg/cm 2, then speed of reaction is quite slow, if but this dividing potential drop surpasses 100kg/cm 2, then the N-ethyl acetamide that obtains from the hydrogenation production of N-vinyl carboxylic acid acid amides increases and equipment becomes expensive more.
When adding catalyzer and making its fluidisation, the felicity condition of fluid space speed is according to hydrogen partial pressure, temperature of reaction and N-1, the content of 3-butadienyl carboxylic acid amide, but fluid space speed preferably 0.05 to 1000.If this speed surpasses 1000, N-1, the conversion of 3-butadienyl carboxylic acid amide is inadequate, if but this speed is lower than 0.05, and the usefulness of reaction is lowered.
The reaction method that uses among the present invention can carry out continuously or intermittently carry out, and reaction vessel is not particularly limited on structure formation.Can use any gas-solid contact, gas-liquid-solid contact and solid-liquid contact reactor still, preferably can make the solid-liquid reaction device of raw material and catalyzer uniform contact under gentle relatively condition.When carrying out solid-liquid reaction, hydrogen is dissolved in the thick N-vinyl carboxylic acid amide solution in advance so that provide reaction required hydrogen.
After the hydrogenation, reaction soln contains the by product that is accompanied by the product of producing by hydrogenation.The method of purification reaction solution comprises, for example, rectifying, by the piezocrystallization of refrigerative recrystallization and solution, these methods can be used separately or be used in combination.Except these methods, if can easily by product and the isolating any method of N-vinyl carboxylic acid acid amides all can be used and be not particularly limited.
As mentioned above, N-1,3-butadienyl carboxylic acid amide have cis and transconfiguration and because their difference on physical properties or reactivity, its separation degree can change in the present invention.In this case, N-1, the reaction of the cis-trans isomer of 3-butadienyl carboxylic acid amide can be carried out under the appropriate reaction condition that cooperates aforesaid operations such as lock out operation.
Under any circumstance, N-vinyl carboxylic acid acid amides causes solvolysis or hydrolysis when acid exists.Therefore, the utility appliance that it preferably places the present invention to use under rare gas element (nitrogen) or dry air atmosphere, as production unit, separating device, head tank is in product container and the filtrate tank.And, for fear of the hydrolysis reaction of N-vinyl carboxylic acid acid amides, can in raw material, add siccative such as sal epsom in a small amount.
When having alkali, can cause dimerization reaction.Therefore, preferred pH value with N-vinyl carboxylic acid amide solution is adjusted to 3 to 11 before distillation and adsorption operations, and is preferred 4 to 10, and more preferably 5 to 6.When thick N-vinyl carboxylic acid amide solution is acidity, regulate its pH value by adding basic cpd.The example of basic cpd comprises sodium salt such as yellow soda ash, sodium bicarbonate, sodium hydroxide; phosphoric acid (hydrogen) sodium and sodium acetate; sylvite such as salt of wormwood, saleratus, potassium hydroxide; phosphoric acid (hydrogen) potassium and potassium acetate; with aromatic amine such as N-phenyl-a-naphthylamine, 4,4 '-two (α; α-Er Jiajibianji) diphenylamine; N-phenyl-N '-(1, the 3-dimethylbutyl)-right-phenylenediamine, N-phenyl-N '-sec.-propyl-right-phenylenediamine; N-phenyl-N '-(1-methylheptyl)-right-phenylenediamine; N-phenyl-N '-cyclohexyl-right-phenylenediamine, N, N '-phenylbenzene-right-phenylenediamine; N; N '-two-betanaphthyl-right-phenylenediamine, N, N '-two (1; 4-dimethyl amyl group)-right-phenylenediamine; N, N '-two (1-ethyl-3-methyl amyl)-right-phenylenediamine, N; N '-two (1-methylheptyl)-right-phenylenediamine and N-phenyl-N '-(ptoluene-sulfonyl)-right-phenylenediamine, wherein preferred especially sodium hydroxide.
The add-on of basic cpd is preferably 1 to 10000ppm, and more preferably 10 to 1000ppm.If add-on surpasses 10000ppm, under the situation of inorganic salt, the salt of this quantity can not dissolve fully, and excessive adding does not obtain the effect of desirable increase.Under the situation of aromatic amine, be difficult to remove fully aromatic amine in purification step, the polymerizability of N-vinyl carboxylic acid acid amides is lowered.If the quantity that adds is less than 1ppm, then almost do not obtain stabilization.
When thick N-vinyl carboxylic acid amide solution was alkalescence, solution was regulated by adding acidic cpd.The example of acidic cpd comprises acid mineral compound example hydrochloric acid, sulfuric acid, and nitric acid, phosphoric acid and salt thereof and acidic organic compound comprise carboxylic acid such as acetate, phthalic acid and citric acid, phenylic acid such as phenol, quinhydrones and catechol, and their salt.
In the method that the present invention uses, reduce or remove the raw materials for production that are contained in N-vinyl carboxylic acid acid amides or the N-1 in the intermediate, the method for 3-butadienyl carboxylic acid amide or its precursor is described below.When all precursors are converted to N-1, during 3-butadienyl carboxylic acid amide before body burden N-1, the content of 3-butadienyl carboxylic acid amide is represented.
In the inventive method, the raw materials for production of N-vinyl carboxylic acid acid amides or intermediate comprise N-(1-alkoxyethyl) carboxylic acid amide, aldehyde contract dialkyl group alcohol (dialkylacetal) and ethylene carboxylic acid amide.The example of the alkoxyl group in N-(1-alkoxyethyl) carboxylic acid amide and aldehyde contract dialkyl group alcohol (dialkylacetal) comprises aliphatics alkoxyl group such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy and sec-butoxy.The example of the carboxylic acyloxy amido in N-(1-alkoxyethyl) carboxylic acid amide and ethylene carboxylic acid amide comprises methane amide, N-methylformamide, ethanamide, N-methylacetamide, propionic acid amide, butyramide and isobutyramide.The example of corresponding compounds comprises: as N-(1-alkoxyethyl) carboxylic acid amide be, N-(1-methoxy ethyl) ethanamide, N-(1-methoxy ethyl) methane amide, N-(1-ethoxyethyl group) ethanamide, N-(1-ethoxyethyl group) methane amide, N-(1-isopropoxy ethyl) ethanamide and N-(1-isopropoxy ethyl) methane amide; As what aldehyde contracted dialkyl group alcohol (dialkylacetal) be methylal, aldehyde diethyl acetal and the aldehyde diisopropanol that contracts; Be ethylene ethanamide, ethylene methane amide, ethylene (N-methylformamide) and ethylene propionic acid amide as the ethylene carboxylic acid amide.
