CA1228442A - Aqueous dispersions of graft polymers or copolymers, a process for their production and their use as hydrophobizing and oleophobizing agents for textiles - Google Patents
Aqueous dispersions of graft polymers or copolymers, a process for their production and their use as hydrophobizing and oleophobizing agents for textilesInfo
- Publication number
- CA1228442A CA1228442A CA000474570A CA474570A CA1228442A CA 1228442 A CA1228442 A CA 1228442A CA 000474570 A CA000474570 A CA 000474570A CA 474570 A CA474570 A CA 474570A CA 1228442 A CA1228442 A CA 1228442A
- Authority
- CA
- Canada
- Prior art keywords
- monomers
- ethylenically unsaturated
- perfluoroalkyl
- graft
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
Abstract
AQUEOUS DISPERSIONS OF GRAFT POLYMERS OR COPOLYMERS, A PROCESS FOR THEIR PRODUCTION AND THEIR USE AS
HYDROPHOBIZING AND OLEOPHOBIZING AGENTS FOR TEXTILES
ABSTRACT OF THE INVENTION
The present invention relates to aqueous dispersions of graft polymers or graft copolymers containing as the graft base an aqueous polyurethane dispersion optionally containing block polyisocyanates in dispersed form as crosslinker and, as the graft covering, a polymer or a copolymer of ethylenically unsaturated monomers, characterized in that the graft covering is a polymer of ethylenically unsaturated perfluoroalkyl monomers having a molecular weight above 367 or a copolymer of perfluoroalkyl monomers such as these with comonomers free from perfluoroalkyl groups.
The present invention also relates to a process for producing these dispersions and to their use as hydrophobizing and oleophobizing agents for textiles.
HYDROPHOBIZING AND OLEOPHOBIZING AGENTS FOR TEXTILES
ABSTRACT OF THE INVENTION
The present invention relates to aqueous dispersions of graft polymers or graft copolymers containing as the graft base an aqueous polyurethane dispersion optionally containing block polyisocyanates in dispersed form as crosslinker and, as the graft covering, a polymer or a copolymer of ethylenically unsaturated monomers, characterized in that the graft covering is a polymer of ethylenically unsaturated perfluoroalkyl monomers having a molecular weight above 367 or a copolymer of perfluoroalkyl monomers such as these with comonomers free from perfluoroalkyl groups.
The present invention also relates to a process for producing these dispersions and to their use as hydrophobizing and oleophobizing agents for textiles.
Description
Moe Lea 22,890 AQUEOUS DISPERSIONS OF GRAFT POLYMERS OR COPOLYMERS, A PROCESS FOR THEIR PRODUCTION AND THEIR USE AS
HYDROPHOBIZING AND OLEOPHOBIZING AGENTS FOR TEXTILES
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to aqueous dispersions ox graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers containing aqueous polyurethane dispersions as the graft base, to a process for producing these dispersions by polymerizing or copolymerizing ethylenically unsaturated perfluoro-alkyd monomers and, optionally, comonomers free from perfluoroalkyl groups in aqueous polyurethane dispersions as the graft base and to their use as hydrophobizing and oleophobizing agents for textiles.
Description of the Prior Art Polymers containing perfluoroalkyl groups are suitable substances for hydrophobizing and oleophobizing (making oil or grease resistant) textiles or carpets. These polymers may be used in the form of aqueous emulsions. However, the production of aqueous emulsions by known methods of emulsion polymerization is difficult because ethylenically unsaturated perfluoroalkyl monomers are completely insoluble in water and stable emulsions cannot be obtained in water.
USES 3 403 122 describes an emulsion polyp merization process for producing perfluoroalkyl polymers in aqueous media which contain from 5 to 50%
of water-soluble, organic substances, for example acetone or methanol, to increase the volubility of the monomers in water. However, coarse, unstable dispersions are obtained in this way. In addition, Moe Lea 22,890 -Us %
HYDROPHOBIZING AND OLEOPHOBIZING AGENTS FOR TEXTILES
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to aqueous dispersions ox graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers containing aqueous polyurethane dispersions as the graft base, to a process for producing these dispersions by polymerizing or copolymerizing ethylenically unsaturated perfluoro-alkyd monomers and, optionally, comonomers free from perfluoroalkyl groups in aqueous polyurethane dispersions as the graft base and to their use as hydrophobizing and oleophobizing agents for textiles.
Description of the Prior Art Polymers containing perfluoroalkyl groups are suitable substances for hydrophobizing and oleophobizing (making oil or grease resistant) textiles or carpets. These polymers may be used in the form of aqueous emulsions. However, the production of aqueous emulsions by known methods of emulsion polymerization is difficult because ethylenically unsaturated perfluoroalkyl monomers are completely insoluble in water and stable emulsions cannot be obtained in water.
USES 3 403 122 describes an emulsion polyp merization process for producing perfluoroalkyl polymers in aqueous media which contain from 5 to 50%
of water-soluble, organic substances, for example acetone or methanol, to increase the volubility of the monomers in water. However, coarse, unstable dispersions are obtained in this way. In addition, Moe Lea 22,890 -Us %
- 2 -water-soluble, organic solvents such as acetone or methanol are precipitant for numerous polymers so that this process cannot be applied to many of the copolymerization systems normally used.
USES 3 068 187 describes segmented co-polymers, ire. block or graft copolymers of ethyl enically unsaturated perfluoroalkyl monomers with ethylenically unsaturated monomers containing less than loo of fluorine and also a process for their production lo by emulsion polymerization in which the monomer containing less than 10% of fluorine, for employ butadiene or chloroprene, is prepolymerized in aqueous emulsion, accompanied or followed by polymerization of the perfluoroalkyl monomer onto this pre-emulsion.
However, the addition of water-soluble solvents (such as acetone or methanol) is necessary in this process, too, so that the stability of the emulsion obtained is reduced or, alternatively, complete coagulation may even occur.
I To obviate these disadvantages, corresponding "perfluoroalkyl polymer emulsions" are generally prepared by solution polymerization in solvents which are insoluble in water (for example, methylisobutyl kitten, halogenated hydrocarbons or acetic acid esters) and are suitable as solvents both for the monomers and also for the polymers. By emulsifying this polymer solution in water using special emulsifying units or homogenizers it is generally possible to obtain sufficiently fine, stable dispersions. However, this process it made complicated and expensive by the need for the additional step of emulsification, so that there is still a need for a technically simpler emulsion polymerization process.
Moe Lea 22,890 It has now been found that hydrophobizing and oleophobizing dispersions which are stable in storage can be obtained by subjecting the ethylenically unsaturated perfluoroalkyl monomers described in detail hereinafter, preferably in combination with other vinyl monomers, to graft polymerization in the process of aqueous polyurethane dispersions. Irrespective ox the Greta yield, the total quantity of polymerized monomers is referred to as the "graft covering."
Although DEMOS 19 53 345, DEMOS 19 53 348 and Do OX 19 53 34g describe the production of aqueous dispersions of polymers of ethylenically unsaturated monomers in aqueous polyurethane or oligourethane dispersions, the discovery according to the invention (that it is possible to produce storable dispersions of graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers) must be regarded as surprising, even in the light of the disclosure of the above-mentioned prior publications, because stable polymer emulsions can also be produced by other methods from the monomers mentioned in these prior publications so that it could not have been expected that the above-mentioned difficulties involved in the production of aqueous dispersions of perfluoroalkyl polymers would be overcome by using aqueous polyp urethane dispersions as the graft base. The dispersions according to the invention described in more detail hereinafter are further distinguished from the dispersions according to the above-mentioned prior publications by the fact that they are outstanding oleophobizing agents for textiles.
