CA2224947A1 - Preparation of n-vinylcaprolactam polymers - Google Patents
Preparation of n-vinylcaprolactam polymers Download PDFInfo
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- CA2224947A1 CA2224947A1 CA002224947A CA2224947A CA2224947A1 CA 2224947 A1 CA2224947 A1 CA 2224947A1 CA 002224947 A CA002224947 A CA 002224947A CA 2224947 A CA2224947 A CA 2224947A CA 2224947 A1 CA2224947 A1 CA 2224947A1
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- 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
- C08F26/06—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 heterocyclic ring containing nitrogen
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Abstract
The invention provides a process for preparing polymers of N-vinylcaprolactam by polymerizing A) 40 - 100 % by weight of N-vinylcaprolactam and B) 0 - 60 % by weight of a further monoethylenically unsaturated monomer which is copolymerizable with N-vinylcaprolactam and also polymers prepared by this process.
Description
BASF AktiengesellschCA 02224947 1998-01-23 O.Z. OOSO/47693 Preparation of N-vinylcaprolactam polymers 5 The present invention relates to a process for preparing polymers of N-vinylcaprolactam, to polymers prepared by this process, and to their use.
DE 43 42 281 A1 discloses a process for preparing pulverulent 10 polymers based on N-vinylcaprolactam in which said monomer or the monomers is or are polymerized in aqueous medium or in CH30H, the CH30H - if used - being subsequently exchanged for H20. The preparation of a polymer which is free from organic solvents and is pulverulent after drying is necessary for the utility 15 envisaged by DE 43 42 281 Al, namely that of hair cosmetics.
Using the process disclosed in DE 43 42 281 Al, polymers with a low K value can be prepared only with molecular weight regulators.
20 The documents DE 24 56 807 C3, DE 25 14 127 B2 and DE 24 39 196 disclose processes for preparing polyvinylpyrrolidone, in which specific conditions, such as the use of coactivators, special techniques of addition, or particular pressures and/or residence times, are used to obtain polymers having low K values and a low 25 residual monomer content and meeting high requirements for pharmaceutical or cosmetic applications (free from impurities).
Wo 95/32 356 discloses additives for the control of clathrate hydrates in liquid systems. Additives employed are commercially 30 obtAin~hle polymers. Polyvinylcaprolactams are mentioned along with other polymers.
It is an object of the present invention to provide a process for 35 preparing polymers based on N-vinylcaprolactam which makes it possible to obtain polymers of low K value in high yields and with low levels of trace contaminants.
We have found that this object is achieved by the process 40 referred to at the outset for preparing polymers of N-vinylcaprolactam by polymerizing A) 40 - 100 % by weight of N-vinylcaprolactam and 45 B) 0 - 60 % by weight of another monoethylenically unsaturated monomer which can be copolymerized with N-vinylcaprolactam, which comprises polymerizing the monomers A and B in a solvent at from 100 to 200~C with a peroxide which at 95~C has a decomposition half-life of least 10 h.
5 Peroxides advantageously employed are dialkyl, diaryl or arylalkyl peroxide, monoalkyl hydroperoxides, dialkyl-diperoxoalkanes or peroxo esters.
lO It is preferred if the alkyl, aryl or arylalkyl groups of the peroxide have 1 to 8 carbons. The peroxides can also be in the form of mixtures. It i9 preferred to carry out polymerization at 110 - 160~C.
15 The temperatures are generally above the boiling point of the particular solvent used, BO as to give an autogenous pressure of more than 1 bar. It is also possible, however, to raise the pressure in the reaction zone by injecting nitrogen or another inert gas, for example. An upper-level for the pres~ure at which 20 polymerization i8 to be conducted cannot be given. The upper pressure limit is predetermined by the configuration of the particular apparatus used. It is usual to operate at pressures of from 2 to 20 bar, preferably from 3 to 10 bar.
25 Solvents preferably employed are ~olvents which have a good regulating action and readily transferable hydrogens, especially alcohols or ether alcohols. These solvents can also be used as a mixture with H2O.
30 Examples of solvents are:
methanol, ethanol, isopropanol, n-propanol, tertiary-butanol, n-butanol, secondary-butanol and higher straight-chain, branched 35 or cyclic monoalcohols; ethylene glycol, propylene glycol, glycerol and higher straight-chain, branched or cyclic diols, triols or polyfunctional alcohols; diethylene glycol, triethylene glycol, and higher homologs consisting of ethylene oxide and propylene oxide units; n-heY~ne, n-heptane, cycloheYAne, 40 isooctane and higher straight-chain, branched or cyclic AlkAnes;
benzene, toluene, ethylbenzene, xylene and higher alkylbenzenes;
phenol, cresol, resorcinol and higher mono- and difunctional (alkyl)benzenes; acetone, methyl ethyl ketone, acetophenone, cyclohexanone and higher straight-chain, branched or cyclic 45 aliphatic and aromatic ketones; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, dimethyl sulfoxide and other customary organic solvents. Also suitable in principle are natural or synthe~ic waxes, oils, fats and emulsifiers which are liquid under the polymerization conditions - both as solvents for the monomers and as a mixture with the above-listed organic solvents or with water.
