CA2156502A1 - Homopolymers and copolymers of 1-vinylimidazole, method of producing them and their use - Google Patents
Homopolymers and copolymers of 1-vinylimidazole, method of producing them and their useInfo
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- CA2156502A1 CA2156502A1 CA002156502A CA2156502A CA2156502A1 CA 2156502 A1 CA2156502 A1 CA 2156502A1 CA 002156502 A CA002156502 A CA 002156502A CA 2156502 A CA2156502 A CA 2156502A CA 2156502 A1 CA2156502 A1 CA 2156502A1
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- vinylimidazole
- polymerization
- water
- mixture
- vinylpyrrolidone
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Detergent Compositions (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention concerns homopolymers and copolymers of 1-vinylimidazole and a method of producing low-molecular-weight homopolymers of 1-vinylimidazole and copolymers of 1-vinylimidazole and 1-vinylpyrrolidone by the radical-mechanism polymerization of 1-vinylimidazole or mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in C1 to C4 alcohol, water or a mixture of water and at least one C1 to C4 alcohol in the presence ofpolymerization regulators containing bound sulphur. Obtained are solutions of low-molecular-weight polymers which are low in residual monomers. The invention also concerns the use of these polymers as dye-transfer inhibiters in washing products.
Description
- BASF Aktiengesellschaf~ o.z. 0050/44033 2~56~02 Homo- and copolymers of l-vinylimidazole, the preparation and use thereof 5 The present invention relates to homo- and copolymers of 1-vinyl-imidazole, to a process for preparing low molecular weight poly-mers of l-vinylimidazole by free-radical polymerization of 1-vinylimidazole or of mixtures of l-vinylimidazole and l-vinyl-pyrrolidone in C1-C4-alcohols, water or mixtures of water and at 10 least one C1-C4-alcohol and to the use of the polymers in deter-gents.
The preparation of homopolymers of l-vinylimidazole and of co-polymers of 1-vinylimidazole and 1-vinylpyrrolidone by polymer-15 ization of the monomers in bulk or in solvents is known, cf.DE-A-2 814 287. The polymers of l-vinylimidazole described in the literature still contain relatively large amounts of unpolymer-ized vinylimidazole so that the polymers have a very unpleasant odor which is perceptible even at high dilution. In order to iso-20 late and purify the polymers after their preparation they aresubjected to an elaborate precipitation operation which is im-practical on the industrial scale.
It is an object of the present invention to provide novel sub-25 stances and an industrially straightforward process for preparing low molecular weight homopolymers, with a low residual monomer content, of l-vinylimidazole and copolymers of l-vinylimidazole and l-vinylpyrrolidone.
30 We have found that this object is achieved according to the in-vention by homopolymers of l-vinylimidazole and copolymers of 1-vinylimidazole and l-vinylpyrrolidone when they each contain sulfur in bound form and have a K value of from lO to 40 (deter-mined by the method of H. Fikentscher in 0.1 N aqueous sodium 35 chloride solution at 25 C with a polymer concentration of 1% by weight).
The said homopolymers of 1-vinylimidazole and the copolymers of 1-vinylimidazole and 1-vinylpyrrolidone are moreover obtainable 40 by free-radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in Cl-C4-alcohols, water or mixtures of water and at least one C1-C4-alcohol in the presence of polymerization regulators which contain sulfur in bound form.
BASF Aktiengesellschaf~ 2 15 6 5 0 2 .Z. 0050/44033 _- 2 The present invention moreover relates to a process for preparing low molecular weight polymers of l-vinylimidazole by free-radical polymerization of l-vinylimidazole or of mixtures of l-vinylimid-azole and l-vinylpyrrolidone in Cl-C4-alcohols, water or mixtures 5 of water and at least one Cl-C4-alcohol, the polymerization being carried out in the presence of polymerization regulators which contain sulfur in bound form. Polymerization regulators which are preferably employed are mercapto compounds, dialkyl sulfides, dialkyl disulfides and/or diaryl sulfides.
The homo- and copolymers described above are used as color trans-fer inhibitors in detergents.
The process according to the invention is used to prepare low 15 molecular weight homopolymers and copolymers of l-vinylimidazole and l-vinylpyrrolidone. The homo- and copolymers have K values of 10 - 40, preferably 13 - 30 (determined by the method of H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25 C
with a polymer concentration of 1% by weight). The polymerization 20 of the monomers normally takes place under an atmosphere of inert gas, eg. nitrogen, argon or helium. Care is generally taken that the reactants are thoroughly mixed during the polymerization. The polymerization is carried out in Cl-C4-alcohols, water or mixtures of water and at least one Cl-C4-alcohol. The solvent preferably 25 used is water or mixtures of water and at least one Cl-C4-alcohol in any desired ratio. Suitable alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and isobutanol.
Isopropanol is preferably employed.
30 For the preparation of copolymers of l-vinylimidazole and l-vinylpyrrolidone it is possible to employ the monomers in any desired ratio in the copolymerization. The monomer mixtures employed in the copolymerization preferably contain from 5 to 99.9% by weight of l-vinylimidazole and from 0.1 to 95% by weight 35 of l-vinylpyrrolidone. The polymerization is preferably carried out in the range from 50 to 100 C. If the polymerization is car-ried out at higher temperatures, eg. at up to 150 C, it is carried out in apparatus which is closed pressure-tight.
40 The monomers undergo free-radical polymerization, ie. it is nec-essary to initiate the homo- and copolymerization with compounds which form free radicals under the polymerization conditions.