Molly Lea 22,890 I
SUMMARY OF THE INVENTION
The present invention relates to aqueous dispersions of graft polymers or graft copolymers containing as the graft base an aqueous polyurethane dispersion optionally containing block polyisocyanates in dispersed form as cross linker and, as the graft covering, a polymer or a copolymer of e~hylenically unsaturated monomers, characterized in that the graft covering is a polymer of ethylenically unsaturated perfluoroalkyl monomers having a molecular weight above 367 or a copolymer of perfluoroalkyl monomers such as these with comonomers free from perfluoroalkyl groups.
The present invention also relates to a process for producing these dispersions by the polyp merization or copolymerization of ethylenicallyunsaturated monomers or of mixtures of ethylenically unsaturated monomers in aqueous polyurethane dispersions optionally containing blocked pulse-sonnets in dispersed form as cross linker, characterized in that ethylenically unsaturated perfluoroalkyl monomers having a molecular weight above 367 or mixtures of perfluoroalkyl monomers such as these with ethylenically unsaturated monomers free from perfluoroalkyl groups in a ratio by weight of per-fluoroalkyl monomers to monomers free from perfluoro~alkyl groups of at least 3:2 are used as the ethyl-enically unsaturated monomers.
The present invention also relates to the use of these dispersions as hydrophobizing and Leo-phobizing agents for textiles.
Moe yea 22,890 DETAILED DESCRIPTION OF THE INVENTION
Aqueous polyurethane solutions suitable for use as the graft base in the process according Jo the invention are any aqueous dispersions of polyurethane 5 or polyurethane pullers. These dispersions generally have a solids content of about 5 to 60% by weight end preferably about 30 to 50% by weight. Aqueous disk pensions of polyurethane containing chemically incorpo-rated ionic and/or non ionic hydrophilic centers are 10 particularly suitable. Dispersions such as these and -their production are described, for example, in USES
USES 3 068 187 describes segmented co-polymers, ire. block or graft copolymers of ethyl enically unsaturated perfluoroalkyl monomers with ethylenically unsaturated monomers containing less than loo of fluorine and also a process for their production lo by emulsion polymerization in which the monomer containing less than 10% of fluorine, for employ butadiene or chloroprene, is prepolymerized in aqueous emulsion, accompanied or followed by polymerization of the perfluoroalkyl monomer onto this pre-emulsion.
However, the addition of water-soluble solvents (such as acetone or methanol) is necessary in this process, too, so that the stability of the emulsion obtained is reduced or, alternatively, complete coagulation may even occur.
I To obviate these disadvantages, corresponding "perfluoroalkyl polymer emulsions" are generally prepared by solution polymerization in solvents which are insoluble in water (for example, methylisobutyl kitten, halogenated hydrocarbons or acetic acid esters) and are suitable as solvents both for the monomers and also for the polymers. By emulsifying this polymer solution in water using special emulsifying units or homogenizers it is generally possible to obtain sufficiently fine, stable dispersions. However, this process it made complicated and expensive by the need for the additional step of emulsification, so that there is still a need for a technically simpler emulsion polymerization process.
Moe Lea 22,890 It has now been found that hydrophobizing and oleophobizing dispersions which are stable in storage can be obtained by subjecting the ethylenically unsaturated perfluoroalkyl monomers described in detail hereinafter, preferably in combination with other vinyl monomers, to graft polymerization in the process of aqueous polyurethane dispersions. Irrespective ox the Greta yield, the total quantity of polymerized monomers is referred to as the "graft covering."
Although DEMOS 19 53 345, DEMOS 19 53 348 and Do OX 19 53 34g describe the production of aqueous dispersions of polymers of ethylenically unsaturated monomers in aqueous polyurethane or oligourethane dispersions, the discovery according to the invention (that it is possible to produce storable dispersions of graft polymers or copolymers of ethylenically unsaturated perfluoroalkyl monomers) must be regarded as surprising, even in the light of the disclosure of the above-mentioned prior publications, because stable polymer emulsions can also be produced by other methods from the monomers mentioned in these prior publications so that it could not have been expected that the above-mentioned difficulties involved in the production of aqueous dispersions of perfluoroalkyl polymers would be overcome by using aqueous polyp urethane dispersions as the graft base. The dispersions according to the invention described in more detail hereinafter are further distinguished from the dispersions according to the above-mentioned prior publications by the fact that they are outstanding oleophobizing agents for textiles.
Molly Lea 22,890 I
SUMMARY OF THE INVENTION
The present invention relates to aqueous dispersions of graft polymers or graft copolymers containing as the graft base an aqueous polyurethane dispersion optionally containing block polyisocyanates in dispersed form as cross linker and, as the graft covering, a polymer or a copolymer of e~hylenically unsaturated monomers, characterized in that the graft covering is a polymer of ethylenically unsaturated perfluoroalkyl monomers having a molecular weight above 367 or a copolymer of perfluoroalkyl monomers such as these with comonomers free from perfluoroalkyl groups.
The present invention also relates to a process for producing these dispersions by the polyp merization or copolymerization of ethylenicallyunsaturated monomers or of mixtures of ethylenically unsaturated monomers in aqueous polyurethane dispersions optionally containing blocked pulse-sonnets in dispersed form as cross linker, characterized in that ethylenically unsaturated perfluoroalkyl monomers having a molecular weight above 367 or mixtures of perfluoroalkyl monomers such as these with ethylenically unsaturated monomers free from perfluoroalkyl groups in a ratio by weight of per-fluoroalkyl monomers to monomers free from perfluoro~alkyl groups of at least 3:2 are used as the ethyl-enically unsaturated monomers.
The present invention also relates to the use of these dispersions as hydrophobizing and Leo-phobizing agents for textiles.
Moe yea 22,890 DETAILED DESCRIPTION OF THE INVENTION
Aqueous polyurethane solutions suitable for use as the graft base in the process according Jo the invention are any aqueous dispersions of polyurethane 5 or polyurethane pullers. These dispersions generally have a solids content of about 5 to 60% by weight end preferably about 30 to 50% by weight. Aqueous disk pensions of polyurethane containing chemically incorpo-rated ionic and/or non ionic hydrophilic centers are 10 particularly suitable. Dispersions such as these and -their production are described, for example, in USES
3 479 310, RIPS 1 495 745, DE-AS 14 95 847, USES
3 920 598, USES 3 905 929, USES 4 108 81~, USES
3 920 598, USES 3 905 929, USES 4 108 81~, USES
4 092 286, USES 190 566, USES 4 237 26~, USES
15 4 238 378, DEMOS 27 25 589, DEMOS 27 32 131, DEMOS
28 11 1~8, USES 4 269 748, USES 4 292 226 or DEMOS
31 37 748 which corresponds to USES 4 452 834. Par-titularly high-grade dispersions according to the invention are obtained when aqueous polyurethane disk 20 pensions containing blocked polyisocyanates in dispersed form as cross linker are used as the graft base. The production of polyurethane dispersions such as these is described in the last of the above-mentioned prior publications (DEMOS 31 37 748 and USES 4 452 834).
The ethylenically unsaturated perfluoroalkyl monomers essential to the invention are any ethyl-enically unsaturated compounds containing at least 5 per fluorinated carbon atoms in the form of perfluoro-alkyd groups, "perfluoroalkyl groups" being understood 30 to be saturated, per fluorinated aliphatic radicals which may have a linear, branched or cyclic structure.