5 Comonomers preferably employed are monomers of complete or limited solubility in water, for example:
acrylamide, acrylonitrile, methacrylonitrile, N,N-dimethylacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylacetamide, 10 N-vinylpropionamide, N-methyl-N-vinylacetamide, vinyl acetate, vinyl propionate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, vinylpyridine, N-vinyloxazolinone, vinylpyridine N-oxide, vinylimidazole, methylvinylimidazole, dimethylA inoethyl (meth)acrylate, 15 dimethylaminopropyl (meth)acrylate~ dimethylaminoethylacrylamide, dimethylaminopropylacrylamide. Particular preference is given to acrylamide and N-vinyl heterocycles, for example N-vinylpyrrolidone.
Less preferred are water-insoluble comonomers, for example:
20 branched or straight-chain C3-Cl8-alkyl (meth)acrylates, branched or straight-chain C4-Cl8-alkyl(meth)acryl~ i~es, branched or straight-chain C4-Cl8 carboxylic acid vinyl esters, and styrene.
25 Preferred free-radical polymerization initiators are:
di-tertiary-butyl peroxide, tertiary-butyl hydroperoxide, di-tertiary-amyl peroxide, tertiary-amyl hydroperoxide, dicumyl peroxide, tertiary-butyl cumyl peroxide, 2,2-di-tertiary-butylperoxybutane, t-butyl perbenzoate or 30 2,5-dimethylhexane-2,5-di-t-butyl peroxide. Di-tertiary-butyl peroxide is particularly advantageous. The concentration of initiator is in general from 0.1 to 30 % by weight, preferably from 0.5 to 15 % by weight and, with particular preference, from 1 to 10 % by weight, based on the monomers.
Although regulators are not necessary to achieve the object of the invention they can be employed in addition. Example~ of those suitable are:
formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and 40 isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate, hydroxylammonium phosphate, di-n-butyl sulfida, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, di-t-butyl trisulfide, n-butyl mercaptan, n-hexyl mercaptan, 45 n-dodecyl mercaptan, ethyl thioglycolate, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, diethanol sulfide, thiodiglycol, ethylthioethanol, thiourea, allyl alcohol, allyl bromide, benzyl chloride, chloroform and tetrachloromethane.
5 The reaction mixture may already include the entire amount of the free-radical polymerization initiator; however, an alternative possibility is to supply the polymerization initiator at various points in the reaction zone to the mixture that is to be polymerized.
The actual polymerization is conducted as follows: all of the components of the mixture can be included in the initial charge to a closed system, judiciously a pressure vessel tested to 15 20 bar, and the air contained in the solutions can be removed by evacuation or by blowing an inert gas through them. The temperature is then raised to 100 to 200~C, preferably 110 -160~C, and the mixture is polymerized for about 3 to 4 hours.
20 In a particularly preferred embodiment the monomer can be added successively during the polymerization, this making it possible to reduce the K value still further. This feed technique can also be realized by running in, in succe~sion, mixtures of monomer, solvent and peroxide. The duration of the feed can be from 1 to 25 5 hour5.
The novel process produces polymers having molar weights of from about 1000 to 50,000 ~Mw determined by light scattering)~ or K
values of from 8 to 30. K values of 8 to 20 are po~sible, in 30 particular, if the abovementioned measures relating to the metered addition are employed.
Continuous sampling and determination of residual vinylpyrrolidone make it easy to monitor the progress of the 35 polymerization. When the residual content of vinylpyrrolidone has fallen well below 0.1 %, the polymerization can be terminated.
Tbe postpolymerization time is in general from 5 to 15 hours.
40 The invention also relates to polymers of 40 - 100 % by weight of N-vinylcaprolactam and 0 - 60 % by weight of another monoethylenically unsaturated monomer which can be copolymerized with N-vinylcaprolactam, having a R value of from 8 to 30, prepared by the novel process.
~ CA 02224947 1998-01-23 Using the novel process it is possible with advantage to prepare polymers having a Mw of from 1000 to 2800 g/mol.
It has surprisingly been found that N-vinylcaprolactams, although 5 having an unstable ring system, can be polymerized by the novel process at 100 - 200~C, preferably from 110 to 160~C, with good results to form polymers having low K values, the yields being high and the content of trace impurities remaining low.