Such initiators which form free radicals are all conventional peroxy and azo compounds, for example peroxides, hydroperoxides 45 and peroxy esters, such as hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxypiva-late and t-butyl peroxy-2-ethylhexanoate as well as azo compounds ~ BASF Aktiengesellschaf~ 215 6 5 0 2 - Z 0050/44033 such as 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azo-bis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis-isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and dimethyl 2,2'-azobis(2-methylpropionate). It is also, of course, possible 5 to use mixtures of initiators or the known redox initiators. The initiators are employed in conventional quantities, eg. in quan-tities of from 0.3 to 6% of the weight of the monomers to be polymerized. Where the polymerization is carried out in water or in mixtures of water and at least one of the abovementioned alco-10 hols as solvent, water-soluble azo initiators are preferably used.
The polymerization is carried out according to the invention in the presence of polymerization regulators which contain sulfur in 15 bound form. Examples of compounds of this type are inorganic bi-sulfites, disulfites and dithionites or organic sulfides, disul-fides, polysulfides, sulfoxides, sulfones and mercapto compounds.
The following polymerization regulators are mentioned by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sul-20 fide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, 2,2'-dithiodiethanol, di-t-butyl trisulfide and dimethyl sulfox-ide. The compounds preferably employed as polymerization regula-tors are mercapto compounds, dialkyl sulfides, dialkyl disulfides 25 and/or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercapto-1,2-propanediol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglyc-erol, thioacetic acid, thiourea and alkyl mercaptans such as 30 n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan. Po-lymerization regulators which are particularly preferably employed are mercapto alcohols and mercapto carboxylic acids. The polymerization regulators which contain sulfur in bound form are used in amounts of from 0.1 to 15, preferably O.S to 10, % of the 35 weight of the monomers employed in the polymerization. It is, of course, also possible to use mixtures of the polymerization regu-lators according to the invention in the polymerization.
The monomers can be polymerized by the conventional processes, 40 eg. by batch polymerization in which either l-vinylimidazole or mixtures of l-vinylimidazole and l-vinylpyrrolidone, regulator and initiator are introduced into a solvent and heated to the polymerization temperature. The mixture is stirred at the poly-merization temperature until the conversion is more than 99.9%.
45 In this process it is also possible where appropriate to add the initiator only after the polymerization temperature is reached.
BASF Aktiengesellschaf~ 21~ 6 5 0 2 Z. 0050/44033 other variants of the polymerization process are the addition methods, which are preferably employed. In these variants, a solution of the polymerization regulator which contains sulfur in bound form, and an initiator solution are added, continuously or 5 in portions, to a mixture of vinylimidazole, or a mixture of vinylimidazole and vinylpyrrolidone, and a solvent at the poly-merization temperature within a defined time. However, it is also possible to meter a mixture of regulator and initiator into the initial mixture at the polymerization temperature. Another method 10 comprises adding the initiator below or at the polymerization temperature to the initial mixture and introducing within a pre-set time only the regulator or a solution of the regulator into the reaction mixture after the polymerization temperature is reached. Another variant of the addition technique comprises 15 heating the initial mixture to a temperature at which polymeriza-tion takes place and then adding regulator, initiator and mono-mers separately or together. With this technique the initial mix-ture preferably comprises water or a mixture of water, monomer andtor initiator and/or regulator. A procedure which is particu-20 larly preferred according to the invention is one in which thepolymerization regulators cont~; n; ng sulfur in bound form are metered in continuously or in portions during the polymerization.
The weight average molecular weight Mw of the homo- and copolymers 25 of 1-vinylimidazole prepared in this way is in the range from 2 000 to 50 000, preferably 5 000 to 40 000. These polymers have K values of from 10 to 40 (determined by the method of H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25 C
with a polymer concentration of 1% by weight). The concentration 30 of the monomers in the aqueous medium is normally from 10 to 50 and is preferably in the range from 20 to 45% by weight. The solutions resulting from the polymerization can be subjected after the polymerization process to a physical or chemical de-odorization. This means, inter alia, a subsequent treatment of 35 the polymer solution by steam distillation, where volatile im-purities are removed from the solution with steam, or nitrogen stripping. For a subsequent chemical treatment, polymerization initiators or mixtures of a plurality of polymerization initia-tors are added and the polymer solution is heated where appropri-40 ate to temperatures above the polymerization temperature.
The process according to the invention results in polymer solu-tions which have a low residual monomer content and which can be directly marketed. Polymer solutions of this type are used, for 45 example, as additives to detergents. Their effect is, when colored and white textiles are washed, to inhibit transfer of color to the uncolored textiles. Detergents of this type contain, ~ BASF Aktiengesellschaf~ 21 S 6 5 0 2 .Z. 0050/44033 S
for example, from 0.1 to 10, preferably 0.2 to 3, % by weight of homopolymers of l-vinylimidazole or of copolymers of l-vinylimid-azole and l-vinylpyrrolidone. The homo- and copolymers of l-viny-limidazole which can be obtained by the process according to the 5 invention are distinguished by being very compatible with conven-tional detergent ingredients and have a low residual monomer con-tent. The residual content of l-vinylimidazole monomer normally does not exceed 0.02% by weight. The copolymer solutions normally contain less than 0.02% by weight of l-vinylpyrrolidone. Compared 10 with previously disclosed polymer solutions, the polymers obtain-able according to the invention additionally have a better color.