Moe Lea 22,890 ,. I. ., I
Suitable perfluoroalkyl monomers have a monomer weight above 367, i.e. of a least 368. Suitable purrer alkyd monomers such as these are, in particular, acrylates or methacrylates corresponding to the following general formulae CnF2n+lCH2CH20c-c SHEA
O R
or CnF2n+lS2N, CH2CH20C-C=CH2 R' O R
in which R represents hydrogen or a methyl group, R' represents hydrogen or an alkyd group containing from 1 to 6 carbon atoms and n = 5 or is an integer of greater than 5, preferably from 5 to 12.
Examples of perfluoroalkyl monomers such as these are N-methyl-N-perfluoropentane sulfonamidoethyl methacrylate, N-methyl perfluorooctane sulfonamidoethyl acrylate, N-methyl-N-perfluorooctane sulfonamidoethyl methacrylate, N-ethyl-N-perfluorooctane sulfonamide-ethyl methacrylate, N-propyl-N-perfluorooctane cellophane-amidoethyl acrylate, ~-hexyl-N-perfluorododecane sulfonamidoethyl acrylate or perfluoropentyl-, perfluorooctyl- or perfluorododecyl-substituted in the 2-position of the ethyl radical of ethyl acrylates or methacrylates. Mixtures of the perfluoroalkyl monomers mentioned by way of example may of course also be used.
In addition to the perfluoroalkyl monomers melltioned by way of example, other comonomers free from Moe Lea 22,89 perfluoroalkyl groups may also be used. If comonomers such as these are used, the ratio by weight of perfluoroalkyl monomers to comonomers free from perfluoroalkyl groups is at least about 3:2 and preferably at least about 2:1.
Suitable comonomers free from perfluoroalkyl groups include butadiene, isoprene, chloroprene, styrenes methyl styrenes p-methyl styrenes vinyl halides (such as vinyl chloride, vinylidene chloride or Jo vinylidene fluoride), vinyl esters (such as vinyl acetate, vinyl preappoint, vinyl Stewart or vinyl methyl kitten), acrylic acid, methacrylic acid, malefic acid android, acrylic acid esters or methacrylic acid esters (such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propel acrylate, bottle acrylate, 2-ethylhexyl acrylate or methacrylate, decal acrylate, laurel acrylate or methacrylate, stroll methacrylate, N,~-dimethylaminoethyl moth-acrylate, 2-hydroxyethyl methacrylate, 2-hydro~ypropyl methacrylate or glycidyl methacrylate), acrylamide, methacrylamide, N-methylol acrylamide, acrylonitrile, methacrylonitrile or substituted malefic immediacy.
Mixtures of these comonomers are also suitable.
In the practical application of the process according to the invention, the total quantity of ethylenically unsaturated monomers is gauged in such a way that about 25 to 900 parts by weight and preferably about 50 to 500 parts by weight of the ethylenically unsaturated monomers are available per 100 parts by weight of dispersed polyurethane solids.
The graft reaction is normally carried out by initially introducing the polyurethane dispersion as Mob Lea 22,B90 the graft base and subsequently introducing the ethyl-enically unsaturated perfluoroalkyl monomers and, optionally, the comonomers free from perfluoroalkyl groups in liquid form (for example, in the form of a monomer mixture, solution or aqueous emulsion) and polymerizing or grafting these monomers onto the graft base using radical initiators. The solution or aqueous emulsion is preferably prepared using substantially or completely water-insoluble, preferably polar solvents lo which are also suitable as solvents for the perfluoro-alkyd monomers and the optionally used comonomers free from perfluoroalkyl groups. Examples of these solvents include kittens such as methyl isobutyl kitten; fatty acid esters such as methyl acetate, ethyl acetate, bottle acetate or ethyl preappoint; or halogenated hydrocarbons such as ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, fluorotri-chloromethane or 1,1,2-trifluoro-1,2,2-trichloro-ethanes Mixtures of the solvents mentioned by way of example may of course also be used. It is particularly preferred to use the monomers in the form of aqueous monomer emulsions which may be obtained for example, by intensively mixing a solution of the monomers in one of the solvents mentioned by way of example with water in the presence of suitable emulsifiers of the type mentioned by way of example in the following. In general, about 10 to 60% by weight solution or emulsions of the monomers are used in the practical application of the process according to the invention.
It is of course also possible to use the (liquid) optional comonomer free from perfluoroalkyl groups as solvent for the perfluoroalkyl monomers.
My 26l~8 Lea 22,890 The graft reaction is preferably carried out in the presence of standard radical-forming initiators such as water-soluble initiators which include potassium, sodium or ammonium persulate or hydrogen peroxide; redo systems of per sulfate; and sodium disulfite, sodium hydrogen sulfite or sulfur dioxide.
Particularly suitable initiators are oil-soluble initiators such as dibenzoyl peroxide, dustily peroxide, dilauroyl peroxide, di-tert.-butyl peroxide, lo tert.-butyl hydroperoxide, cumin hydroperoxide, left.-utile peroctoate, azoiso~utyrodinitrile, etc.
To improve the graft yields, it is possible to use so-called graft activators, i.e. special substances or monomers having a high transfer activity which are capable of considerably increasing the graft yields even when used in small quantities. Examples of graft activators are olefins (such as propylene or isobutylene), vinyl chloride, vinyl acetate or triallyl sonority. It is also possible to use so-called regulators (such as ally compounds or mercaptans) for regulating the molecular weights.
Standard anionic, cat ionic or non ionic emulsifiers may be used for stabilizing the dispersions according to the invention and also for preparing the monomer emulsions used in the process according to the invention. Examples of anionic emulsifiers are alkyd sulfonates, alkyd aureole sulfonates, fatty alcohol sulfates or sulfosuccinic acid esters or emulsifiers containing perfluoroalkyl groups (such as ammonium or tetraethylammonium salts of perfluorooctane sulfonic acid or the potassium salt of N-ethyl-~-per1uoro-octane sulfonyl Gleason). Examples of cat ionic Moe Lea 22,890 emulsifiers are qua ternary ammonium of pyridinium salts such as stroll dim ethyl ben~ylammonium chloride or N,N,N-trimethyl-N-perfluorooctane sulfonamidopropyl-ammonium chloride. Examples of non ionic emulsifiers are polyglycol esters (such as ethylene oxide/propylene oxide block polymers or copolymers), alkoxylation products, particularly ethoxylation products of fatty alcohols, alkyd phenols, fatty acids, fatty acid aTn-ldes, sorbitan moonlit or N-alkyl-N-perfluoro-octane sulfonyl Gleason. Combinations of nonionicemulsifiers with anion-active or cation-active emulsifiers of the type mentioned by way of example are particularly suitable.
The process according to the invention is generally carried out at a temperature of about 20 to 120C and preferably at a temperature of about 50 to 100C, optionally in an inert gas atmosphere (nitrogen) and optionally under pressure. The monomers and also the auxiliaries and additives are generally incorporated in the polyurethane dispersion with continuous stirring. By virtue of the outstanding stability of the dispersions according to the invention, it is readily possible to remove solvents or volatile residual monomers by degas sing in standard distillation apparatus (such as for example rotary evaporators or thin-layer evaporators) without the coagulation which normally affects known emulsions of perfluoroalkyl polymers. Odorless, storable dispersions are obtained after degas sing. The solids content of the dispersions according to the invention generally amounts to between about 5 and 50~ by weight and preferably between about 10 and 30~ by weight, Moe Lea 22,890 I
depending upon the concentration of the polyurethane dispersion initially introduced and the quantity of water (and any solvent not removed) introduced with the monomers. The fluorine content in the solid generally amounts to between about 6 and 50% by weight and preferably between about lo and 30% by weight.