By known method such as thermo-cracking or catalytic pyrolysis N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide are changed into N-vinyl carboxylic acid acid amides.Reaction conditions is for example, to make reaction use gas phase or liquid phase.Temperature of reaction is from 60 to 600 ℃, and the reaction times is 0.3 second to 2 hours, and reaction pressure is to normal atmosphere from 0.1mmHg.The example of the catalyzer that uses under the situation of catalytic pyrolysis comprises an alkali metal salt of carboxylic acid such as the oxide compound of potassium acetate and basic metal or alkaline-earth metal, as magnesium oxide.
N-1,3-butadienyl carboxylic acid amide is by N-(1,3-dialkoxy butyl) thermo-cracking of carboxylic acid amide or catalytic pyrolysis cause that two pure molecules eliminate and produce, and perhaps thermo-cracking by 3-alkoxyl group butylidene dicarboxylic acid acid amides or catalytic pyrolysis cause that the elimination of alcohol and carboxylic acid acid amides produces.N-(1,3-dialkoxy butyl) carboxylic acid amide and 3-alkoxyl group butylidene dicarboxylic acid acid amides pass through 1,1, the reaction production of 3-tri-alkoxy butane and carboxylic acid amide.
Therefore, in the present invention, N-1, the example of the precursor of 3-butadienyl carboxylic acid amide comprises 1,1,3-tri-alkoxy butane, N-(1,3-dialkoxy butyl) example of carboxylic acid amide and 3-alkoxyl group butylidene dicarboxylic acid acid amides and alkoxyl group in these precursors and carboxylic acyloxy amido comprises corresponding in the above-described N-vinyl carboxylic acid amide precursor those.Therefore, 1,1,3-tri-alkoxy butane comprises 1,1,3-trimethoxy butane, 1,1,3-triethoxybutane and 1,1,3 three isopropoxy butane; N-(1,3-dialkoxy butyl) carboxylic acid amide comprises N-(1,3-dimethoxy butyl) ethanamide, and N-(1,3-dimethoxy butyl) methane amide, N-(1,3-diethoxy butyl) ethanamide, N-(1,3-diethoxy butyl) methane amide, N-(1,3-diisopropoxy butyl) ethanamide and N-(1,3-diisopropoxy butyl) methane amide; Comprise 3-methoxyl group butylidene diethylamide with 3-alkoxyl group butylidene dicarboxylic acid acid amides, 3-methoxyl group butylidene diformamide, 3-oxyethyl group butylidene diethylamide, 3-oxyethyl group butylidene diformamide, 3-isopropoxy butylidene diethylamide and 3-isopropoxy butylidene diformamide.
In the raw materials for production of N-vinyl carboxylic acid acid amides or intermediate, reduce N-1,3-butadienyl carboxylic acid amide or its preceding body burden comprise to 30ppm or embodiment still less, for example, rectificating method, the recrystallization method of the precursor solution by cooling N-vinyl carboxylic acid acid amides, the piezocrystallization method of this precursor, by using sorbent material such as the physical adsorption method of this precursor of activated carbon treatment and the method for this precursor of chemical treatment, these methods can be used separately or be used in combination.Also can use additive method and have no particular limits, as long as N-1,3-butadienyl carboxylic acid amide or its precursor can be easily separated from the raw materials for production of N-vinyl carboxylic acid acid amides or intermediate.
And, by the production method of N-vinyl carboxylic acid acid amides with good polymerizability having been carried out the result of broad research, the inventor has been found that, when producing in the N-vinyl carboxylic acid acid amides process at thermo-cracking or catalytic pyrolysis by N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide, the 33wt% pH value of aqueous solution (following be called simply " pH ") that the N-vinyl carboxylic acid amide content of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is reduced to 10wt% or lower and N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is adjusted at 5 to 10 o'clock, produces the N-vinyl carboxylic acid acid amides that obtains being used for the synthetic macromolecule weight polymers.
More particularly, the invention provides the production method of N-vinyl carboxylic acid acid amides with good polymerizability, wherein, when thermo-cracking or the catalytic pyrolysis when producing of N-vinyl carboxylic acid acid amides by N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide, the N-vinyl carboxylic acid amide content of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is reduced to 10wt% or lower, preferred 5wt% or lower, more preferably 3wt% or lower, the pH value of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is adjusted to 5 to 10, preferred 6 to 8, more preferably 6.3 to 7.5, more preferably, N-vinyl carboxylic acid amide content is reduced to 3wt% or lower, and its pH value is adjusted to 6.3 to 7.5 simultaneously.
The N-vinyl carboxylic acid acid amides that N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide contain usually above 10wt% has many reasons.
Reason is to purify when separating by distillation procedure or the like when the reaction soln that contains N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide that obtains by above-described synthetic method, and part N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide are cracked into N-vinyl carboxylic acid acid amides.
Another reason is when thermo-cracking or the synthetic N-vinyl carboxylic acid acid amides of catalytic pyrolysis by N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide and when separating the N-vinyl carboxylic acid, and unreacted N-(1-alkoxyethyl) carboxylic acid amide or the ethylene carboxylic acid amide that contain the N-vinyl carboxylic acid are recycled cracking.
The N-vinyl carboxylic acid amide content that reduction N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide are described below is to 10wt% or lower method.
This method is not particularly limited, so long as the N-vinyl carboxylic acid amide content that reduces N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide to 10wt% or lower method just.This method comprises, for example, handle N-(1-alkoxyethyl) carboxylic acid amide, ethylene carboxylic acid amide or their solution by rectificating method, Azotropic distillation method, recrystallization method or piezocrystallization method, these methods can be used separately or be used in combination.Except these methods, can use any other method and without any restriction, as long as these methods can separate easily N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide and N-vinyl carboxylic acid acid amides.
The N-vinyl carboxylic acid amide content that is described in more detail below reduction N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is to 10wt% or lower embodiment.
In the inventive method, separating the water distilling apparatus that uses by rectificating method is not particularly limited, can use that to have theoretical plate number be 1 to 50 column plate post or packed column, but preferably use rectifying column, because rectifying column build-up of pressure loss and have good rectifying performance hardly.The example of this rectifying column is to use the packed column of conventional fillers.N-(1-alkoxyethyl) carboxylic acid amide, ethylene carboxylic acid amide and N-vinyl carboxylic acid acid amides are because heating is apt to deteriorate.Therefore, preferably under alap temperature, distill.Therefore, under 0.01 to 100mmHg decompression, distill.