The polymers can be isolated from the aqueous polymerization medium for example by spray drying. Other drying methods, for ex-ample evaporation of the polymer solution and milling the residue 15 or freeze drying are likewise possible.
The K values indicated in the examples were determined by the method of H. Fikentscher, Cellulose-Chemie, 13 (1932) 58 - 64 and 71 - 74, in 0.1 N aqueous sodium chloride solution at 25 C with a 20 polymer concentration of 1% by weight. The percentages in the ex-amples are based on weight. The residual monomer content in the polymers was determined by gas chromatography, and the weight average molecular weight was determined by light scattering.
25 Example 1 A mixture of 200 g of l-vinylpyrrolidone (VP), 50 g of l-vinyl-imidazole (VI) and 600 g of water is introduced into a stirring apparatus and heated to 65 C while stirring under a nitrogen atmo-30 sphere. As soon as this tpmpprature is reached, 5 g of 2,2'-azo-bis(2-amidinopropane) dihydrochloride dissolved in 30 ml of water are added. Subsequently, over the course of 1 hour, a solution of 5 g of mercaptoethanol in 30 ml of water is continuously metered in. After the addition is complete, the mixture is stirred at 65 C
35 for 2 hours, then 1.25 g of 2,2'-azobis(2-amidinopropane) dihy-drochloride are added, and the mixture is stirred at 65 C for a further 3 hours. A pale yellow viscous polymer solution with a faint odor is obtained. The K value of the copolymer is 27.4, and the molecular weight is 28 000. The aqueous polymer solution has 40 a solids content of 30% and contains less than 50 ppm VI and less than 50 ppm VP.
~ BASF Aktiengesellschaf~- O.Z. 0050/44033 _ 6 Example 2 Example 1 is repeated with the exception that the initial mixture 5 is composed of 175 g of l-vinylpyrrolidone, 75 g of l-vinylimid-azole and 600 g of water. A clear pale yellow polymer solution without the typical odor of l-vinylimidazole is obtained. The co-polymer has a K value of 22.3 and a molecular weight of 20 000.
The aqueous solution has a solids content of 29% and contains lO less than 50 ppm VI and less than 50 ppm VP.
Example 3 A mixture of 150 g of l-vinylpyrrolidone, 100 g of l-vinylimid-15 azole and 600 g of water is introduced into an apparatus which is equipped for operating under a nitrogen atmosphere and is pro-vided with a stirrer and heated to 70 C while stirring under a ni-trogen atmosphere. As soon as this temperature is reached, 6 g of 2,2'-azobis(2-amidinopropane) dihydrochloride dissolved in 35 ml 20 of water are added. Subsequently, over the course of 1 hour, a solution of 7.6 g of 2,2'-dithiodiethanol in 40 ml of water is metered in continuously. The mixture is then stirred at 70 C for 2 hours, 1.5 g of 2,2'-azobis(2-amidinopropane) dihydrochloride are added and the mixture is stirred at 70 C for a further 4 hours 25 to result in a yellow aqueous polymer solution with a faint odor.
The K value of the copolymer is 24.7 and the molecular weight is 26 000. The aqueous polymer solution has a solids content of 28%
and contains 110 ppm VI and 150 ppm VP.
30 Example 4 Example 1 is repeated with the exception that the initial mixture is composed of 125 g of VP, 125 g of VI and 600 g of water. The added regulator comprises a solution of 5 g of mercaptoacetic 35 acid in 30 ml of water. A yellow polymer solution which is clear and has a faint odor is obtained. The K value of the copolymer is 26.8 and the molecular weight is 34 000. The aqueous polymer solution has a solids content of 30% and contains less than 50 ppm VI and less than 50 ppm VP.
Example 5 125 g of VP, 125 g of VI and 600 g of water are introduced into a stirring apparatus and, while flushing with nitrogen and stir-45 ring, heated to 75 C. As soon as the mixture has reached 70 C asolution 1 composed of 5 g of 2,2'-azobis(2-amidinopropane) dihy-drochloride in 100 ml of water is metered in over the course of BASF Aktiengesellschaf~ O.Z. 0050/44033 100 minutes and a solution 2 composed of 10 g of mercaptoethanol in 50 ml of water is metered in over the course of 70 minutes.
After the addition of the initiator is complete, the mixture is stirred at 75 C for 75 minutes, then 1.25 g of 2,2'-azo-5 bis(2-amidinopropane) dihydrochloride are added and the mixture is stirred at 75 C for a further 2 hours. The resulting clear yel-low polymer solution with a solids content of 26.4% has a faint odor and a low residual monomer content. It contains less than 50 ppm VI and less than 50 ppm VP. The copolymer has a K value of lO 19.4 and a molecular weight of 12 000.
Example 6 A mixture of 10 g of VP, 10 g of VI, l.S g of mercaptoethanol and 15 65 g of water is heated in a polymerization apparatus to 75 C
while stirring and passing in nitrogen. After this temperature is reached, a mixture 1 composed of 135 g of VP, 135 g of VI, 16.2 g of mercaptoethanol and 485 g of water, and a solution 2 composed of 5.7 g of 2,2'-azobis(2-amidinopropane) dihydrochloride in 20 100 g of water are metered in over the course of 3 hours. The mixture is subsequently stirred at 75 C for 30 minutes and then an aqueous solution of 1.5 g of 2,2'-azobis(2-amidinopropane) dihy-drochloride in 10 g of water is added over the course of 5 min-utes and the mixture is stirred at 75 C for 2.5 hours. A clear 25 yellow polymer solution with a faint odor and a solids content of 33% is obtained. It contains less than 50 ppm VI and less than 50 ppm VP. The copolymer has a K value of 15 and a molecular weight of 6 000.