Films characterized by outstanding hydrophobicity and oleophobicity may be obtained from the dispersions according to the invention. The lo dispersions are eminently suitable or use as impregnating agents for oleophobizing and hydrophobizing textiles of natural and synthetic gibers, carpets, papers and leather.
Dispersions according to the invention containing blocked polyisocyanates in dispersed form may be processed by brief heating of the coatings prepared from them to temperatures above 100C to form high-grade, cross linked coatings.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
The following polyurethane dispersions were used in the Examples:
polyurethane Dispersion A
Constituents:
900 g of a 2000 MY polyester dill based on adipic acid, hexane dill and neopentyl glycol (molar ratio of glycols 65:35) 200 g of N-methylpyrrolidone 13.4 g of trimethylol propane Moe Lea 22,890 53.6 g of dimethylolpropionic acid 40.4 g of triethylamine 393 g of 4,4'-diisocyanatodicyclohexylmethane 39.2 g of acetone amine 1788 g of demineralized water.
A homogeneous, clear mixture was prepared at 60C from the polyester dehydrated in vacua at 100C, the N-methyl pyrrolidone, the trimethylol propane, the dimethylol prop ionic acid and the triethylamine. The diisocyanate was then added followed by stirring for about 2 hours at 80C until a (corrected) NCO-content of 2.6% was reached.
After cooling to 60C, the acetone amine was added to the prepolymer obtained. ale water was then added with thorough stirring. The resultant finely divided dispersion was stirred for 5 hours at 70C. It had a solids content of 40~ and a Ford cup viscosity (4 mm orifice) of 30 seconds.
Polyurethane Dispersion B
Constituents:
1200 g of 2000 MY polyester dill based on adipic acid, hexane dill and neopentyl glycol (molar ratio of glycols 65:35) 100 g of N-methyl pyrrolidone 53.6 g of dimethylol prop ionic acid 40.4 g of triethylamine 393 g of 4,4'-diisocyanatodicyclohexylmethane 146 g of blocked polyisocyanate ) 39.2 g of acetone amine 2446 g of demineralized water.
A homogeneous, clear mixture was prepared at 60C from the polyester dehydrated in vacua at 100C, Moe Lea 22,890 I
the N-methyl pyrrolidone, the dimethylol prop ionic acid and the triethylamine. The diisocyanate was then added, followed by stirring for 2 to 3 hours at 80C
until a (corrected NCO-content of 2.3% was reached. After cooling to 60C, the blocked polyp isocyanatel) and the acetone amine were successively added to the prepolymer obtained. The water was then added with thorough stirring, resulting in the formation of a finely divided dispersion which was stirred for 5 hours at 70C.
The dispersion thus obtained had a solids content of 40% and a Ford cup viscosity I mm orifice) of 18 seconds.
1) The blocked polyisocyanate was prepared as hollows:
425 g of butanone oxide diluted with 345 g of ethyl glycol acetate were added with cooling to 1000 g of a 90% solution of an isocyanurate polyisocyanate obtained by the trimerization of hexamethylene diisocyanate (NCO-content 20.5%, solvent: ethyl glycol acetate) and the mixture was left to react at 60C until the IR-spectrum no longer showed an NC0-band (2250 cm 1). The blocked polyisocyanate obtained was in the form of a 75% solution.
2) The NCO-content determined by amine-acid titration in the usual way is inaccurate because of the presence of triethylamine in the prepolymer.
Accordingly, the stated NCO-contents have been corrected.
I._ The following solutions were prepared at 70C:
Moe Lea 22,890 I 34~2 Solution 1 92.8 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 23.2 g of stroll methacrylate
15 4 238 378, DEMOS 27 25 589, DEMOS 27 32 131, DEMOS
28 11 1~8, USES 4 269 748, USES 4 292 226 or DEMOS
31 37 748 which corresponds to USES 4 452 834. Par-titularly high-grade dispersions according to the invention are obtained when aqueous polyurethane disk 20 pensions containing blocked polyisocyanates in dispersed form as cross linker are used as the graft base. The production of polyurethane dispersions such as these is described in the last of the above-mentioned prior publications (DEMOS 31 37 748 and USES 4 452 834).
The ethylenically unsaturated perfluoroalkyl monomers essential to the invention are any ethyl-enically unsaturated compounds containing at least 5 per fluorinated carbon atoms in the form of perfluoro-alkyd groups, "perfluoroalkyl groups" being understood 30 to be saturated, per fluorinated aliphatic radicals which may have a linear, branched or cyclic structure.
Moe Lea 22,890 ,. I. ., I
Suitable perfluoroalkyl monomers have a monomer weight above 367, i.e. of a least 368. Suitable purrer alkyd monomers such as these are, in particular, acrylates or methacrylates corresponding to the following general formulae CnF2n+lCH2CH20c-c SHEA
O R
or CnF2n+lS2N, CH2CH20C-C=CH2 R' O R
in which R represents hydrogen or a methyl group, R' represents hydrogen or an alkyd group containing from 1 to 6 carbon atoms and n = 5 or is an integer of greater than 5, preferably from 5 to 12.
Examples of perfluoroalkyl monomers such as these are N-methyl-N-perfluoropentane sulfonamidoethyl methacrylate, N-methyl perfluorooctane sulfonamidoethyl acrylate, N-methyl-N-perfluorooctane sulfonamidoethyl methacrylate, N-ethyl-N-perfluorooctane sulfonamide-ethyl methacrylate, N-propyl-N-perfluorooctane cellophane-amidoethyl acrylate, ~-hexyl-N-perfluorododecane sulfonamidoethyl acrylate or perfluoropentyl-, perfluorooctyl- or perfluorododecyl-substituted in the 2-position of the ethyl radical of ethyl acrylates or methacrylates. Mixtures of the perfluoroalkyl monomers mentioned by way of example may of course also be used.
In addition to the perfluoroalkyl monomers melltioned by way of example, other comonomers free from Moe Lea 22,89 perfluoroalkyl groups may also be used. If comonomers such as these are used, the ratio by weight of perfluoroalkyl monomers to comonomers free from perfluoroalkyl groups is at least about 3:2 and preferably at least about 2:1.
Suitable comonomers free from perfluoroalkyl groups include butadiene, isoprene, chloroprene, styrenes methyl styrenes p-methyl styrenes vinyl halides (such as vinyl chloride, vinylidene chloride or Jo vinylidene fluoride), vinyl esters (such as vinyl acetate, vinyl preappoint, vinyl Stewart or vinyl methyl kitten), acrylic acid, methacrylic acid, malefic acid android, acrylic acid esters or methacrylic acid esters (such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propel acrylate, bottle acrylate, 2-ethylhexyl acrylate or methacrylate, decal acrylate, laurel acrylate or methacrylate, stroll methacrylate, N,~-dimethylaminoethyl moth-acrylate, 2-hydroxyethyl methacrylate, 2-hydro~ypropyl methacrylate or glycidyl methacrylate), acrylamide, methacrylamide, N-methylol acrylamide, acrylonitrile, methacrylonitrile or substituted malefic immediacy.
Mixtures of these comonomers are also suitable.
In the practical application of the process according to the invention, the total quantity of ethylenically unsaturated monomers is gauged in such a way that about 25 to 900 parts by weight and preferably about 50 to 500 parts by weight of the ethylenically unsaturated monomers are available per 100 parts by weight of dispersed polyurethane solids.