The polymers prepared in accordance with the invention can be used for a host of applications, for example:
Stripping and leveling assistants for textiles coloring, albumin 15 complexes, enrichment/separation of (noble) metals, antioxidant~
(complexes with), brighteners (textiles printing), recording media, concrete additives, binders for transfer printing, charge transfer cathodes, coating of polyolefins, coatings, disinfectants and preservatives, diazotypes, dispersing 20 auxiliaries, printing inks, noble metal crystallization nuclei for precipitating silver, electrically conducting layers, electrogels and skin adhesion gels, removal of polyvalent cations, removal of t~nni~/phenols, enzyme complexes and protein complexes, recovery of petroleum from oil-cont~ining water, 25 increasing the wettability of surfaces, coloring of polyolefins, color mixing inhibitors for photographic, diffusion transfer materials, color transfer inhibitors, solid batteries (for example lithium batteries), solid electrolytes, fish food granules, fixatives for perfume oils, flexographic printing 30 plates, flocculants, photographic processes, photo papers, gas analysis, plaster bandages, glass and glass fibers (binder, coating, lubricant)~ adhesion promoters for colorants, auxiliaries in the extraction of petroleum and natural gas and their transportation, assistants in the photographic industry, 35 hydrophilicization of surfaces, immunochemicals, or as an agent which releases the active principle in pharmaceutical preparations, inhibition of gas hydrates in natural gas extraction, ion exchangers, isomerization inhibitor~, jet inks, graphics inks and ballpoint pen pastes, catalysts, coating of 40 catheters, binders for ceramics, scale inhibitors or scale removers, adhesive for nutrient beds, adhesive base materials, adhesives and adhesive sticks, complexation with organic compounds, for increasing adsorbability/hydrophobicity, complexes with inorganic compounds, complexes with halogen, complexes with metals/ metal salts, complexes with polymers, pre~ervatives, contact lenses, corrosion protection, plastics additives, coatings auxiliaries, photosensitive materials, lithography, ., solubilizers, air filters, membrane preparation, metal casting and metal hardening, metal colloids (stabilization of), metal complexes for reverse oxygen absorption, metal quenching baths, microencapsulation, removal of oil and colorant from water, oil 5 recovery, paper assistants (specialty papers), colored paper slips, phase transfer catalysts, phenol complexes, photoimaging, pigment dispersions, proton conductors (water-free), wastewater cleaning compositions, rust inhibitors or removers of rust from metallic surfaces, seed dressing and seed coating, lubricant 10 additives, protective colloid, silver halide emulsions, slow-release fertilizer formulations, soil release, stabilization of peroxides, synthetic fibers, tannin complexes, tertiary petroleum recovery, textile auxiliaries, ink-jet recording media, separation of hydrocarbon mixtures, improved coloring of fibers, 15 thickeners or film-formers in hair lacquer, hairsetting or hairspray additives, in cosmetic skin preparations, heat-resistant layers, heat-sensitive layers, heat-sensitive resistors, detergent additives, water-soluble films and cigarette filters.
The invention is illustrated in more detail by the following examples. The K values were determined by the method of Fikentscher, Cellulose-Chemie 13, 58-64 and 71-74 (1932) in 5%
strength aqueous solutions at 20~C, where X=k-103. The molecular 25 weights given in the examples are weight averages and were measured using a small angle light scattering instrument KMX 6, 6-7~, 633 nm. The parts and percentages in the examples are by weight.
Example 1 First of all a first mixture (feed stream 1) was prepared from 1080 g of vinylcaprolactam, 120 g of acrylamide (as a 50%
35 strength solution in 120 g of H20) and 360 g of CH30H. In a reaction vessel, 165 g of feed stream 1, 8.0 g of di-tertiary-butyl peroxide (dtBP) and 450 g of CH30H were rendered inert by threefold injection of 3 bar of N2, and then O.S bar of N2 was injected. The initial charges were heated to 130~C ~nd the 40 remainder of feed stream l was metered in over ~ h. At the ~ame time, a feed stream 2 comprising 130 g of CH30H ~nd 8.0 g of dtBP
was metered in over 5 h. After the end of the feedJ, th- b-tch was postpolymerized at 130~C for one hour. Then a feed str-am 3 of 81 g of CH30H and 8.0 g of dtBP was added and th- m1~ture ~-~
45 postpolymerized at 130~C for 10 h. Then the reacto~ w-s cooled and let down and the polymer solution was removed.
The conditions of this example and of the correspondingly conducted Examples 2, 3, 4 and 5, and the properties of the resulting polymers, are given in Table 1 below.
BASF Aktiengesellschaft 961011 O.Z. 0050/47693 P.