30 Example 7 Example 1 is repeated with the exception that the initial mixture is composed of 75 g of VP, 175 g of VI and 600 g of water. A yel-low viscous polymer solution with a faint odour and a solids con-35 tent of 28.4% is obtained. The copolymer has a K value of 32.5and a molecular weight of 39 000. The aqueous polymer solution has a low residual monomer concentration, ie. 100 ppm VI and less than 50 ppm VP.
40 Example 8 A mixture of 300 g of VI and 400 g of water is heated in a poly-merization apparatus to 80 C while stirring under a nitrogen at-mosphere. After this temperature is reached, a solution 1 com-45 posed of 9 g of mercaptoethanol in 50 g of water is metered inover the course of 2 hours and a solution 2 composed of 7.5 g of azobis(2-methylbutyronitrile) in 70 g of isopropanol is metered BASF Aktiengesellschaf~ 2 15 65 0 2 O.Z. 0050/44033 _ 8 in over the course of 3 hours. The mixture is subsequently stirred at 80 C for 1 hour, then a solution of 1.5 g of azo-bis(2-methylbutyronitrile) in a little isopropanol is added and the mixture is stirred at 80 C for a further 3 hours. The iso-5 propanol is subsequently removed from the mixture by steam dis-tillation to result in a yellow polymer solution with a faint odor, a solids content of 40% and a low residual monomer con-centration (80 ppm). The vinylimidazole homopolymer has a K value of 21.5 and a molecular weight of 23 000.
Comparative Examples according to DE-A-28 14 287 Comparative Example 1 15 In accordance with the statements in Example 6 in DE-A-28 14 287, a mixture of 9.4 g of VI, 22.2 g of VP and 120 g of methanol was copolymerized at the boiling point of the mixture while passing through nitrogen in the presence of 0.6 g of azobisisobutyro-nitrile as initiator. A polymer solution with an intense odor and 20 a solids content of 24.6% was obtained. The copolymer had a K value of 49. The polymer solution contained 650 ppm VI and 6 600 ppm VP.
Comparative Example 2 In accordance with the method indicated in Example 5 of DE-A-28 14 287, a mixture of 18.8 g of VI, 11.1 g of VP and 120 g of methanol was copolymerized with 6 g of azobisisobutyronitrile as initiator at the boiling point of the mixture. A polymer solu-30 tion with an intense odor and a solids content of 22.3% was ob-tained. The solution contained 1.15% of unpolymerized VI and 0.62% of unpolymerized VP. The K value of the copolymer was 42.6 Comparative Example 3 78 g of VI, 78 g of water and 2 g of azobisisobutyronitrile were introduced into a flask with a capacity of 500 ml and stirred at 80 C under a nitrogen atmosphere for 6 hours. A polymer solution with an intense odor and a solids content of 50.6% was obtained.
40 The VI content of the solution was 0.42%. The VI homopolymer had a K value of 43.9.
As the comparative examples demonstrate, the polymer solutions obtained in accordance with the examples of DE-A-28 14 287 do not 45 have a low molecular weight or a low residual monomer content.
The preparation of homopolymers of l-vinylimidazole and of co-polymers of 1-vinylimidazole and 1-vinylpyrrolidone by polymer-15 ization of the monomers in bulk or in solvents is known, cf.DE-A-2 814 287. The polymers of l-vinylimidazole described in the literature still contain relatively large amounts of unpolymer-ized vinylimidazole so that the polymers have a very unpleasant odor which is perceptible even at high dilution. In order to iso-20 late and purify the polymers after their preparation they aresubjected to an elaborate precipitation operation which is im-practical on the industrial scale.
It is an object of the present invention to provide novel sub-25 stances and an industrially straightforward process for preparing low molecular weight homopolymers, with a low residual monomer content, of l-vinylimidazole and copolymers of l-vinylimidazole and l-vinylpyrrolidone.
30 We have found that this object is achieved according to the in-vention by homopolymers of l-vinylimidazole and copolymers of 1-vinylimidazole and l-vinylpyrrolidone when they each contain sulfur in bound form and have a K value of from lO to 40 (deter-mined by the method of H. Fikentscher in 0.1 N aqueous sodium 35 chloride solution at 25 C with a polymer concentration of 1% by weight).
The said homopolymers of 1-vinylimidazole and the copolymers of 1-vinylimidazole and 1-vinylpyrrolidone are moreover obtainable 40 by free-radical polymerization of 1-vinylimidazole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolidone in Cl-C4-alcohols, water or mixtures of water and at least one C1-C4-alcohol in the presence of polymerization regulators which contain sulfur in bound form.
BASF Aktiengesellschaf~ 2 15 6 5 0 2 .Z. 0050/44033 _- 2 The present invention moreover relates to a process for preparing low molecular weight polymers of l-vinylimidazole by free-radical polymerization of l-vinylimidazole or of mixtures of l-vinylimid-azole and l-vinylpyrrolidone in Cl-C4-alcohols, water or mixtures 5 of water and at least one Cl-C4-alcohol, the polymerization being carried out in the presence of polymerization regulators which contain sulfur in bound form. Polymerization regulators which are preferably employed are mercapto compounds, dialkyl sulfides, dialkyl disulfides and/or diaryl sulfides.