The present invention can carry out continuously or off and on, still, from throughput and operational safety, preferably uses operate continuously.Reflux ratio is not particularly limited, and can set according to the content of N-vinyl carboxylic acid acid amides and the capacity of kind and distillation column.But, reflux ratio normally 0.1 to 20, preferred 0.5 to 10.
In the inventive method, when separating by cooling N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide solution, can use recrystallization solvent, the apparatus and method of above-described relevant N-vinyl carboxylic acid acid amides recrystallization method according to recrystallization method.
The method of the pH value of adjusting N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide to 5-10 is described below.
Owing to wherein have carboxylic acid such as acetate, the pH value of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is lower than 5.Although people also do not know clearly why wherein be mixed with carboxylic acid, but it is believed that this is because due to the oxidation of the acetaldehyde that uses in N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide synthetic, or owing to pass through due to the production of carboxylic acid amide of solvolysis.
The pH value of adjusting N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide to the method for 5-10 is not particularly limited.This method comprises, for example, by rectificating method, Azotropic distillation method, recrystallization method, piezocrystallization method, the physical method that uses sorbent treatment or the use method based on acid or alkali neutral chemical process processing N-(1-alkoxyethyl) carboxylic acid amide, ethylene carboxylic acid amide or their solution, these methods can be used separately or be used in combination.
In these methods, physical method comprises the treatment process by rectificating method, Azotropic distillation method, recrystallization method or piezocrystallization method, can carry out with the same way as relevant with the above-described N-of removing vinyl carboxylic acid acid amides.Use the method for sorbent material to comprise the method for anionite-exchange resin of using as sorbent material.
The example that is used for antacid basic cpd in chemical process comprises sodium salt such as yellow soda ash, sodium bicarbonate, sodium hydroxide, phosphoric acid (hydrogen) sodium and sodium acetate and sylvite such as salt of wormwood, saleratus, potassium hydroxide, phosphoric acid (hydrogen) potassium and potassium acetate.
When N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide solution are alkalescence, regulate its pH value by adding acidic cpd.The example of acidic cpd comprises acid mineral compound example hydrochloric acid, sulfuric acid, and nitric acid, phosphoric acid and salt thereof and acidic organic compound comprise carboxylic acid such as acetate, phthalic acid and citric acid, phenylic acid such as phenol, quinhydrones and catechol, and salt.
N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide are undertaken by above-described thermo-cracking or catalytic pyrolysis to the conversion of N-vinyl carboxylic acid acid amides.
Among the present invention, N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide cause solvolysis or hydrolysis when having acid.Therefore, be preferably the present invention and dispose auxiliary equipment, as production equipment, tripping device, head tank, product vessel and filtrate tank, and the present invention placed under rare gas element (nitrogen) or the dry air atmosphere.And, for fear of the hydrolysis reaction of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide, small quantity of drying such as sal epsom can be added in the raw material.
Among the present invention, when the thermo-cracking of passing through N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide or catalytic pyrolysis production N-vinyl carboxylic acid acid amides, the N-vinyl carboxylic acid amide content of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is reduced to 10wt% or lower, preferred 5wt% or lower, more preferably 3wt% or lower, the pH value of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is adjusted to 5 to 10, preferred 6 to 8, more preferably 6.3 to 7.5, and more preferably, N-vinyl carboxylic acid amide content is reduced to 3wt% or lower, the pH value is adjusted to 6.3 to 7.5 simultaneously, obtains having the N-vinyl carboxylic acid acid amides of required polymerizability thus.If N-vinyl carboxylic acid amide content surpasses above-mentioned scope, thermo-cracking by N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide or catalytic pyrolysis often are difficult to obtain can height polymeric N-vinyl carboxylic acid acid amides.Equally, if the pH value surpasses above-mentioned scope, thermo-cracking by N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide or catalytic pyrolysis often are difficult to obtain can height polymeric N-vinyl carboxylic acid acid amides.
The invention provides the above-described N-vinyl carboxylic acid acid amides of use and produce the homopolymer of N-vinyl carboxylic acid acid amides or the method for multipolymer.
By using wherein thick N-vinyl carboxylic acid acid amides to have 30ppm or lower N-1,3 butadienyl carboxylic acid amide content can height polymeric N-vinyl carboxylic acid acid amides, can obtain the multipolymer of the homopolymer of high-molecular weight N-vinyl carboxylic acid acid amides or it and other copolymerisable monomers.
When using in this article, " highly polymerization " refers to that the viscosity of measuring as the method for the following examples 1 is 30cps or bigger, preferred 60cps or bigger and also refer to that the appearance time of measuring as the method for the following examples 13 is 15 hours or shorter simultaneously, preferred 10 hours or shorter.Term " high molecular " refers to that weight-average molecular weight is 500000 or bigger, preferred 1000000 or bigger.