The graft reaction is normally carried out by initially introducing the polyurethane dispersion as Mob Lea 22,B90 the graft base and subsequently introducing the ethyl-enically unsaturated perfluoroalkyl monomers and, optionally, the comonomers free from perfluoroalkyl groups in liquid form (for example, in the form of a monomer mixture, solution or aqueous emulsion) and polymerizing or grafting these monomers onto the graft base using radical initiators. The solution or aqueous emulsion is preferably prepared using substantially or completely water-insoluble, preferably polar solvents lo which are also suitable as solvents for the perfluoro-alkyd monomers and the optionally used comonomers free from perfluoroalkyl groups. Examples of these solvents include kittens such as methyl isobutyl kitten; fatty acid esters such as methyl acetate, ethyl acetate, bottle acetate or ethyl preappoint; or halogenated hydrocarbons such as ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, fluorotri-chloromethane or 1,1,2-trifluoro-1,2,2-trichloro-ethanes Mixtures of the solvents mentioned by way of example may of course also be used. It is particularly preferred to use the monomers in the form of aqueous monomer emulsions which may be obtained for example, by intensively mixing a solution of the monomers in one of the solvents mentioned by way of example with water in the presence of suitable emulsifiers of the type mentioned by way of example in the following. In general, about 10 to 60% by weight solution or emulsions of the monomers are used in the practical application of the process according to the invention.
It is of course also possible to use the (liquid) optional comonomer free from perfluoroalkyl groups as solvent for the perfluoroalkyl monomers.
My 26l~8 Lea 22,890 The graft reaction is preferably carried out in the presence of standard radical-forming initiators such as water-soluble initiators which include potassium, sodium or ammonium persulate or hydrogen peroxide; redo systems of per sulfate; and sodium disulfite, sodium hydrogen sulfite or sulfur dioxide.
Particularly suitable initiators are oil-soluble initiators such as dibenzoyl peroxide, dustily peroxide, dilauroyl peroxide, di-tert.-butyl peroxide, lo tert.-butyl hydroperoxide, cumin hydroperoxide, left.-utile peroctoate, azoiso~utyrodinitrile, etc.
To improve the graft yields, it is possible to use so-called graft activators, i.e. special substances or monomers having a high transfer activity which are capable of considerably increasing the graft yields even when used in small quantities. Examples of graft activators are olefins (such as propylene or isobutylene), vinyl chloride, vinyl acetate or triallyl sonority. It is also possible to use so-called regulators (such as ally compounds or mercaptans) for regulating the molecular weights.
Standard anionic, cat ionic or non ionic emulsifiers may be used for stabilizing the dispersions according to the invention and also for preparing the monomer emulsions used in the process according to the invention. Examples of anionic emulsifiers are alkyd sulfonates, alkyd aureole sulfonates, fatty alcohol sulfates or sulfosuccinic acid esters or emulsifiers containing perfluoroalkyl groups (such as ammonium or tetraethylammonium salts of perfluorooctane sulfonic acid or the potassium salt of N-ethyl-~-per1uoro-octane sulfonyl Gleason). Examples of cat ionic Moe Lea 22,890 emulsifiers are qua ternary ammonium of pyridinium salts such as stroll dim ethyl ben~ylammonium chloride or N,N,N-trimethyl-N-perfluorooctane sulfonamidopropyl-ammonium chloride. Examples of non ionic emulsifiers are polyglycol esters (such as ethylene oxide/propylene oxide block polymers or copolymers), alkoxylation products, particularly ethoxylation products of fatty alcohols, alkyd phenols, fatty acids, fatty acid aTn-ldes, sorbitan moonlit or N-alkyl-N-perfluoro-octane sulfonyl Gleason. Combinations of nonionicemulsifiers with anion-active or cation-active emulsifiers of the type mentioned by way of example are particularly suitable.
The process according to the invention is generally carried out at a temperature of about 20 to 120C and preferably at a temperature of about 50 to 100C, optionally in an inert gas atmosphere (nitrogen) and optionally under pressure. The monomers and also the auxiliaries and additives are generally incorporated in the polyurethane dispersion with continuous stirring. By virtue of the outstanding stability of the dispersions according to the invention, it is readily possible to remove solvents or volatile residual monomers by degas sing in standard distillation apparatus (such as for example rotary evaporators or thin-layer evaporators) without the coagulation which normally affects known emulsions of perfluoroalkyl polymers. Odorless, storable dispersions are obtained after degas sing. The solids content of the dispersions according to the invention generally amounts to between about 5 and 50~ by weight and preferably between about 10 and 30~ by weight, Moe Lea 22,890 I
depending upon the concentration of the polyurethane dispersion initially introduced and the quantity of water (and any solvent not removed) introduced with the monomers. The fluorine content in the solid generally amounts to between about 6 and 50% by weight and preferably between about lo and 30% by weight.
Films characterized by outstanding hydrophobicity and oleophobicity may be obtained from the dispersions according to the invention. The lo dispersions are eminently suitable or use as impregnating agents for oleophobizing and hydrophobizing textiles of natural and synthetic gibers, carpets, papers and leather.
Dispersions according to the invention containing blocked polyisocyanates in dispersed form may be processed by brief heating of the coatings prepared from them to temperatures above 100C to form high-grade, cross linked coatings.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
The following polyurethane dispersions were used in the Examples:
polyurethane Dispersion A
Constituents:
900 g of a 2000 MY polyester dill based on adipic acid, hexane dill and neopentyl glycol (molar ratio of glycols 65:35) 200 g of N-methylpyrrolidone 13.4 g of trimethylol propane Moe Lea 22,890 53.6 g of dimethylolpropionic acid 40.4 g of triethylamine 393 g of 4,4'-diisocyanatodicyclohexylmethane 39.2 g of acetone amine 1788 g of demineralized water.
A homogeneous, clear mixture was prepared at 60C from the polyester dehydrated in vacua at 100C, the N-methyl pyrrolidone, the trimethylol propane, the dimethylol prop ionic acid and the triethylamine. The diisocyanate was then added followed by stirring for about 2 hours at 80C until a (corrected) NCO-content of 2.6% was reached.
After cooling to 60C, the acetone amine was added to the prepolymer obtained. ale water was then added with thorough stirring. The resultant finely divided dispersion was stirred for 5 hours at 70C. It had a solids content of 40~ and a Ford cup viscosity (4 mm orifice) of 30 seconds.
Polyurethane Dispersion B
Constituents:
1200 g of 2000 MY polyester dill based on adipic acid, hexane dill and neopentyl glycol (molar ratio of glycols 65:35) 100 g of N-methyl pyrrolidone 53.6 g of dimethylol prop ionic acid 40.4 g of triethylamine 393 g of 4,4'-diisocyanatodicyclohexylmethane 146 g of blocked polyisocyanate ) 39.2 g of acetone amine 2446 g of demineralized water.
A homogeneous, clear mixture was prepared at 60C from the polyester dehydrated in vacua at 100C, Moe Lea 22,890 I
the N-methyl pyrrolidone, the dimethylol prop ionic acid and the triethylamine. The diisocyanate was then added, followed by stirring for 2 to 3 hours at 80C
until a (corrected NCO-content of 2.3% was reached. After cooling to 60C, the blocked polyp isocyanatel) and the acetone amine were successively added to the prepolymer obtained. The water was then added with thorough stirring, resulting in the formation of a finely divided dispersion which was stirred for 5 hours at 70C.
The dispersion thus obtained had a solids content of 40% and a Ford cup viscosity I mm orifice) of 18 seconds.