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a ~ ~ o h h ~ ~ h C C
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o ~ o _ o ~ o ~ o O C~ o o o C~ o ~) o ~ o _I
a) Example 6 5 In a reaction vessel, 1800 g of CH30H and 150 g of dtBP were rendered inert by threefold injection of 3 bar of N2 and then were heated to 130~C. A mixture of 500 g of vinylpyrrolidone and 1500 g of vinylcaprolactam and a second mixture of 200 g of CH30H and 100 g of dtBP were metered in over 4 h; the mixture was then 10 postpolymerized at 130~C for 10 h. The vessel was then cooled and let down and the polymer solution was removed.
The conditions of this example and of the correspondingly conducted Examples 7, 8, 9 and 10, and the properties of the 15 resulting polymers, are given in Table 2 below.
BASF AXtiengesellschaft 961011 O.Z. 0050/47693 _I
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Example 11 First of all a mixture (feed stream 1) was prepared from 2500 g of vinylcaprolactam and 400 g of CH30H.
In a reaction vessel, 400 g of feed stream 1, 1900 g of CH30H and 170 g of dtBP were rendered inert by threefold injection of N2, 10 and then 0.5 bar of N2 was injected. This initial charge was heated to 130~C, and the re ?inAer of feed stream 1 was metered in over 2 h and a feed stream 3 of 250 g of CH30H and 80 g of dtBP
was metered in over 4 h. After the end of the feeds, the mixture was po~tpolymerized at 130~C for 10 h and worked up as in 15 EXample 1.
The conditions of this example and of the correspondingly conducted Examples 12 - 16 are given in Table 3 below.
BASF Aktiengesellschaft 961011 O.Z. 0050/47693 ~4 _I
a --o o ~n ~ o ~ o o o o -- ~ ~ ~ V V V
fi.
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1 3 ~ ~ ~ o C ~ o o _I _I _I _I
C C C C
~ t ~ _~
C C~ C~ o4 '~ ~4 4 _l ~ ~ O
o a~
a C C
~J ~ U U ~- ~--- -- _I ~ O O
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DE 43 42 281 A1 discloses a process for preparing pulverulent 10 polymers based on N-vinylcaprolactam in which said monomer or the monomers is or are polymerized in aqueous medium or in CH30H, the CH30H - if used - being subsequently exchanged for H20. The preparation of a polymer which is free from organic solvents and is pulverulent after drying is necessary for the utility 15 envisaged by DE 43 42 281 Al, namely that of hair cosmetics.
Using the process disclosed in DE 43 42 281 Al, polymers with a low K value can be prepared only with molecular weight regulators.
20 The documents DE 24 56 807 C3, DE 25 14 127 B2 and DE 24 39 196 disclose processes for preparing polyvinylpyrrolidone, in which specific conditions, such as the use of coactivators, special techniques of addition, or particular pressures and/or residence times, are used to obtain polymers having low K values and a low 25 residual monomer content and meeting high requirements for pharmaceutical or cosmetic applications (free from impurities).
Wo 95/32 356 discloses additives for the control of clathrate hydrates in liquid systems. Additives employed are commercially 30 obtAin~hle polymers. Polyvinylcaprolactams are mentioned along with other polymers.
It is an object of the present invention to provide a process for 35 preparing polymers based on N-vinylcaprolactam which makes it possible to obtain polymers of low K value in high yields and with low levels of trace contaminants.
We have found that this object is achieved by the process 40 referred to at the outset for preparing polymers of N-vinylcaprolactam by polymerizing A) 40 - 100 % by weight of N-vinylcaprolactam and 45 B) 0 - 60 % by weight of another monoethylenically unsaturated monomer which can be copolymerized with N-vinylcaprolactam, which comprises polymerizing the monomers A and B in a solvent at from 100 to 200~C with a peroxide which at 95~C has a decomposition half-life of least 10 h.
5 Peroxides advantageously employed are dialkyl, diaryl or arylalkyl peroxide, monoalkyl hydroperoxides, dialkyl-diperoxoalkanes or peroxo esters.
lO It is preferred if the alkyl, aryl or arylalkyl groups of the peroxide have 1 to 8 carbons. The peroxides can also be in the form of mixtures. It i9 preferred to carry out polymerization at 110 - 160~C.
15 The temperatures are generally above the boiling point of the particular solvent used, BO as to give an autogenous pressure of more than 1 bar. It is also possible, however, to raise the pressure in the reaction zone by injecting nitrogen or another inert gas, for example. An upper-level for the pres~ure at which 20 polymerization i8 to be conducted cannot be given. The upper pressure limit is predetermined by the configuration of the particular apparatus used. It is usual to operate at pressures of from 2 to 20 bar, preferably from 3 to 10 bar.
25 Solvents preferably employed are ~olvents which have a good regulating action and readily transferable hydrogens, especially alcohols or ether alcohols. These solvents can also be used as a mixture with H2O.