The present invention can comprise with the specific examples of the representative monomers of N-vinyl carboxylic acid acid amides copolymerization:
An alkali metal salt of acrylic or methacrylic acid such as sodium salt or sylvite; The alkyl ester of this an alkali metal salt, as methyl ester, ethyl ester, propyl diester, butyl ester, amyl group ester, polyhexamethylene, heptyl ester, octyl group ester, nonyl ester, decyl ester, stearyl ester and palmityl ester; The hydroxyl low-grade alkyl ester of this an alkali metal salt, as hydroxyethyl ester, hydroxypropyl ester and hydroxyl butyl ester; The lower alkyl esters of this an alkali metal salt that is replaced by low-grade alkyl amino, as the dimethylaminomethyl ester, the dimethyl aminoethyl ester, the dimethylaminopropyl ester, the dimethylamino butyl ester, diethylamino methyl ester, diethylamino ethyl ester, diethylamino propyl diester and diethylamino butyl ester; The lower alkyl esters halogenide that is replaced by quaternary ammonium group of this an alkali metal salt (preferred muriate of halogenide or bromide), as trimethyl ammonium ethyl ester halogenide, trimethyl ammonium propyl diester halogenide, triethyl ammonium ethyl ester halogenide and triethyl ammonium propyl diester halogenide; The acid amides of this an alkali metal salt; The acid amides that is replaced by low-grade alkyl amino of this an alkali metal salt, as the dimethylaminomethyl acid amides, the dimethyl aminoethyl acid amides, the dimethylaminopropyl acid amides, the dimethylamino butyl amide, diethylamino methyl acid amides, diethylamino buserelin, diethylamino propyl amides and diethylamino butyl amide; The low alkyl group acid amides that is replaced by quaternary ammonium group of this an alkali metal salt, as trimethyl ammonium buserelin halogenide, triethyl ammonium propyl amides halogenide, triethyl ammonium buserelin halogenide and triethyl ammonium propyl amides halogenide; The low alkyl group acid amides that is replaced by sulfonic acid or alkali metal sulfonate of this an alkali metal salt, as the sulfo group methyl nitrosourea, sulfo group buserelin, sulfo group propyl amides, the sulfo group butyl amide, sulfo group methyl nitrosourea sodium, sulfo group buserelin sodium, sulfo group propyl amides potassium, sulfo group butyl amide potassium, sulfo group methyl nitrosourea potassium, sulfo group buserelin potassium, sulfo group propyl amides potassium and sulfo group butyl amide potassium; Vinyl cyanide; Vinyl ether such as methylvinylether, ethyl vinyl ether, propyl vinyl ether and butyl vinyl ether; Vinyl ketone such as methyl vinyl ketone and ethyl vinyl ketone; Low-stage ethylene yl carboxylic acid ester such as vinyl-acetic ester and vinyl propionate base ester; Maleic anhydride; Toxilic acid; Sodium maleate; And maleic acid potassium.
(methyl) vinylformic acid wherein preferably, (methyl) sodium acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid trimethyl ammonium diethylaluminum monochloride, acrylamide, sulfo group propyl group acrylamide sodium, sulfo group butyl acrylamide sodium, vinyl cyanide, methylvinylether, ethyl vinyl ether, methyl vinyl ketone, ethyl vinyl ketone, vinyl-acetic ester, N-vinyl-2-Pyrrolidone and maleic anhydride.When using in this article, " (methyl) vinylformic acid " refers to acrylic or methacrylic acid.
Among the present invention, can use the cross-linking monomer of the compound that in a molecule, has two or more unsaturated groups or linking agent as can with the monomer of N-vinyl carboxylic acid acid amides copolymerization.
Polymerization process needn't be restricted, and can use conventional currently known methods.Usually, preferably use solution polymerization process, inverse suspension polymerization method or inverse emulsion polymerization method.
For example, in solution polymerization process, monomer component and linking agent are by in water-soluble, organic solvent or their mixed solvent equably, by vacuum outgas or by remove the dissolved oxygen in the system with rare gas element such as nitrogen or carbon dioxide displacement, in system, add polymerization starter then and begin reaction.Normally about-10 to 60 ℃ of polymerization kick off temperatures, the reaction times is about 1 to 10 hour.
N-1 of the present invention, 3-butadienyl carboxylic acid amide is by mass spectrum (electron-bombardment method and chemical ioning method), infrared absorption spectrum and ultra-violet absorption spectrum checking and definite.For example, N-1,3-butadienyl ethanamide is determined by following.
N-1, the physical properties of 3-butadienyl carboxylic acid amide:
Mass spectrum (electron-bombardment method): 111,69,54,43
Mass spectrum (chemical ioning method): 112
Infrared absorption spectrum (cm -1): 3099,1732,1654,1471
Ultra-violet absorption spectrum (nm): 237,276
Among the present invention, N-1, the quantitative analysis of 3-butadienyl carboxylic acid amide is preferably undertaken by the high-speed liquid column chromatography, but the present invention is not limited to this method.For example, the operational condition of preferred following high-speed liquid column chromatography.Except as otherwise noted, quantitative analysis is carried out under these conditions in the embodiment of the invention.
Post: SHODEX SIL5B (Showa Denko K.K.)
Elutriant: normal hexane/Virahol (9/1), 1 ml/min
Detector: UV-detector, 254nm
The present invention is by being described in more detail with reference to the following examples and comparative example, and still, the present invention should not be considered to limited by they.
Embodiment 1
In the three-necked flask that thermometer and dry ice-ethanol trap is housed (200 milliliters), add 5.9 gram (0.1 mole) ethanamides, 40 gram (0.67 mole) Virahols, 2.16 gram (15 mmole) ethylene ethanamide and 14.6 gram (0.1 mole) acetaldehyde aldehyde diisopropanols (acetaldehyde diisopropylacetal) that contract, mixture stirred and under 45 to 48 ℃ temperature dissolving become evenly up to mixture.Add and to contain 0.43 gram (based on the 0.1wt% of inlet amount) vitriol oil and be dissolved in solution in 2 gram (33 mmole) Virahols (in the following example identical with it), after the stirring, wherein add 17.6 gram (0.4 mole) acetaldehyde with 3 fens clockwise by dropping funnel.After the dropping, mixture is reacted 3 hours with catalyst neutralisation at 50 ℃.Reaction mixture finds that by gas chromatographic analysis the ethanamide transformation efficiency is 88% then, the selectivity of N-(1-propoxy-ethyl) ethanamide be 94% and the ethylene ethanamide be the reaction soln of 5.3%. as the selectivity of by product from obtaining, obtain N-(1-propoxy-ethyl) ethanamide and be thermally cracked to N-vinyl acetamide and Virahol under the residence time condition by distillation under reduced pressure at 450 ℃ and 1 second.Cracked solution is cooled to 20 ℃, and in the high pressure crystal device at 1800kg/cm 2With separate mother liquor under 20 ℃ of conditions. it is 99.9% and N-1 that the result obtains purity, and 3-butadienyl content is the N-vinyl acetamide of 1ppm.In order to measure the polymerizability of N-vinyl acetamide, obtain 17wt% concentration solution to wherein adding distilled water, after the nitrogen exhaust, to wherein adding 500ppmV-50 (N, N '-azo two-(2-amidine propane) dihydrochloride immerses container in 45 ℃ of waters bath with thermostatic control.After 10 minutes, system is with the dilution of the 1% quinhydrones aqueous solution of 9wt%, uses BL-type (rotation) viscometer measurement viscosity and discovery viscosity to be 130cps under 30 ℃ and 30rpm rotation number condition.