1) The blocked polyisocyanate was prepared as hollows:
425 g of butanone oxide diluted with 345 g of ethyl glycol acetate were added with cooling to 1000 g of a 90% solution of an isocyanurate polyisocyanate obtained by the trimerization of hexamethylene diisocyanate (NCO-content 20.5%, solvent: ethyl glycol acetate) and the mixture was left to react at 60C until the IR-spectrum no longer showed an NC0-band (2250 cm 1). The blocked polyisocyanate obtained was in the form of a 75% solution.
2) The NCO-content determined by amine-acid titration in the usual way is inaccurate because of the presence of triethylamine in the prepolymer.
Accordingly, the stated NCO-contents have been corrected.
I._ The following solutions were prepared at 70C:
Moe Lea 22,890 I 34~2 Solution 1 92.8 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 23.2 g of stroll methacrylate
5 174 g of methyl isobutyl kitten
6.0 g of ethoxylated sorb Ian moonlit containing approximately 80 ethylene oxide units per molecule.
Solution 2 302 g of deionized water 6.0 g of potassium salt of N-ethyl-N-perfluoro-octane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser, a monomer emulsion 3 was prepared for use in the following reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. The following components were uniformly added over a period of 2 hours at 75C:
600 g of monomer emulsion 3 and as solution 4 9 6.0 g of dilauroyl peroxide in 100 g of methyl isobutyl kitten.
After stirring for 1 hour at 75C, the mixture was diluted with 200 g of deionized water and a stable dispersion was obtained without any precipitation of solids.
For degas sing, approximately 400 g of distillate were removed in a rotary evaporator at 60C/200 mar. 800 g of a stable, substantially odorless dispersion having the following analytical data were obtained as residue:
Solids content: 30.2%
Moe Lea 22,890 Fluorine content in solid: 17.8%
The following solutions were prepared at 70C:
Solution 1 69.6 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 46.4 g of butylacrylate 174 g of methyl issuable kitten 6.0 g of ethoxylated sorbitan moonlit lo containing approximately 80 ethylene oxide units per molecule.
Solution 2 302 g of deionized water 6.0 g of the potassium salt of N-ethyl-N-per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using a high-speed mixer, a monomer emulsion 3 was prepared for use in the following grafting reaction.
300 g of polyurethane dispersion B were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 600 g of monomer emulsion 3 and also a solution of 5.0 g of dilauroyl peroxide in lo g of methyl isobutyl kitten were uniformly added over a period of 2 hours at 75C. After stirring for 1 hour at 75C, the mixture was diluted with 400 g of deionized water and a stable dispersion was obtained without any precipitation of solids.
The dispersion was degassed by removing approximately 400 g of distillate in a rotary evaporator at 60C/200 mar. 1000 g of a stable, substantially odorless dispersion having the following analytical data were obtained:
Moe Lea 22,890 Solids content: 24.5%
Fluorine content in the solid: 13.6%
The following solutions were prepared at 60C:
Solution 1 92.8 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 23.2 g of twirl methacrylate 174 g of ethyl acetate 6.0 g of ethoxylated sorbitan moonlit containing approximately 80 ethylene oxide units per molecule.
Solution 2 600 g of deionized water 6.0 g of the potassium salt of N-ethyl-N per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser, a monomer emulsion 3 was prepared for the subsequent grafting reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 900 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of ethyl acetate were uniformly added over a period of 2 hours at 75C.
After stirring for 1 hour at 75C, 300 g of distillate were removed in a rotary evaporator at 60C/200 mar with the addition of 300 g of deionized water. 1200 g of a stable dispersion having the following analytical data were obtained:
Solids content: 20.2%
Fluorine content in the solid: 18.0%
Moe Lea 22,890 I
The following solutions were prepared at 70~C:
Solution 1 92.8 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 23.2 g of stroll methacrylate 1.2 g of triallyl sonority 174 g of methyl isobutyl kitten 6.0 g of ethoxylated sorbitan moonlit containing approximately 80 ethylene oxide units per molecule.
Solution 2 302 g of deionized water 6.0 g of the potassium salt of N-ethyl-N-per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser 9 a monomer emulsion 3 was prepared for use in the following grafting reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 600 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of methylisobutyl kitten were uniformly added over a period of 3 hours at 75C. After stirring for 30 minutes at 80C, 300 g of distillate were removed in a rotary evaporator at 60C/200 mar with the addition of 300 g of deionized water. 1000 g of a stable dispersion having the following analytical data were obtained:
30 Solids content: 24.4%
Fluorine content in the solid: 17,3%
Moe Let 22,890 The following solutions were prepared at 70C:
Solution 1 97.4 g of N-n-propyl-N-perfluorooctane sulfonamidoethyl acryla~e 18.6 g of ethyl acrylate 0.8 g of triallyl sonority 175 g of methyl isobutyl kitten 5.6 g of ethoxylated sorbitan moonlit containing approximately 80 ethylene oxide units per molecule, Solution 2 305 g of deionized water 5.6 g of the potassium salt of N-ethyl-N-per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser, a monomer emulsion 3 was prepared for use in the subsequent grafting reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 600 g of monomer emulsion 3 and a solution of 5.0 g of dilauroyl peroxide in 80 g of methyl isobutyl kitten were uniformly added over a period of 3 hours at 75C.
After stirring for 30 minutes at 80C, 300 g of distillate were distilled off in a rotary evaporator at 60C/200 mar with the addition of 300 g of deionized water. 1000 g of a stable dispersion having the following analytical data are obtained:
Solids content: 23.8%
Fluorine content in the solid: 17.9%
Moe Lea 22,890 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be S made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
owe Lea 22,890
Solution 2 302 g of deionized water 6.0 g of potassium salt of N-ethyl-N-perfluoro-octane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser, a monomer emulsion 3 was prepared for use in the following reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. The following components were uniformly added over a period of 2 hours at 75C:
600 g of monomer emulsion 3 and as solution 4 9 6.0 g of dilauroyl peroxide in 100 g of methyl isobutyl kitten.
After stirring for 1 hour at 75C, the mixture was diluted with 200 g of deionized water and a stable dispersion was obtained without any precipitation of solids.
For degas sing, approximately 400 g of distillate were removed in a rotary evaporator at 60C/200 mar. 800 g of a stable, substantially odorless dispersion having the following analytical data were obtained as residue:
Solids content: 30.2%
Moe Lea 22,890 Fluorine content in solid: 17.8%
The following solutions were prepared at 70C:
Solution 1 69.6 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 46.4 g of butylacrylate 174 g of methyl issuable kitten 6.0 g of ethoxylated sorbitan moonlit lo containing approximately 80 ethylene oxide units per molecule.
Solution 2 302 g of deionized water 6.0 g of the potassium salt of N-ethyl-N-per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using a high-speed mixer, a monomer emulsion 3 was prepared for use in the following grafting reaction.
300 g of polyurethane dispersion B were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 600 g of monomer emulsion 3 and also a solution of 5.0 g of dilauroyl peroxide in lo g of methyl isobutyl kitten were uniformly added over a period of 2 hours at 75C. After stirring for 1 hour at 75C, the mixture was diluted with 400 g of deionized water and a stable dispersion was obtained without any precipitation of solids.
The dispersion was degassed by removing approximately 400 g of distillate in a rotary evaporator at 60C/200 mar. 1000 g of a stable, substantially odorless dispersion having the following analytical data were obtained:
Moe Lea 22,890 Solids content: 24.5%
Fluorine content in the solid: 13.6%
The following solutions were prepared at 60C:
Solution 1 92.8 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 23.2 g of twirl methacrylate 174 g of ethyl acetate 6.0 g of ethoxylated sorbitan moonlit containing approximately 80 ethylene oxide units per molecule.