30 Examples of solvents are:
methanol, ethanol, isopropanol, n-propanol, tertiary-butanol, n-butanol, secondary-butanol and higher straight-chain, branched 35 or cyclic monoalcohols; ethylene glycol, propylene glycol, glycerol and higher straight-chain, branched or cyclic diols, triols or polyfunctional alcohols; diethylene glycol, triethylene glycol, and higher homologs consisting of ethylene oxide and propylene oxide units; n-heY~ne, n-heptane, cycloheYAne, 40 isooctane and higher straight-chain, branched or cyclic AlkAnes;
benzene, toluene, ethylbenzene, xylene and higher alkylbenzenes;
phenol, cresol, resorcinol and higher mono- and difunctional (alkyl)benzenes; acetone, methyl ethyl ketone, acetophenone, cyclohexanone and higher straight-chain, branched or cyclic 45 aliphatic and aromatic ketones; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, dimethyl sulfoxide and other customary organic solvents. Also suitable in principle are natural or synthe~ic waxes, oils, fats and emulsifiers which are liquid under the polymerization conditions - both as solvents for the monomers and as a mixture with the above-listed organic solvents or with water.
5 Comonomers preferably employed are monomers of complete or limited solubility in water, for example:
acrylamide, acrylonitrile, methacrylonitrile, N,N-dimethylacrylamide, N-isopropylacrylamide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylacetamide, 10 N-vinylpropionamide, N-methyl-N-vinylacetamide, vinyl acetate, vinyl propionate, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, vinylpyridine, N-vinyloxazolinone, vinylpyridine N-oxide, vinylimidazole, methylvinylimidazole, dimethylA inoethyl (meth)acrylate, 15 dimethylaminopropyl (meth)acrylate~ dimethylaminoethylacrylamide, dimethylaminopropylacrylamide. Particular preference is given to acrylamide and N-vinyl heterocycles, for example N-vinylpyrrolidone.
Less preferred are water-insoluble comonomers, for example:
20 branched or straight-chain C3-Cl8-alkyl (meth)acrylates, branched or straight-chain C4-Cl8-alkyl(meth)acryl~ i~es, branched or straight-chain C4-Cl8 carboxylic acid vinyl esters, and styrene.
25 Preferred free-radical polymerization initiators are:
di-tertiary-butyl peroxide, tertiary-butyl hydroperoxide, di-tertiary-amyl peroxide, tertiary-amyl hydroperoxide, dicumyl peroxide, tertiary-butyl cumyl peroxide, 2,2-di-tertiary-butylperoxybutane, t-butyl perbenzoate or 30 2,5-dimethylhexane-2,5-di-t-butyl peroxide. Di-tertiary-butyl peroxide is particularly advantageous. The concentration of initiator is in general from 0.1 to 30 % by weight, preferably from 0.5 to 15 % by weight and, with particular preference, from 1 to 10 % by weight, based on the monomers.
Although regulators are not necessary to achieve the object of the invention they can be employed in addition. Example~ of those suitable are:
formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and 40 isobutyraldehyde, formic acid, ammonium formate, hydroxylammonium sulfate, hydroxylammonium phosphate, di-n-butyl sulfida, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, di-t-butyl trisulfide, n-butyl mercaptan, n-hexyl mercaptan, 45 n-dodecyl mercaptan, ethyl thioglycolate, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, diethanol sulfide, thiodiglycol, ethylthioethanol, thiourea, allyl alcohol, allyl bromide, benzyl chloride, chloroform and tetrachloromethane.
5 The reaction mixture may already include the entire amount of the free-radical polymerization initiator; however, an alternative possibility is to supply the polymerization initiator at various points in the reaction zone to the mixture that is to be polymerized.
The actual polymerization is conducted as follows: all of the components of the mixture can be included in the initial charge to a closed system, judiciously a pressure vessel tested to 15 20 bar, and the air contained in the solutions can be removed by evacuation or by blowing an inert gas through them. The temperature is then raised to 100 to 200~C, preferably 110 -160~C, and the mixture is polymerized for about 3 to 4 hours.
20 In a particularly preferred embodiment the monomer can be added successively during the polymerization, this making it possible to reduce the K value still further. This feed technique can also be realized by running in, in succe~sion, mixtures of monomer, solvent and peroxide. The duration of the feed can be from 1 to 25 5 hour5.
The novel process produces polymers having molar weights of from about 1000 to 50,000 ~Mw determined by light scattering)~ or K
values of from 8 to 30. K values of 8 to 20 are po~sible, in 30 particular, if the abovementioned measures relating to the metered addition are employed.
Continuous sampling and determination of residual vinylpyrrolidone make it easy to monitor the progress of the 35 polymerization. When the residual content of vinylpyrrolidone has fallen well below 0.1 %, the polymerization can be terminated.
Tbe postpolymerization time is in general from 5 to 15 hours.