The comparative example 1
It is 97.5% and N-1 that the thermo-cracking solution that will obtain in embodiment 1 obtains purity through simple distillation under 0.5mmHg pressure, and 3-butadienyl ethanamide content is the N-vinyl acetamide of 200ppm.According to embodiment 1 in identical mode carry out polymerizability and measure, measure and find that its viscosity is 10cps or lower.
Embodiment 2
Synthesizing of acetal:
Have 25 grades glass Oldershaw type rectifying column on add with the quantity of 180 grams per hour in several the 5th grade and contain 0.5wt% vitriolic methanol solution, in last several the 15th grade with the quantity adding acetaldehyde of 27 grams per hour.In rectifying column bottom, 500 ml flasks that wherein are placed with 100 gram water have been installed, with its 100 ℃ of heating with the material in the quantity distilling flasks of 29 grams per hour.The solution that distills out from flask is substantially free of organic thing.From the top of post, be 2 to distill out the methylal-methanol mixture of 221 Grams Per Hours with reflux ratio.Steam liquid and be substantially free of water and aldehyde.Acetaldehyde conversion is 100%, and the productive rate of dimethyl-acetal is 100%.
The separation of acetal
Have 25 grades glass Oldershaw type rectifying column on add normal hexanes with the quantity of 56 grams per hour in several the 1st grade, in last several the 10th grade, contain the methylal of 28wt% methyl alcohol with the quantity addings of 71 grams per hour.With the heating of this post so that column top temperature remains on 50 ℃ and reflux ratio is 6.Rectifying column than lower part, 500 ml flasks that wherein are placed with 100 gram methylals have been installed, it is immersed in the oil bath 110 ℃ of heating with the material in the quantity distilling flasks of 47 grams per hour.The solution that distills out from flask is the methylal that is substantially free of normal hexane and contains 0.3% methyl alcohol.From the top of post, steam the methylal-methyl alcohol-normal hexane mixture of 80 Grams Per Hours.Steam liquid and bottoms and be substantially free of water or acetaldehyde respectively.
Synthesizing of N-(1-methoxy ethyl) ethanamide:
Highly purified methylal that will obtain in the acetal separation method and the methylal that contains methyl alcohol that obtains in the Methanol Recovery method mix, and dissolve the exsiccant ethanamide therein with the reaction raw materials solution of preparation ethanamide/dimethyl-acetal/methyl alcohol with mol ratio 1/20/3.From have 40 millimeters internal diameters and be equipped with 60 milliliters of strong-acid ion exchange resin Amberlist 15 reaction tubes add this solution than lower part with 5 milliliters quantity per hour.In the chuck of reaction tubes, it is 55 ℃ with control reaction temperature with 55 ℃ hot water circulation.The reaction soln that will obtain from the top outlet of reaction vessel carries out quantitative analysis, found that, reaction soln has about 0/19/4/0.9 the mole that comprises ethanamide/dimethyl-acetal/methyl alcohol/MEA and forms, the ethanamide transformation efficiency is 98%, and the productive rate of N-(1-methoxy ethyl) ethanamide (MEA) is 90%.
The recovery of acetal:
Inject the film-type successive flash vaporization device of chuck under the decompression of reaction soln at 100mmHg that will in the synthesis step of N-(1-methoxy ethyl) ethanamide, obtain with 0.04 square metre of heating-surface area with the quantity of 600 grams per hour.In chuck, circulate with thermal medium.With per hour 17 the gram quantity be the evaporation residuum of N-(1-methoxy ethyl) ethanamide basically.Obtain comprising the methylal that contains 7wt% methyl alcohol and by the solution of condensing volatile constituent with the quantity of 583 grams per hour.
The recovery of methyl alcohol:
Have 25 grades glass Oldershaw type rectifying column on be added in the methylal that contains 7wt% methyl alcohol that the acetal recycling step obtains with the quantity of 200 grams per hour in several the 10th grade and steam the liquid cut.With the heating of this post so that column top temperature remains on 58 ℃ and reflux ratio is 6.Rectifying column than lower part, 500 ml flasks have been installed, it is immersed in the oil bath 110 ℃ of heating with the material in the quantity distilling flasks of 185 grams per hour.The solution that distills out from flask is the methylal that contains 5.6wt% methyl alcohol.From the top of post, with per hour 15 the gram quantity steam methylal-methanol azeotropic mixture (methyl alcohol; 24wt%).
Synthesizing of N-vinyl carboxylic acid acid amides:
What will obtain in the acetal recycling step is that the solution of N-(1-methoxy ethyl) ethanamide injects with the quantity of 20 milliliters of per minutes that to have internal diameter be that 20 millimeters and total length are 6 meters stainless steel reaction pipe basically, this reaction tubes under the decompression of 100mmHg 450 ℃ of heating.To also reclaim by N-vinyl acetamide and methanol mixture condensation in the condenser that the outlet of reaction tubes is installed that heat scission reaction is produced.The transformation efficiency of N-(1-methoxy ethyl) ethanamide is 92%.
Concentrating of N-vinyl acetamide:
Have 10 grades glass Oldershaw type rectifying column in several the 10th grade, be added in the reaction soln that obtains in the synthesis step of N-vinyl acetamide with the quantity of 200 grams per hour.Pressure be under the 200mmHg with the heating of this post so that column top temperature remains on 40 ℃ and reflux ratio is 2.Rectifying column than lower part 500 ml flasks have been installed, it is immersed in the oil bath 80 ℃ of heating with the material in the quantity distilling flasks of 155 grams per hour.The solution that distills out from flask is the thick N-vinyl acetamide solution that contains the N-vinyl acetamide of 94wt%.Steam methyl alcohol from the top of post with the quantity of 45 grams per hour.Thick N-vinyl acetamide contains 70ppmN-1,3-butadienyl ethanamide.
The purification of N-vinyl acetamide:
Have 10 grades glass Oldershaw type rectifying column on be added in the thick N-vinyl acetamide solution that obtains in the enrichment step of N-vinyl acetamide in several the 5th grade, be to carry out rectifying under 3 the condition in the decompression of 0.15mmHg and reflux ratio.The result obtains containing 4ppmN-1, and the purity of 3-butadienyl ethanamide is 98% N-vinyl acetamide.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, measure and find that its viscosity is 100cps.
Embodiment 3
What will obtain in the enrichment step of the N-vinyl acetamide among the embodiment 2 contains 70ppmN-1, and the thick N-vinyl acetamide of 3-butadienyl ethanamide is adjusted to 50 ℃, and in the high pressure crystal device at 1800kg/cm 2With separate mother liquor under 50 ℃ of conditions.It is 99.9% and N-1 that the result obtains purity, and 3-butadienyl ethanamide content is the N-vinyl acetamide of 1ppm.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, measure and find that its viscosity is 150cps.