The homo- and copolymers described above are used as color trans-fer inhibitors in detergents.
The process according to the invention is used to prepare low 15 molecular weight homopolymers and copolymers of l-vinylimidazole and l-vinylpyrrolidone. The homo- and copolymers have K values of 10 - 40, preferably 13 - 30 (determined by the method of H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25 C
with a polymer concentration of 1% by weight). The polymerization 20 of the monomers normally takes place under an atmosphere of inert gas, eg. nitrogen, argon or helium. Care is generally taken that the reactants are thoroughly mixed during the polymerization. The polymerization is carried out in Cl-C4-alcohols, water or mixtures of water and at least one Cl-C4-alcohol. The solvent preferably 25 used is water or mixtures of water and at least one Cl-C4-alcohol in any desired ratio. Suitable alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and isobutanol.
Isopropanol is preferably employed.
30 For the preparation of copolymers of l-vinylimidazole and l-vinylpyrrolidone it is possible to employ the monomers in any desired ratio in the copolymerization. The monomer mixtures employed in the copolymerization preferably contain from 5 to 99.9% by weight of l-vinylimidazole and from 0.1 to 95% by weight 35 of l-vinylpyrrolidone. The polymerization is preferably carried out in the range from 50 to 100 C. If the polymerization is car-ried out at higher temperatures, eg. at up to 150 C, it is carried out in apparatus which is closed pressure-tight.
40 The monomers undergo free-radical polymerization, ie. it is nec-essary to initiate the homo- and copolymerization with compounds which form free radicals under the polymerization conditions.
Such initiators which form free radicals are all conventional peroxy and azo compounds, for example peroxides, hydroperoxides 45 and peroxy esters, such as hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxypiva-late and t-butyl peroxy-2-ethylhexanoate as well as azo compounds ~ BASF Aktiengesellschaf~ 215 6 5 0 2 - Z 0050/44033 such as 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azo-bis[2-(2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis-isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and dimethyl 2,2'-azobis(2-methylpropionate). It is also, of course, possible 5 to use mixtures of initiators or the known redox initiators. The initiators are employed in conventional quantities, eg. in quan-tities of from 0.3 to 6% of the weight of the monomers to be polymerized. Where the polymerization is carried out in water or in mixtures of water and at least one of the abovementioned alco-10 hols as solvent, water-soluble azo initiators are preferably used.
The polymerization is carried out according to the invention in the presence of polymerization regulators which contain sulfur in 15 bound form. Examples of compounds of this type are inorganic bi-sulfites, disulfites and dithionites or organic sulfides, disul-fides, polysulfides, sulfoxides, sulfones and mercapto compounds.
The following polymerization regulators are mentioned by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sul-20 fide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, 2,2'-dithiodiethanol, di-t-butyl trisulfide and dimethyl sulfox-ide. The compounds preferably employed as polymerization regula-tors are mercapto compounds, dialkyl sulfides, dialkyl disulfides 25 and/or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercapto-1,2-propanediol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglyc-erol, thioacetic acid, thiourea and alkyl mercaptans such as 30 n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan. Po-lymerization regulators which are particularly preferably employed are mercapto alcohols and mercapto carboxylic acids. The polymerization regulators which contain sulfur in bound form are used in amounts of from 0.1 to 15, preferably O.S to 10, % of the 35 weight of the monomers employed in the polymerization. It is, of course, also possible to use mixtures of the polymerization regu-lators according to the invention in the polymerization.
The monomers can be polymerized by the conventional processes, 40 eg. by batch polymerization in which either l-vinylimidazole or mixtures of l-vinylimidazole and l-vinylpyrrolidone, regulator and initiator are introduced into a solvent and heated to the polymerization temperature. The mixture is stirred at the poly-merization temperature until the conversion is more than 99.9%.
45 In this process it is also possible where appropriate to add the initiator only after the polymerization temperature is reached.
BASF Aktiengesellschaf~ 21~ 6 5 0 2 Z. 0050/44033 other variants of the polymerization process are the addition methods, which are preferably employed. In these variants, a solution of the polymerization regulator which contains sulfur in bound form, and an initiator solution are added, continuously or 5 in portions, to a mixture of vinylimidazole, or a mixture of vinylimidazole and vinylpyrrolidone, and a solvent at the poly-merization temperature within a defined time. However, it is also possible to meter a mixture of regulator and initiator into the initial mixture at the polymerization temperature. Another method 10 comprises adding the initiator below or at the polymerization temperature to the initial mixture and introducing within a pre-set time only the regulator or a solution of the regulator into the reaction mixture after the polymerization temperature is reached. Another variant of the addition technique comprises 15 heating the initial mixture to a temperature at which polymeriza-tion takes place and then adding regulator, initiator and mono-mers separately or together. With this technique the initial mix-ture preferably comprises water or a mixture of water, monomer andtor initiator and/or regulator. A procedure which is particu-20 larly preferred according to the invention is one in which thepolymerization regulators cont~; n; ng sulfur in bound form are metered in continuously or in portions during the polymerization.