40 The invention also relates to polymers of 40 - 100 % by weight of N-vinylcaprolactam and 0 - 60 % by weight of another monoethylenically unsaturated monomer which can be copolymerized with N-vinylcaprolactam, having a R value of from 8 to 30, prepared by the novel process.
~ CA 02224947 1998-01-23 Using the novel process it is possible with advantage to prepare polymers having a Mw of from 1000 to 2800 g/mol.
It has surprisingly been found that N-vinylcaprolactams, although 5 having an unstable ring system, can be polymerized by the novel process at 100 - 200~C, preferably from 110 to 160~C, with good results to form polymers having low K values, the yields being high and the content of trace impurities remaining low.
The polymers prepared in accordance with the invention can be used for a host of applications, for example:
Stripping and leveling assistants for textiles coloring, albumin 15 complexes, enrichment/separation of (noble) metals, antioxidant~
(complexes with), brighteners (textiles printing), recording media, concrete additives, binders for transfer printing, charge transfer cathodes, coating of polyolefins, coatings, disinfectants and preservatives, diazotypes, dispersing 20 auxiliaries, printing inks, noble metal crystallization nuclei for precipitating silver, electrically conducting layers, electrogels and skin adhesion gels, removal of polyvalent cations, removal of t~nni~/phenols, enzyme complexes and protein complexes, recovery of petroleum from oil-cont~ining water, 25 increasing the wettability of surfaces, coloring of polyolefins, color mixing inhibitors for photographic, diffusion transfer materials, color transfer inhibitors, solid batteries (for example lithium batteries), solid electrolytes, fish food granules, fixatives for perfume oils, flexographic printing 30 plates, flocculants, photographic processes, photo papers, gas analysis, plaster bandages, glass and glass fibers (binder, coating, lubricant)~ adhesion promoters for colorants, auxiliaries in the extraction of petroleum and natural gas and their transportation, assistants in the photographic industry, 35 hydrophilicization of surfaces, immunochemicals, or as an agent which releases the active principle in pharmaceutical preparations, inhibition of gas hydrates in natural gas extraction, ion exchangers, isomerization inhibitor~, jet inks, graphics inks and ballpoint pen pastes, catalysts, coating of 40 catheters, binders for ceramics, scale inhibitors or scale removers, adhesive for nutrient beds, adhesive base materials, adhesives and adhesive sticks, complexation with organic compounds, for increasing adsorbability/hydrophobicity, complexes with inorganic compounds, complexes with halogen, complexes with metals/ metal salts, complexes with polymers, pre~ervatives, contact lenses, corrosion protection, plastics additives, coatings auxiliaries, photosensitive materials, lithography, ., solubilizers, air filters, membrane preparation, metal casting and metal hardening, metal colloids (stabilization of), metal complexes for reverse oxygen absorption, metal quenching baths, microencapsulation, removal of oil and colorant from water, oil 5 recovery, paper assistants (specialty papers), colored paper slips, phase transfer catalysts, phenol complexes, photoimaging, pigment dispersions, proton conductors (water-free), wastewater cleaning compositions, rust inhibitors or removers of rust from metallic surfaces, seed dressing and seed coating, lubricant 10 additives, protective colloid, silver halide emulsions, slow-release fertilizer formulations, soil release, stabilization of peroxides, synthetic fibers, tannin complexes, tertiary petroleum recovery, textile auxiliaries, ink-jet recording media, separation of hydrocarbon mixtures, improved coloring of fibers, 15 thickeners or film-formers in hair lacquer, hairsetting or hairspray additives, in cosmetic skin preparations, heat-resistant layers, heat-sensitive layers, heat-sensitive resistors, detergent additives, water-soluble films and cigarette filters.
The invention is illustrated in more detail by the following examples. The K values were determined by the method of Fikentscher, Cellulose-Chemie 13, 58-64 and 71-74 (1932) in 5%
strength aqueous solutions at 20~C, where X=k-103. The molecular 25 weights given in the examples are weight averages and were measured using a small angle light scattering instrument KMX 6, 6-7~, 633 nm. The parts and percentages in the examples are by weight.
Example 1 First of all a first mixture (feed stream 1) was prepared from 1080 g of vinylcaprolactam, 120 g of acrylamide (as a 50%
35 strength solution in 120 g of H20) and 360 g of CH30H. In a reaction vessel, 165 g of feed stream 1, 8.0 g of di-tertiary-butyl peroxide (dtBP) and 450 g of CH30H were rendered inert by threefold injection of 3 bar of N2, and then O.S bar of N2 was injected. The initial charges were heated to 130~C ~nd the 40 remainder of feed stream l was metered in over ~ h. At the ~ame time, a feed stream 2 comprising 130 g of CH30H ~nd 8.0 g of dtBP
was metered in over 5 h. After the end of the feedJ, th- b-tch was postpolymerized at 130~C for one hour. Then a feed str-am 3 of 81 g of CH30H and 8.0 g of dtBP was added and th- m1~ture ~-~
45 postpolymerized at 130~C for 10 h. Then the reacto~ w-s cooled and let down and the polymer solution was removed.