Embodiment 4
What will obtain in the synthesis step of the N-vinyl acetamide among the embodiment 2 contains 70ppmN-1, and the methanol solution of the N-vinyl acetamide of 3-butadienyl ethanamide is with the LHSV of 2Hr-1 and at room temperature add and be equipped with in the post of gac.The solution that obtains contains the N-1 of 9ppm, 3-butadienyl ethanamide.The solution that obtains is under reduced pressure carried out simple distillation.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that steams, measure and find that its viscosity is 70cps.
Embodiment 5
Contain the N-1 of 200ppm to 50 weight parts that in comparative example 1, obtain, add 50 parts by weight of toluene in the N-vinyl acetamide of 3-butadienyl ethanamide and under nitrogen atmosphere at 40 ℃ with its dissolving.Mixture is cooled to after 4 ℃, by filtering separation crystalline deposit and drying under reduced pressure.The N-vinyl acetamide that obtains contains the N-1 of 8ppm, 3-butadienyl ethanamide.According to embodiment 1 in identical mode measure the polymerizability of this product, measure and find that its viscosity is 80cps.
Embodiment 6
To the N-1 that contains 70ppm that in the synthesis step of the N-of embodiment 2 vinyl acetamide, obtains, adding para benzoquinone in the methanol solution of the N-vinyl acetamide of 3-butadienyl ethanamide obtains 97ppm and (is equivalent to 1.5 equivalent N-1,3-butadienyl ethanamide) solution of concentration, and at room temperature stirred 1 hour.Reaction soln contains the N-1 of 9ppm, 3-butadienyl ethanamide.Solution is under reduced pressure carried out simple distillation.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that steams, measure and find that its viscosity is 70cps.
Embodiment 7
5 grams are contained the solid catalyst of the 0.5wt% palladium that loads on the alumina supporter and the N-1 that 50 grams contain 70ppm, 3-butadienyl ethanamide, the N-vinyl acetamide of 55wt%, the N-of 15wt% (1-methoxy ethyl) ethanamide, the thick N-vinyl acetamide of the ethanamide of 7wt% and 20wt% methyl alcohol places 200 ml flasks, and reaction stirring simultaneously in 30 minutes under hydrogen atmosphere at room temperature.After reacting completely, by filtering separating catalyst and analysis filtrate from reaction soln.Analyze N-1 by HPLC, 3-butadienyl ethanamide, other components are by gas chromatographic analysis.Reaction soln has 1ppm or lower N-1,3-butadienyl ethanamide content and the N-ethyl acetamide that contains 0.4wt%.
Decompression is down by after the distillation for removing methanol, in the high pressure crystal device at 2000kg/cm 2Pressure under with the crystallization of N-vinyl acetamide, separate mother liquors at 40 ℃.The N-vinyl acetamide that obtains has purity and 1ppm or the lower N-1 of 99.3wt%, 3-butadienyl ethanamide content.According to embodiment 1 in identical mode measure its polymerizability, found that its viscosity is 160cps.
Embodiment 8
The solid catalyst (2.5 gram) that will contain the 0.5wt% palladium that loads on the alumina supporter is added in the hydrogenation reactor under the nitrogen atmosphere.Under nitrogen atmosphere, 95kg is contained the N-1 of 400ppm, 3-butadienyl ethanamide, the N-vinyl acetamide of 55wt%, the thick N-vinyl acetamide of the N-of 15wt% (1-methoxy ethyl) ethanamide and 20wt% methyl alcohol in reaction vessel with 60Hr -1Liquid space velocity (LHSV) circulation 6 hours.Reaction soln has 1ppm or lower N-1,3-butadienyl ethanamide content and the N-ethyl acetamide that contains 0.3wt%.
Decompression is removed from the reaction soln that obtains after the methyl alcohol by distillation down, in the high pressure crystal device at 1800kg/cm 2With separate mother liquor under 30 ℃ of conditions.The result obtains purity to be 99.5wt% and to have 1ppm or a lower N-1, the N-vinyl acetamide of 3-butadienyl ethanamide content.
According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, found that its viscosity is 170cps.
Embodiment 9
The solid catalyst (25 gram) that will contain the 0.5wt% palladium that loads on the alumina supporter is added in the hydrogenation reactor under the nitrogen atmosphere, the N-1 that will contain 400ppm, 3-butadienyl ethanamide, the N-vinyl acetamide of 55wt%, the N-of 15wt% (1-methoxy ethyl) ethanamide, the thick N-vinyl acetamide of the ethanamide of 7wt% and 20wt% methyl alcohol circulates in reaction vessel.Reaction soln has 1ppm or lower N-1,3-butadienyl ethanamide content and the N-ethyl acetamide that contains 0.5wt%.
From the reaction soln that obtains, remove after the methyl alcohol, in the high pressure crystal device at 1800kg/cm 2With separate mother liquor under 30 ℃ of conditions.The result obtains purity to be 99.5wt% and to have 1ppm or a lower N-1, the N-vinyl acetamide of 3-butadienyl ethanamide content.
According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, found that its viscosity is 170cps.
Embodiment 10
Become 1 hour except use contains catalyzer and the reaction times that the catalyzer of the palladium that loads on the 0.05wt% on the alumina supporter and 0.3wt% silver replaces containing the 0.5wt% palladium that loads on the alumina supporter, according to embodiment 7 in identical mode carry out this experiment.Reaction soln has 1ppm or lower N-1,3-butadienyl ethanamide content and the N-ethyl acetamide that contains 0.4wt%.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, found that its viscosity is 170cps.
Embodiment 11
The methylal that contains 7wt% methyl alcohol that will obtain in the acetal recycling step of embodiment 2 is returned in the acetal separating step and separation of methanol from acetal.The acetal that obtains contains 1,1 of 250ppm, 3-trimethoxy butane.It is that 20 packed column is that 5 these acetals of distillation obtain containing 1,1 of 12ppm, the acetal of 3-trimethoxy butane with reflux ratio that use has theoretical plate number.With the treating processes after acetal process that obtains as the 1-methoxy ethyl ethanamide synthesis step of in embodiment 3, describing.But, in this embodiment, in N-vinyl acetamide purification step, replace rectifying with simple distillation.The N-vinyl acetamide that obtains contains the N-1 of 10ppm, 3-butadienyl ethanamide.According to embodiment 1 in identical mode measure the polymerizability of the product that obtains, found that its viscosity is 70cps.