The weight average molecular weight Mw of the homo- and copolymers 25 of 1-vinylimidazole prepared in this way is in the range from 2 000 to 50 000, preferably 5 000 to 40 000. These polymers have K values of from 10 to 40 (determined by the method of H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25 C
with a polymer concentration of 1% by weight). The concentration 30 of the monomers in the aqueous medium is normally from 10 to 50 and is preferably in the range from 20 to 45% by weight. The solutions resulting from the polymerization can be subjected after the polymerization process to a physical or chemical de-odorization. This means, inter alia, a subsequent treatment of 35 the polymer solution by steam distillation, where volatile im-purities are removed from the solution with steam, or nitrogen stripping. For a subsequent chemical treatment, polymerization initiators or mixtures of a plurality of polymerization initia-tors are added and the polymer solution is heated where appropri-40 ate to temperatures above the polymerization temperature.
The process according to the invention results in polymer solu-tions which have a low residual monomer content and which can be directly marketed. Polymer solutions of this type are used, for 45 example, as additives to detergents. Their effect is, when colored and white textiles are washed, to inhibit transfer of color to the uncolored textiles. Detergents of this type contain, ~ BASF Aktiengesellschaf~ 21 S 6 5 0 2 .Z. 0050/44033 S
for example, from 0.1 to 10, preferably 0.2 to 3, % by weight of homopolymers of l-vinylimidazole or of copolymers of l-vinylimid-azole and l-vinylpyrrolidone. The homo- and copolymers of l-viny-limidazole which can be obtained by the process according to the 5 invention are distinguished by being very compatible with conven-tional detergent ingredients and have a low residual monomer con-tent. The residual content of l-vinylimidazole monomer normally does not exceed 0.02% by weight. The copolymer solutions normally contain less than 0.02% by weight of l-vinylpyrrolidone. Compared 10 with previously disclosed polymer solutions, the polymers obtain-able according to the invention additionally have a better color.
The polymers can be isolated from the aqueous polymerization medium for example by spray drying. Other drying methods, for ex-ample evaporation of the polymer solution and milling the residue 15 or freeze drying are likewise possible.
The K values indicated in the examples were determined by the method of H. Fikentscher, Cellulose-Chemie, 13 (1932) 58 - 64 and 71 - 74, in 0.1 N aqueous sodium chloride solution at 25 C with a 20 polymer concentration of 1% by weight. The percentages in the ex-amples are based on weight. The residual monomer content in the polymers was determined by gas chromatography, and the weight average molecular weight was determined by light scattering.
25 Example 1 A mixture of 200 g of l-vinylpyrrolidone (VP), 50 g of l-vinyl-imidazole (VI) and 600 g of water is introduced into a stirring apparatus and heated to 65 C while stirring under a nitrogen atmo-30 sphere. As soon as this tpmpprature is reached, 5 g of 2,2'-azo-bis(2-amidinopropane) dihydrochloride dissolved in 30 ml of water are added. Subsequently, over the course of 1 hour, a solution of 5 g of mercaptoethanol in 30 ml of water is continuously metered in. After the addition is complete, the mixture is stirred at 65 C
35 for 2 hours, then 1.25 g of 2,2'-azobis(2-amidinopropane) dihy-drochloride are added, and the mixture is stirred at 65 C for a further 3 hours. A pale yellow viscous polymer solution with a faint odor is obtained. The K value of the copolymer is 27.4, and the molecular weight is 28 000. The aqueous polymer solution has 40 a solids content of 30% and contains less than 50 ppm VI and less than 50 ppm VP.
~ BASF Aktiengesellschaf~- O.Z. 0050/44033 _ 6 Example 2 Example 1 is repeated with the exception that the initial mixture 5 is composed of 175 g of l-vinylpyrrolidone, 75 g of l-vinylimid-azole and 600 g of water. A clear pale yellow polymer solution without the typical odor of l-vinylimidazole is obtained. The co-polymer has a K value of 22.3 and a molecular weight of 20 000.
The aqueous solution has a solids content of 29% and contains lO less than 50 ppm VI and less than 50 ppm VP.
Example 3 A mixture of 150 g of l-vinylpyrrolidone, 100 g of l-vinylimid-15 azole and 600 g of water is introduced into an apparatus which is equipped for operating under a nitrogen atmosphere and is pro-vided with a stirrer and heated to 70 C while stirring under a ni-trogen atmosphere. As soon as this temperature is reached, 6 g of 2,2'-azobis(2-amidinopropane) dihydrochloride dissolved in 35 ml 20 of water are added. Subsequently, over the course of 1 hour, a solution of 7.6 g of 2,2'-dithiodiethanol in 40 ml of water is metered in continuously. The mixture is then stirred at 70 C for 2 hours, 1.5 g of 2,2'-azobis(2-amidinopropane) dihydrochloride are added and the mixture is stirred at 70 C for a further 4 hours 25 to result in a yellow aqueous polymer solution with a faint odor.
The K value of the copolymer is 24.7 and the molecular weight is 26 000. The aqueous polymer solution has a solids content of 28%
and contains 110 ppm VI and 150 ppm VP.
30 Example 4 Example 1 is repeated with the exception that the initial mixture is composed of 125 g of VP, 125 g of VI and 600 g of water. The added regulator comprises a solution of 5 g of mercaptoacetic 35 acid in 30 ml of water. A yellow polymer solution which is clear and has a faint odor is obtained. The K value of the copolymer is 26.8 and the molecular weight is 34 000. The aqueous polymer solution has a solids content of 30% and contains less than 50 ppm VI and less than 50 ppm VP.
Example 5 125 g of VP, 125 g of VI and 600 g of water are introduced into a stirring apparatus and, while flushing with nitrogen and stir-45 ring, heated to 75 C. As soon as the mixture has reached 70 C asolution 1 composed of 5 g of 2,2'-azobis(2-amidinopropane) dihy-drochloride in 100 ml of water is metered in over the course of BASF Aktiengesellschaf~ O.Z. 0050/44033 100 minutes and a solution 2 composed of 10 g of mercaptoethanol in 50 ml of water is metered in over the course of 70 minutes.