The conditions of this example and of the correspondingly conducted Examples 2, 3, 4 and 5, and the properties of the resulting polymers, are given in Table 1 below.
BASF Aktiengesellschaft 961011 O.Z. 0050/47693 P.
.~ ~ o o o o o o o ~ ~ ~ ~ u~ ~ o a!,-- ~ N ~r a) X
~ ~~
d~ C
~ O
L
o c a ~ u~
C-, ~ h ~ ~ a Q - ~ ~ ~ ~ ~ ~
O ~ ~ ~ ~ o 3 C ~ ~ ~ o r~ ~ O O O
C C C C
~ J ~ ~ ~ ~
_I ., .
o ~ ~ ~ ~ ~
C C
~ 'C
a ~ ~ o h h ~ ~ h C C
h ~ ~ U ~~ ~~
o ~ o _ o ~ o ~ o O C~ o o o C~ o ~) o ~ o _I
a) Example 6 5 In a reaction vessel, 1800 g of CH30H and 150 g of dtBP were rendered inert by threefold injection of 3 bar of N2 and then were heated to 130~C. A mixture of 500 g of vinylpyrrolidone and 1500 g of vinylcaprolactam and a second mixture of 200 g of CH30H and 100 g of dtBP were metered in over 4 h; the mixture was then 10 postpolymerized at 130~C for 10 h. The vessel was then cooled and let down and the polymer solution was removed.
The conditions of this example and of the correspondingly conducted Examples 7, 8, 9 and 10, and the properties of the 15 resulting polymers, are given in Table 2 below.
BASF AXtiengesellschaft 961011 O.Z. 0050/47693 _I
_l Ei o o ~q ~ o o_~ o ~ o ~ ~ ~ ~ -~ _I o ~ u.
.. . . . . .
r ~ ~ ~ ~ ~ ~
-- 3 --~ --IN ~ _~
~O~ r S ~ ~ .C J~
O tD JU~ ~UQ) J J
r cr~ r c' O C
~ ~ ~ ~ ~ J
., .,., .,., ~~
~ O G O ~1 _I
~ * ~ D.C4 ~0 ~0 r~ r~ ~ r~
o o ~ u~ ~ o --o o o o ~ o c~ o ~ --~
~ .. ..
Q o *
Example 11 First of all a mixture (feed stream 1) was prepared from 2500 g of vinylcaprolactam and 400 g of CH30H.
In a reaction vessel, 400 g of feed stream 1, 1900 g of CH30H and 170 g of dtBP were rendered inert by threefold injection of N2, 10 and then 0.5 bar of N2 was injected. This initial charge was heated to 130~C, and the re ?inAer of feed stream 1 was metered in over 2 h and a feed stream 3 of 250 g of CH30H and 80 g of dtBP
was metered in over 4 h. After the end of the feeds, the mixture was po~tpolymerized at 130~C for 10 h and worked up as in 15 EXample 1.
The conditions of this example and of the correspondingly conducted Examples 12 - 16 are given in Table 3 below.
BASF Aktiengesellschaft 961011 O.Z. 0050/47693 ~4 _I
a --o o ~n ~ o ~ o o o o -- ~ ~ ~ V V V
fi.
O a7 ~ ~ N _I
~ ~ ~ ~ ~ -~ --r .
1 3 ~ ~ ~ o C ~ o o _I _I _I _I
C C C C
~ t ~ _~
C C~ C~ o4 '~ ~4 4 _l ~ ~ O
o a~
a C C
~J ~ U U ~- ~--- -- _I ~ O O
O C~ O O L
~4 C4 U U U --I --I
~ . ~ C C
C ~ C C ~~
~ o ~ o _I _I _I ~ _I ~a ~- ~a ~-o o o o o u o c~o - l e~
Claims (9)
1. A process for preparing polymers of N-vinylcaprolactam by polymerizing A) 40 - 100 % by weight of N-vinylcaprolactam and B) 0 - 60 % by weight of another monoethylenically unsaturated monomer which can be copolymerized with N-vinylcaprolactam which comprises polymerizing monomers A and B in a solvent at from 100 bis 200°C in a peroxide which at 95°C has a decomposition half-life of at least 10 h.
2. A process as claimed in claim 1, wherein the peroxide employed is a dialkyl, diaryl or arylalkyl peroxide, monoalkyl hydroperoxide, dialkyldiperoxoalkane or peroxo ester.
3. A process as claimed in claim 1, wherein the alkyl, aryl or arylalkyl groups of the peroxide have from 1 to 8 carbons.