The comparative example 2
Except the rectifying of omitting acetal according to embodiment 1 in identical mode produce N-vinyl carboxylic acid acid amides.The N-vinyl acetamide that obtains contains the N-1 of 230ppm, 3-butadienyl ethanamide.According to embodiment 1 in identical mode measure polymerizability, found that its viscosity is 10cps or lower.
Embodiment 12
It is that 20 packed column is N-(1-methoxy ethyl) ethanamide that the 6 evaporation residuums distillations of being made up of N-(1-methoxy ethyl) ethanamide in fact that will obtain in the acetal recycling step among the embodiment 2 obtain containing 11ppmN-(1,3-dimethoxy butyl) ethanamide with reflux ratio that use has theoretical plate number.Except in N-vinyl acetamide purification step, replacing the rectifying, with the synthesis step of N-(1-methoxy ethyl) ethanamide process that obtains as the N-vinyl acetamide of in embodiment 3, describing with simple distillation.The N-vinyl acetamide that obtains contains the N-1 of 9ppm, 3-butadienyl ethanamide.According to embodiment 1 in identical mode measure polymerizability, found that its viscosity is 80cps.
The comparative example 3
Except the rectifying of omitting N-(1-methylethyl) ethanamide, according to embodiment 9 in identical mode produce N-vinyl carboxylic acid acid amides.The N-vinyl acetamide that obtains contains the N-1 of 230ppm, 3-butadienyl ethanamide.According to embodiment 1 in identical mode measure polymerizability, found that its viscosity is 10cps or lower.
Embodiment 13
In the reaction vessel of glass, add 745 gram water; N-vinyl acetamide that 250 grams obtain in embodiment 2 and 0.409 gram are as the N of linking agent; N '-(diacetyl)-N, N '-(divinyl)-1,4-two (aminomethyl) hexanaphthene and with they the dissolving.Remove after the dissolved oxygen by nitrogen, add and be dissolved in 5 milliliters of 0.075 grams 2 in the water of sloughing oxygen, 2 '-azo, two 2-(2-tetrahydroglyoxaline-2-yl) propane dihydrochloride, mixture is adiabatic and place.After 7 hours,, reduce gradually owing to this internal temperature of thermosteresis then because the internal temperature in the heat of polymerization reaction vessel reaches 71 ℃.Be called " appearance time " from adding polymerization starter to the time cycle between the internal temperature of reaction vessel is the highest.In this embodiment, appearance time is 7 hours.
The comparative example 4
The N-vinyl acetamide that the N-vinyl acetamide that obtains in being used in comparative example 1 replaces obtaining in embodiment 2, according to embodiment 13 in identical mode carry out polymerization.Even do not observe the rising of the internal temperature that is accompanied by polymerization after 48 hours adding polymerization starter yet.
Embodiment 14
Add 745 gram water in the reaction vessel of glass, the N-vinyl acetamide that 225 grams obtain in embodiment 2 and 27.6 restrains sodium acrylates and they is dissolved.Remove after the dissolved oxygen by nitrogen, add and be dissolved in 5 milliliters of 0.075 grams 2 in the water of sloughing oxygen, 2 '-azo, two 2-(2-tetrahydroglyoxaline-2-yl) propane dihydrochloride, mixture is adiabatic and place.Appearance time is 6 hours.
The comparative example 5
Except the N-vinyl acetamide that replaces in embodiment 2, obtaining with the N-vinyl acetamide, according to embodiment 13 in identical mode carry out polymerization.Even do not observe the rising of the internal temperature that is accompanied by polymerization after 48 hours adding polymerization starter yet.
Embodiment 15
The solution that will have pH and be the ethanamide of 6.5 (with the determination of aqueous solution of 33wt%) and N-(1-methoxy ethyl) ethanamide that contains 98wt% and 2wt% adds with the quantity of per minute 35 grams that to have internal diameter be that 21 millimeters and total length are in 6 meters the stainless steel reaction pipe.Reaction tubes is heated to 400 ℃, and pressure is reduced to 100mmHg.To also reclaim by N-vinyl acetamide and methanol mixture condensation in the condenser that the outlet of reaction tubes is installed that heat scission reaction is produced.The N-vinyl acetamide contains the N-1 of 28ppm, 3-butadienyl ethanamide, and the transformation efficiency of N-(1-methoxy ethyl) ethanamide is 85%.
Have 10 grades glass Oldershaw type rectifying column in several the 10th grade, add the reaction soln that obtains with the quantity of 200 grams per hour.Pressure be under the 200mmHg with the heating of this post so that column top temperature remains on 40 ℃ and reflux ratio is 2.Rectifying column than lower part 500 ml flasks have been installed, it is immersed in the oil bath 80 ℃ of heating with the material in the quantity distilling flasks of 155 grams per hour.The solution that distills out from flask is the thick N-vinyl acetamide solution that contains the N-vinyl acetamide of 94wt%.Steam methyl alcohol from the top of post with the quantity of 45 grams per hour.
Have 10 grades glass Oldershaw type rectifying column on add the thick N-vinyl acetamide solution that obtains in several the 5th grade, be to carry out rectifying under 3 the condition in the decompression of 0.15mmHg and reflux ratio.The result obtains containing the N-1 of 0.9ppm, and 3-butadienyl ethanamide and purity are 98% N-vinyl acetamide.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, measure and find that its viscosity is 100cps.
Reference example 1
By the N-1 that contains 28ppm that distillation obtains from embodiment 15, the methanol solution of the N-vinyl acetamide of 3-butadienyl ethanamide is removed methyl alcohol.Concentrate after the N-vinyl acetamide, with temperature regulation to 50 ℃, in the high pressure crystal device with 1800kg/cm 2Separate mother liquor at 50 ℃.The result obtains containing the N-1 of 2ppm, and 3-butadienyl ethanamide and purity are 99.9% N-vinyl acetamide.According to embodiment 1 in identical mode measure the polymerizability of the N-vinyl acetamide that obtains, measure and find that its viscosity is 80cps.