Solution 2 600 g of deionized water 6.0 g of the potassium salt of N-ethyl-N per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser, a monomer emulsion 3 was prepared for the subsequent grafting reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 900 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of ethyl acetate were uniformly added over a period of 2 hours at 75C.
After stirring for 1 hour at 75C, 300 g of distillate were removed in a rotary evaporator at 60C/200 mar with the addition of 300 g of deionized water. 1200 g of a stable dispersion having the following analytical data were obtained:
Solids content: 20.2%
Fluorine content in the solid: 18.0%
Moe Lea 22,890 I
The following solutions were prepared at 70~C:
Solution 1 92.8 g of N-methyl-N-perfluorooctane sulfonamide-ethyl methacrylate 23.2 g of stroll methacrylate 1.2 g of triallyl sonority 174 g of methyl isobutyl kitten 6.0 g of ethoxylated sorbitan moonlit containing approximately 80 ethylene oxide units per molecule.
Solution 2 302 g of deionized water 6.0 g of the potassium salt of N-ethyl-N-per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser 9 a monomer emulsion 3 was prepared for use in the following grafting reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 600 g of monomer emulsion 3 and a solution of 6.0 g of dilauroyl peroxide in 100 g of methylisobutyl kitten were uniformly added over a period of 3 hours at 75C. After stirring for 30 minutes at 80C, 300 g of distillate were removed in a rotary evaporator at 60C/200 mar with the addition of 300 g of deionized water. 1000 g of a stable dispersion having the following analytical data were obtained:
30 Solids content: 24.4%
Fluorine content in the solid: 17,3%
Moe Let 22,890 The following solutions were prepared at 70C:
Solution 1 97.4 g of N-n-propyl-N-perfluorooctane sulfonamidoethyl acryla~e 18.6 g of ethyl acrylate 0.8 g of triallyl sonority 175 g of methyl isobutyl kitten 5.6 g of ethoxylated sorbitan moonlit containing approximately 80 ethylene oxide units per molecule, Solution 2 305 g of deionized water 5.6 g of the potassium salt of N-ethyl-N-per-fluorooctane sulfonyl Gleason.
By mixing solutions 1 and 2 using an ultrasonic disperser, a monomer emulsion 3 was prepared for use in the subsequent grafting reaction.
300 g of polyurethane dispersion A were introduced into a stirrer-equipped flask and heated under nitrogen to 75C. 600 g of monomer emulsion 3 and a solution of 5.0 g of dilauroyl peroxide in 80 g of methyl isobutyl kitten were uniformly added over a period of 3 hours at 75C.
After stirring for 30 minutes at 80C, 300 g of distillate were distilled off in a rotary evaporator at 60C/200 mar with the addition of 300 g of deionized water. 1000 g of a stable dispersion having the following analytical data are obtained:
Solids content: 23.8%
Fluorine content in the solid: 17.9%
Moe Lea 22,890 Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be S made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
owe Lea 22,890
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous dispersion of graft polymers or graft copolymers containing, as graft base, an aqueous polyurethane dispersion optionally containing blocked polyisocyanates in dispersed form as crosslinker and, as graft covering, a polymer or a copolymer of ethyl-enically unsaturated monomers, wherein said graft covering is a polymer of an ethylenically unsaturated perfluoroalkyl monomer having a molecular weight above 367 or a copolymer of said perfluoroalkyl monomers with a comonomer free from perfluoroalkyl groups in a weight ratio of at least about 3:2.
2. The aqueous dispersion of Claim 1 wherein said dispersion has a solids content of between about 5 and 50% by weight, and wherein the fluorine content of said solids is between about 6 and 50% by weight.
3. The aqueous dispersion of Claim 1 wherein the aqueous dispersion has a solids content between about 10 and 30% by weight and wherein the fluorine content of said solids is between about 10 and 30% by weight.
4. The aqueous dispersion of Claim 1 wherein said aqueous polyurethane dispersion contains a blocked polyisocyanate in dispersed form as crosslinker.
5. A process for producing an aqueous dispersion of graft polymers or copolymers which comprises polymerizing or copolymerizing an ethylenically unsaturated monomer, or a mixture of ethylenically unsaturated monomers in an aqueous polyurethane dispersion optionally containing a blocked polyisocyanate in dispersed form as crosslinker, wherein said ethylenically unsaturated monomer is an ethylenically unsaturated perfluoroalkyl monomer having a molecular weight of greater than 367 or wherein said mixture of said ethylenically unsaturated perfluoro-alkyl monomers or a mixture of said perfluoroalkyl monomers with at least one ethylenically unsaturated monomer which is free from perfluoroalkyl groups in a ratio by weight of perfluoroalkyl monomers to monomers free from perfluoroalkyl groups of at least about 3:2.
6. The process of Claim 5 wherein said ethylenically unsaturated monomer or said mixture of ethylenically unsaturated monomers are used in the form of a solution in a polar solvent or in the form of an aqueous emulsion,
7. The process of Claim 5 wherein said aqueous polyurethane dispersion contains a blocked polyisocyanate in dispersed form as crosslinker.
8. The process of Claim 6 wherein said aqueous polyurethane dispersion contains a blocked polyisocyanate in dispersed form as crosslinker.