4. A process as claimed in claim 1, wherein polymerization is conducted at 110 - 160°C.
5. A process as claimed in claim 1, wherein the solvent employed comprises strongly regulating solvents having readily transferable hydrogens.
6. A process as claimed in claim 1, wherein the comonomer employed is an N-vinylheterocycle or acrylamide.
7. A process as claimed in claim 4, wherein the solvent employed is an alcohol or ether alcohol.
8. A process as claimed in claim 6, wherein the solvents employed are isopropanol, methanol and ethylene glycol.
9. A polymer of 40 - 100 % by weight of N-vinylcaprolactam and 0 - 60 % by weight of another monoethylenically unsaturated monomer which can be copolymerized with N-vinylcaprolactam, having a K value of from 8 to 30, prepared by a process as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19702476.9 | 1997-01-24 | ||
| DE19702476A DE19702476A1 (en) | 1997-01-24 | 1997-01-24 | Process for the preparation of polymers of N-vinylcaprolactam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2224947A1 true CA2224947A1 (en) | 1998-07-24 |
Family
ID=7818249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002224947A Abandoned CA2224947A1 (en) | 1997-01-24 | 1998-01-23 | Preparation of n-vinylcaprolactam polymers |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0855412A3 (en) |
| JP (1) | JPH10212321A (en) |
| AU (1) | AU5273898A (en) |
| CA (1) | CA2224947A1 (en) |
| DE (1) | DE19702476A1 (en) |
| ID (1) | ID19748A (en) |
| NO (1) | NO980316L (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10913813B2 (en) * | 2017-12-29 | 2021-02-09 | Guangzhou Institute Of Energy Conversion, Chinese Academy Of Sciences | Vinylamide block copolymer kinetic hydrate inhibitor and preparation method and use thereof |
| US11629512B2 (en) | 2017-02-03 | 2023-04-18 | Xylo Technologies Ag | Heat-treated PVC-plastic panel |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA111997C2 (en) * | 2012-04-02 | 2016-07-11 | Кроноплюс Текнікал Аг | PANEL WITH COVER DIRECTED BY DIRECT PRINTING METHOD |
| UA111803C2 (en) | 2012-10-05 | 2016-06-10 | Кроноплюс Текнікал Аг | FLOOR PANEL FOR EXTERNAL APPLICATION |
| CN109705246B (en) * | 2018-12-14 | 2020-05-05 | 中国科学院广州能源研究所 | Hydrate kinetic inhibitor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3642633A1 (en) * | 1986-12-13 | 1988-06-23 | Basf Ag | METHOD FOR PRODUCING VINYLPYRROLIDONE POLYMERISATS |
| US5130388A (en) * | 1991-05-06 | 1992-07-14 | Isp Investments Inc. | Precipitation polymerization process |
| DE4342281A1 (en) * | 1993-12-11 | 1995-06-14 | Basf Ag | Process for the preparation of powdery polymers based on N-vinylcaprolactam |
-
1997
- 1997-01-24 DE DE19702476A patent/DE19702476A1/en not_active Withdrawn
-
1998
- 1998-01-13 EP EP98100438A patent/EP0855412A3/en not_active Withdrawn
- 1998-01-22 ID IDP980082A patent/ID19748A/en unknown
- 1998-01-23 NO NO980316A patent/NO980316L/en not_active Application Discontinuation
- 1998-01-23 CA CA002224947A patent/CA2224947A1/en not_active Abandoned
- 1998-01-23 AU AU52738/98A patent/AU5273898A/en not_active Abandoned
- 1998-01-23 JP JP10011139A patent/JPH10212321A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11629512B2 (en) | 2017-02-03 | 2023-04-18 | Xylo Technologies Ag | Heat-treated PVC-plastic panel |
| US11629513B2 (en) | 2017-02-03 | 2023-04-18 | Xylo Technologies Ag | Heat-treated PVC-plastic panel |
| US11629511B2 (en) | 2017-02-03 | 2023-04-18 | Xylo Technologies Ag | Heat-treated PVC-plastic panel |
| US11629510B2 (en) | 2017-02-03 | 2023-04-18 | Xylo Technologies Ag | Heat-treated PVC-plastic panel |
| US10913813B2 (en) * | 2017-12-29 | 2021-02-09 | Guangzhou Institute Of Energy Conversion, Chinese Academy Of Sciences | Vinylamide block copolymer kinetic hydrate inhibitor and preparation method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19702476A1 (en) | 1998-07-30 |
| EP0855412A2 (en) | 1998-07-29 |
| AU5273898A (en) | 1998-07-30 |
| EP0855412A3 (en) | 1999-08-18 |
| NO980316L (en) | 1998-07-27 |
| NO980316D0 (en) | 1998-01-23 |
| ID19748A (en) | 1998-07-30 |
| JPH10212321A (en) | 1998-08-11 |
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