Embodiment 16 to 19 and comparative example 6 to 9
N-(1-methoxy ethyl) ethanamide that contains the N-vinyl acetamide of various concentration except use is as the raw material, according to embodiment 15 in identical mode react.Reaction result, the N-1 afterwards that purifies, the content of 3-butadienyl ethanamide and the polymerizability of N-vinyl acetamide are listed in down in the tabulation 1 together.Table 1
N-vinyl acetamide (%) 33％ pH Transformation efficiency (%) N-butadienyl ethanamide (ppm) Polymerizability (cps)
Embodiment 16 ????3 ????6 ????85 ????2 ????80
Embodiment 17 ????5 ????7 ????84 ????6 ????50
Embodiment 18 ????7 ????8 ????86 ????10 ????30
Embodiment 19 ????1 ????5 ????86 ????10 ????35
The comparative example 6 ????1 ????4 ????87 ????50 ????8
The comparative example 7 ????3 ????4 ????87 ????400 ????5
The comparative example 8 ????11 ????8 ????86 ????40 ????5
The comparative example 9 ????13 ????8 ????86 ????50 ????5
By, for example, (1) dealcoholation of N-(1-alkoxyethyl) carboxylic acid amide, (2) dealcoholation of N-(1-alkoxyethyl) carboxylic acid amide that obtains from carboxylic acid amide, acetaldehyde and alcohol or from carboxylic acid amide and acetaldehyde dialkyl group acetal as intermediate, perhaps (3) obtain thick N-vinyl acetamide as intermediate from the ethylene carboxylic acid amide that acetaldehyde and carboxylic acid amide obtain by cracking ethylene carboxylic acid amide or by cracking.The thick N-vinyl acetamide that obtains by these known method of production does not have good polymerizability.But, as the N-1 in thick N-vinyl acetamide, 3-butadienyl carboxylic acid amide content is reduced to 30ppm or lower, preferred 10ppm or lower, more preferably 1ppm or when lower, then with crude ethylene yl carboxylic acid acid amides through purification processes, obtain having improvement polymerizability can height polymeric N-vinyl carboxylic acid acid amides.
And, by thick N-vinyl carboxylic acid acid amides or its solution being carried out purification processes such as rectificating method, recrystallization method, piezocrystallization method, using physical adsorption method, the diels-Alder reaction method or 1 of acticarbon, the selective hydrogenation method of 3-butadienyl is handled can be with N-1, and 3-butadienyl carboxylic acid amide is reduced to content range recited above.
And, according to the present invention, produce N-vinyl carboxylic acid acid amides by the thermo-cracking or the catalytic pyrolysis of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide, can obtain can height polymeric N-vinyl carboxylic acid acid amides.And, use this can height polymeric monomer can produce the polymkeric substance of high-molecular weight N-vinyl carboxylic acid acid amides.
The present invention is by being described in detail with reference to its specific embodiment, and obviously, those skilled in the art can carry out various variations and improvement and not break away from the spirit and scope of the invention the present invention.

Claims (12)

1. N-1,3-butadienyl carboxylic acid amide content be 30ppm or lower can height polymeric N-vinyl carboxylic acid acid amides.
2. the method that a production can height polymeric N-vinyl carboxylic acid acid amides, this method comprises the N-1 that is reduced in the thick N-vinyl carboxylic acid acid amides, 3-butadienyl carboxylic acid amide content is to 30ppm or lower.
According to the production of claim 2 can height polymeric N-vinyl carboxylic acid acid amides method, wherein N-vinyl carboxylic acid acid amides by N-(1-alkoxyethyl) carboxylic acid amide dealcoholation or by as intermediate from carboxylic acid amide, acetaldehyde and pure or from the contract dealcoholation production of N-(1-alkoxyethyl) carboxylic acid amide that dialkyl group alcohol obtains of carboxylic acid amide and acetaldehyde aldehyde.
According to the production of claim 2 can height polymeric N-vinyl carboxylic acid acid amides method, wherein N-vinyl carboxylic acid acid amides is by cracking ethylene carboxylic acid amide or by the ethylene carboxylic acid amide production that from acetaldehyde and carboxylic acid amide obtains of cracking as intermediate.
According to the production of claim 2 can height polymeric N-vinyl carboxylic acid acid amides method, wherein said reduction step comprises the method for selective hydrogenation that uses rectificating method, recrystallization method, piezocrystallization method, uses physical adsorption method, the diels-Alder reaction method of acticarbon or comprise the 1,3-butadiene base purify thick N-vinyl carboxylic acid acid amides or its solution.
6. the method for the multipolymer of a homopolymer of producing N-vinyl carboxylic acid acid amides or itself and another copolymerisable monomer, this method comprises that polymerization has N-1,3-butadienyl carboxylic acid amide content be 30ppm or lower can height polymeric N-vinyl carboxylic acid acid amides.
According to the production of claim 5 can height polymeric N-vinyl carboxylic acid acid amides method, wherein said purification comprises carries out N-1, the catalytic hydrogenation of 3-butadienyl carboxylic acid amide.
8. the method that a production can height polymeric N-vinyl carboxylic acid acid amides, this method comprises the thermo-cracking of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide or catalytic pyrolysis to produce N-vinyl carboxylic acid acid amides, and wherein the N-vinyl carboxylic acid amide content of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is 10wt% or lower.
9. the method that a production can height polymeric N-vinyl carboxylic acid acid amides, this method comprises the thermo-cracking or the catalytic pyrolysis of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide, and the 33wt% aqueous solution that wherein is used to produce N-(1-alkoxyethyl) carboxylic acid amide of N-vinyl carboxylic acid acid amides or ethylene carboxylic acid amide is adjusted to that to have pH be 5 to 10.
10. the method that a production can height polymeric N-vinyl carboxylic acid acid amides, this method comprises the thermo-cracking or the catalytic pyrolysis of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide, wherein the N-vinyl carboxylic acid amide content of N-(1-alkoxyethyl) carboxylic acid amide or ethylene carboxylic acid amide is that the 10wt% or the 33wt% aqueous solution lower and that be used to produce N-(1-alkoxyethyl) carboxylic acid amide of N-vinyl carboxylic acid acid amides or ethylene carboxylic acid amide are adjusted to that to have pH be 5 to 10.
11. have weight-average molecular weight and be 500000 or the homopolymer of bigger N-vinyl carboxylic acid acid amides or the multipolymer of N-vinyl carboxylic acid acid amides and another copolymerisable monomer, they have N-1 by polymerization, and 3-butadienyl carboxylic acid amide content is 30ppm or lower can preparing by height polymeric N-vinyl carboxylic acid acid amides.
12. according to the product of claim 11, it has weight-average molecular weight is 1000000 or more.
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