After the addition of the initiator is complete, the mixture is stirred at 75 C for 75 minutes, then 1.25 g of 2,2'-azo-5 bis(2-amidinopropane) dihydrochloride are added and the mixture is stirred at 75 C for a further 2 hours. The resulting clear yel-low polymer solution with a solids content of 26.4% has a faint odor and a low residual monomer content. It contains less than 50 ppm VI and less than 50 ppm VP. The copolymer has a K value of lO 19.4 and a molecular weight of 12 000.
Example 6 A mixture of 10 g of VP, 10 g of VI, l.S g of mercaptoethanol and 15 65 g of water is heated in a polymerization apparatus to 75 C
while stirring and passing in nitrogen. After this temperature is reached, a mixture 1 composed of 135 g of VP, 135 g of VI, 16.2 g of mercaptoethanol and 485 g of water, and a solution 2 composed of 5.7 g of 2,2'-azobis(2-amidinopropane) dihydrochloride in 20 100 g of water are metered in over the course of 3 hours. The mixture is subsequently stirred at 75 C for 30 minutes and then an aqueous solution of 1.5 g of 2,2'-azobis(2-amidinopropane) dihy-drochloride in 10 g of water is added over the course of 5 min-utes and the mixture is stirred at 75 C for 2.5 hours. A clear 25 yellow polymer solution with a faint odor and a solids content of 33% is obtained. It contains less than 50 ppm VI and less than 50 ppm VP. The copolymer has a K value of 15 and a molecular weight of 6 000.
30 Example 7 Example 1 is repeated with the exception that the initial mixture is composed of 75 g of VP, 175 g of VI and 600 g of water. A yel-low viscous polymer solution with a faint odour and a solids con-35 tent of 28.4% is obtained. The copolymer has a K value of 32.5and a molecular weight of 39 000. The aqueous polymer solution has a low residual monomer concentration, ie. 100 ppm VI and less than 50 ppm VP.
40 Example 8 A mixture of 300 g of VI and 400 g of water is heated in a poly-merization apparatus to 80 C while stirring under a nitrogen at-mosphere. After this temperature is reached, a solution 1 com-45 posed of 9 g of mercaptoethanol in 50 g of water is metered inover the course of 2 hours and a solution 2 composed of 7.5 g of azobis(2-methylbutyronitrile) in 70 g of isopropanol is metered BASF Aktiengesellschaf~ 2 15 65 0 2 O.Z. 0050/44033 _ 8 in over the course of 3 hours. The mixture is subsequently stirred at 80 C for 1 hour, then a solution of 1.5 g of azo-bis(2-methylbutyronitrile) in a little isopropanol is added and the mixture is stirred at 80 C for a further 3 hours. The iso-5 propanol is subsequently removed from the mixture by steam dis-tillation to result in a yellow polymer solution with a faint odor, a solids content of 40% and a low residual monomer con-centration (80 ppm). The vinylimidazole homopolymer has a K value of 21.5 and a molecular weight of 23 000.
Comparative Examples according to DE-A-28 14 287 Comparative Example 1 15 In accordance with the statements in Example 6 in DE-A-28 14 287, a mixture of 9.4 g of VI, 22.2 g of VP and 120 g of methanol was copolymerized at the boiling point of the mixture while passing through nitrogen in the presence of 0.6 g of azobisisobutyro-nitrile as initiator. A polymer solution with an intense odor and 20 a solids content of 24.6% was obtained. The copolymer had a K value of 49. The polymer solution contained 650 ppm VI and 6 600 ppm VP.
Comparative Example 2 In accordance with the method indicated in Example 5 of DE-A-28 14 287, a mixture of 18.8 g of VI, 11.1 g of VP and 120 g of methanol was copolymerized with 6 g of azobisisobutyronitrile as initiator at the boiling point of the mixture. A polymer solu-30 tion with an intense odor and a solids content of 22.3% was ob-tained. The solution contained 1.15% of unpolymerized VI and 0.62% of unpolymerized VP. The K value of the copolymer was 42.6 Comparative Example 3 78 g of VI, 78 g of water and 2 g of azobisisobutyronitrile were introduced into a flask with a capacity of 500 ml and stirred at 80 C under a nitrogen atmosphere for 6 hours. A polymer solution with an intense odor and a solids content of 50.6% was obtained.
40 The VI content of the solution was 0.42%. The VI homopolymer had a K value of 43.9.
As the comparative examples demonstrate, the polymer solutions obtained in accordance with the examples of DE-A-28 14 287 do not 45 have a low molecular weight or a low residual monomer content.
Claims (7)
1. A homopolymer of 1-vinylimidazole or copolymer of 1-vinylimi-dazole and 1-vinylpyrrolidone, each of which contains sulfur in bound form and has a K value of from 10 to 40 (determined by the method of H. Fikentscher in 0.1 N aqueous sodium chloride solution at 25°C with a polymer concentration of 1%
by weight).
by weight).
2. A homo- or copolymer as claimed in claim 1, obtainable by free-radical polymerization of 1-vinylimidazole or of mix-tures of 1-vinylimidazole and 1-vinylpyrrolidone in C1-C4-alcohols, water or mixtures of water and at least one C1-C4-alcohol in the presence of polymerization regulators which contain sulfur in bound form.