9. A coated heat-resistant substrate wherein the coating comprises the aqueous dispersion of Claim 1.
10. The coated heat-resistant substrate of Claim 9 wherein said aqueous dispersion contains a blocked polyisocyanate in dispersed form as crosslinker and said coating is converted into a crosslinked coating by heating at a temperature above 100°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3407362.0 | 1984-02-29 | ||
| DE19843407362 DE3407362A1 (en) | 1984-02-29 | 1984-02-29 | AQUEOUS DISPERSIONS OF GRAFT POLYMERS OR COPOLYMERS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A HYDROPHOBIC AND OLEOPHOBIC AGENT FOR TEXTILES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1228442A true CA1228442A (en) | 1987-10-20 |
Family
ID=6229162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000474570A Expired CA1228442A (en) | 1984-02-29 | 1985-02-18 | Aqueous dispersions of graft polymers or copolymers, a process for their production and their use as hydrophobizing and oleophobizing agents for textiles |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4636545A (en) |
| EP (1) | EP0156155B1 (en) |
| JP (1) | JPS60206813A (en) |
| CA (1) | CA1228442A (en) |
| DE (2) | DE3407362A1 (en) |
| HU (1) | HUT38662A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1213441B (en) * | 1986-12-30 | 1989-12-20 | Ausimont Spa | POLYURETHANE AND FLUORINATED WATER DISPERSIONS AND THEIR USE FOR TEXTILE COATINGS. |
| DE3712069A1 (en) * | 1987-04-09 | 1988-10-20 | Basf Ag | USE OF GRAFT POLYMERISATS BASED ON POLYESTERS, POLYESTERURETHANES AND POLYESTERAMIDES AS GRAYING INHIBITORS IN DETERGENTS |
| DE3722005A1 (en) * | 1987-07-03 | 1989-01-12 | Herberts Gmbh | METHOD FOR PRODUCING A MULTI-LAYER COATING AND AQUEOUS AQUEOUS COATING AGENT THEREFOR |
| JPH0637754B2 (en) * | 1987-08-10 | 1994-05-18 | 大日精化工業株式会社 | Porous sheet material and method for producing the same |
| DE3939341A1 (en) * | 1989-11-29 | 1991-06-06 | Bayer Ag | HYDROPHOBIC AND OLEOPHOBIC AGENTS |
| DE4012630A1 (en) * | 1990-04-20 | 1991-10-24 | Bayer Ag | Copolymer or graft copolymer with unsatd. per:fluoroalkyl monomer - and unsatd. per:fluoroalkyl-free monomer on dispersion of polyurethane contg. per:fluoroalkyl backbone, used as dressing |
| DE4019798A1 (en) * | 1990-06-21 | 1992-01-02 | Bayer Ag | Paper sizing agents with wide range of applications |
| JPH0559669A (en) * | 1991-08-29 | 1993-03-09 | Teijin Ltd | Production of stain-proofing water-repellent fabric |
| DE4207851A1 (en) * | 1992-03-12 | 1993-09-16 | Bayer Ag | MEANS AND METHOD FOR EQUIPMENT OF TEXTILES |
| EP0608021B1 (en) * | 1993-01-21 | 1997-05-07 | Akzo Nobel N.V. | Water-dispersible hybrid polymer |
| US5652291A (en) * | 1995-07-14 | 1997-07-29 | Seiko Chemical Industries Co., Ltd. | Aqueous dispersion of urethane vinyl composite resin |
| GB9519824D0 (en) * | 1995-09-29 | 1995-11-29 | Secr Defence | Fibre reactive polymers |
| DE19624818A1 (en) * | 1996-06-21 | 1998-01-02 | Bayer Ag | Graft polymers of unsaturated monomers on modified polyureas, processes for their preparation and their use |
| JP4000614B2 (en) * | 1997-02-10 | 2007-10-31 | 大日本インキ化学工業株式会社 | Durable aqueous resin composition, antifouling coating agent and releasable coating agent |
| US6359030B1 (en) * | 1997-10-24 | 2002-03-19 | Daikin Industries, Ltd. | Aqueous resin dispersion composition |
| DE19930067A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Coating material and its use for the production of filler layers and stone chip protection primers |
| DE19930066A1 (en) | 1999-06-30 | 2001-01-11 | Basf Coatings Ag | Color and / or effect multi-layer coating, process for their preparation and their use |
| DE19930664A1 (en) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Clear varnish and its use for the production of clear varnishes and color and / or effect multilayer varnishes |
| DE19930665A1 (en) | 1999-07-02 | 2001-01-11 | Basf Coatings Ag | Basecoat and its use for the production of color and / or effect basecoats and multi-layer coating |
| DE19959923A1 (en) | 1999-12-11 | 2001-06-28 | Basf Coatings Ag | Aqueous primary dispersions and coating materials, processes for their preparation and their use |
| DE10005819A1 (en) * | 2000-02-10 | 2001-08-23 | Basf Coatings Ag | Aqueous primary dispersions, processes for their preparation and their use |
| DE10018078A1 (en) * | 2000-04-12 | 2001-11-08 | Basf Coatings Ag | Molding compositions and process for the production of moldings |
| DE10018601A1 (en) * | 2000-04-14 | 2001-10-25 | Basf Coatings Ag | Aqueous primary dispersion and coating agent useful in motor vehicle manufacture, is prepared by radical (co)polymerization of monomers dispersed in an aqueous dispersion of the cross-linking agent |
| DE10106567A1 (en) * | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Aqueous primary dispersion essentially or completely free of volatile organic substances, process for their preparation and their use |
| DE10106566A1 (en) * | 2001-02-13 | 2002-08-22 | Basf Coatings Ag | Aqueous coating material substantially or completely free of volatile organic substances, process for its preparation and its use |
| DE10126651A1 (en) * | 2001-06-01 | 2002-12-12 | Basf Coatings Ag | Use of copolymers with diphenylethylene units as emulsifiers for the production of powder slurry and coating powder for use in coating materials, adhesives and sealants, e.g. for painting cars |
| DE10126650B4 (en) * | 2001-06-01 | 2005-08-18 | Basf Coatings Ag | Functional organic powders, process for their preparation and their use |
| DE10208567A1 (en) * | 2002-02-27 | 2003-09-11 | Degussa Construction Chem Gmbh | Aqueous fluorine-modified polyurethane system for anti-graffiti and anti-soiling coatings |
| DE10331484A1 (en) * | 2003-07-11 | 2005-03-03 | Construction Research & Technology Gmbh | Polyurethane-polymer hybrid dispersion with improved surface properties, process for their preparation and their use |
| DE102006046368A1 (en) * | 2006-09-29 | 2008-04-03 | Construction Research & Technology Gmbh | New functionalized polyurethane resins, based on fluoro-modified, stabilized oligo- or polyurethane binder, useful for permanent oil-, water- and dirt-repellent coating of surfaces |
| EP3421558A1 (en) * | 2017-06-30 | 2019-01-02 | 3M Innovative Properties Company | Amphiphilic copolymer-based protective coating composition for metal surfaces |
| CN108467471B (en) * | 2018-04-04 | 2020-10-30 | 优美特（北京）环境材料科技股份公司 | Comb-shaped multi-branched aqueous polyurethane dispersion and preparation and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL123950C (en) * | 1959-08-10 | |||
| US3403122A (en) * | 1967-12-22 | 1968-09-24 | Minnesota Mining & Mfg | Emulsion polymerization of water insoluble omega-(n-perfluoroalkanesulfonyl) aminoalkyl acrylates or methacrylates |
| BE757936A (en) * | 1969-10-23 | 1971-04-01 | Bayer Ag | PROCESS FOR PREPARING ANIONIC MODIFIED POLYMERS IN EMULSION |
| DE1953349C3 (en) * | 1969-10-23 | 1975-07-03 | Bayer Ag, 5090 Leverkusen | Process for the preparation of aqueous dispersions of polymers from olefinically unsaturated monomers |
| BE757935A (en) * | 1969-10-23 | 1971-04-01 | Bayer Ag | PROCESS FOR PREPARING EMULSION MODIFIED CATIONIC POLYMERS |
| DE2811148A1 (en) * | 1978-03-15 | 1979-09-20 | Bayer Ag | PROCESS FOR THE PRODUCTION OF Aqueous POLYURETHANE DISPERSIONS AND SOLUTIONS |
| JPS6030796B2 (en) * | 1980-07-29 | 1985-07-18 | 花王株式会社 | darkening agent |
| JPS57139585A (en) * | 1981-02-13 | 1982-08-28 | Kao Corp | Color concentrating agent |
-
1984
- 1984-02-29 DE DE19843407362 patent/DE3407362A1/en not_active Withdrawn
-
1985
- 1985-02-16 DE DE8585101728T patent/DE3560149D1/en not_active Expired
- 1985-02-16 EP EP85101728A patent/EP0156155B1/en not_active Expired
- 1985-02-18 CA CA000474570A patent/CA1228442A/en not_active Expired
- 1985-02-19 US US06/703,011 patent/US4636545A/en not_active Expired - Fee Related
- 1985-02-27 JP JP60036736A patent/JPS60206813A/en active Granted
- 1985-02-28 HU HU85750A patent/HUT38662A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUT38662A (en) | 1986-06-30 |
| EP0156155B1 (en) | 1987-04-29 |
| DE3560149D1 (en) | 1987-06-04 |
| DE3407362A1 (en) | 1985-08-29 |
| EP0156155A1 (en) | 1985-10-02 |
| JPS60206813A (en) | 1985-10-18 |
| US4636545A (en) | 1987-01-13 |
| JPH0457687B2 (en) | 1992-09-14 |
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