3. A process for preparing a polymer as claimed in claim 1 or 2, which comprises free-radical polymerization of 1-vinylimid-zole or of mixtures of 1-vinylimidazole and 1-vinylpyrrolid-one in C1-C4-alcohols, water or mixtures of water and at least one C1-C4-alcohol in the presence of polymerization regulators which contain sulfur in bound form.
4. A process as claimed in claim 3, wherein the polymerization regulators are employed in amounts of from 0.1 to 15% of the weight of the monomers.
5. A process as claimed in claim 3 or 4, wherein mercapto com-pounds, dialkyl sulfides, dialkyl disulfides and/or diaryl sulfides are employed as polymerization regulators.
6. A process as claimed in any of claims 3 to 5, wherein the polymerization regulators are added continuously or in por-tions during the polymerization of the monomers.
7. The use of the polymers as claimed in claim 1 or 2 as color transfer inhibitors in detergents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4316023A DE4316023A1 (en) | 1993-05-13 | 1993-05-13 | Process for the preparation of low molecular weight polymers of 1-vinylimidazole |
| DEP4316023.9 | 1993-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2156502A1 true CA2156502A1 (en) | 1994-11-24 |
Family
ID=6488002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002156502A Abandoned CA2156502A1 (en) | 1993-05-13 | 1994-05-02 | Homopolymers and copolymers of 1-vinylimidazole, method of producing them and their use |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0698046B1 (en) |
| JP (1) | JP3272362B2 (en) |
| AT (1) | ATE149528T1 (en) |
| CA (1) | CA2156502A1 (en) |
| DE (2) | DE4316023A1 (en) |
| DK (1) | DK0698046T3 (en) |
| ES (1) | ES2098144T3 (en) |
| WO (1) | WO1994026796A1 (en) |
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| US7947087B2 (en) | 2006-03-14 | 2011-05-24 | Henkel Ag & Co. Kgaa | Color transfer inhibitors, detergent compositions containing the same and uses therefor |
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| JP5686008B2 (en) * | 2011-03-17 | 2015-03-18 | 凸版印刷株式会社 | Thermal transfer recording medium |
| JP5862378B2 (en) * | 2011-03-17 | 2016-02-16 | 凸版印刷株式会社 | Thermal transfer recording medium |
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| WO2020011627A1 (en) | 2018-07-11 | 2020-01-16 | Basf Se | Process for preparing stable polymers containing vinylimidazole |
| CN115057965B (en) * | 2022-07-01 | 2023-08-01 | 漳州华福化工有限公司 | Preparation method of N-vinylpyrrolidone/1-vinylimidazole copolymer |
| CN115651108B (en) * | 2022-11-03 | 2024-02-23 | 宇昂科技有限公司 | Preparation method of polyvinylpyrrolidone with ultralow molecular weight |
| CN116515040A (en) * | 2023-05-25 | 2023-08-01 | 上海宇昂水性新材料科技股份有限公司 | N-vinylpyrrolidone/1-vinylimidazole copolymer, preparation method thereof and anti-staining agent |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2814287A1 (en) * | 1978-04-03 | 1979-10-11 | Henkel Kgaa | Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive |
| DE3617069A1 (en) * | 1986-05-21 | 1987-11-26 | Basf Ag | METHOD FOR PRODUCING 3-METHYL-1-VINYL IMIDAZOLIUM CHLORIDES AND THE USE THEREOF FOR PRODUCING POLYMERISATES |
-
1993
- 1993-05-13 DE DE4316023A patent/DE4316023A1/en not_active Withdrawn
-
1994
- 1994-05-02 DK DK94916182.2T patent/DK0698046T3/en active
- 1994-05-02 CA CA002156502A patent/CA2156502A1/en not_active Abandoned
- 1994-05-02 JP JP52489094A patent/JP3272362B2/en not_active Expired - Fee Related
- 1994-05-02 DE DE59401959T patent/DE59401959D1/en not_active Expired - Lifetime
- 1994-05-02 ES ES94916182T patent/ES2098144T3/en not_active Expired - Lifetime
- 1994-05-02 WO PCT/EP1994/001390 patent/WO1994026796A1/en active IP Right Grant
- 1994-05-02 AT AT94916182T patent/ATE149528T1/en not_active IP Right Cessation
- 1994-05-02 EP EP94916182A patent/EP0698046B1/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7179778B2 (en) | 2002-12-06 | 2007-02-20 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Liquid acid detergent comprising a phthaloylamino peroxy caproic acid |
| US7947087B2 (en) | 2006-03-14 | 2011-05-24 | Henkel Ag & Co. Kgaa | Color transfer inhibitors, detergent compositions containing the same and uses therefor |
| WO2008031199A1 (en) * | 2006-09-11 | 2008-03-20 | Transfert Plus, S.E.C. | Ionic compounds having bronsted acidity and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0698046A1 (en) | 1996-02-28 |
| JP3272362B2 (en) | 2002-04-08 |
| WO1994026796A1 (en) | 1994-11-24 |
| DK0698046T3 (en) | 1997-07-21 |
| DE4316023A1 (en) | 1994-11-17 |
| ES2098144T3 (en) | 1997-04-16 |
| JPH08510278A (en) | 1996-10-29 |
| DE59401959D1 (en) | 1997-04-10 |
| ATE149528T1 (en) | 1997-03-15 |
| EP0698046B1 (en) | 1997-03-05 |
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