CA1079744A - Process for the production of bisulphite addition products of polyisocyanate prepolymers in water - Google Patents
Process for the production of bisulphite addition products of polyisocyanate prepolymers in waterInfo
- Publication number
- CA1079744A CA1079744A CA260,646A CA260646A CA1079744A CA 1079744 A CA1079744 A CA 1079744A CA 260646 A CA260646 A CA 260646A CA 1079744 A CA1079744 A CA 1079744A
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- Canada
- Prior art keywords
- bisulphite
- water
- polyisocyanate prepolymers
- prepolymers
- polyisocyanate
- 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.)
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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
-
- 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
-
- 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
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A PROCESS FOR THE PRODUCTION OF BISULPHITE ADDITION
PRODUCTS OF POLYISOCYANATE PREPOLYMERS IN WATER
ABSTRACT OF THE DISCLOSURE
The instant invention relates to a new process for the production of bisulphite addition compounds of poly-isocyanate prepolymers containing free isocyanate groups which is carried out in the absence of organic solvents.
In general, the process is characterized by reacting the polyisocyanate prepolymers with water-soluble bisulphites, wherein, a) The polyisocyanate prepolymers used are isocyanate group containing reaction products of low molecular weight organic polyisocyanates with deficits of organic polyhydroxyl compounds which have been modified by the incorporation of non-ionic hydrophilic groups in such a way that the polyisocyanate prepolymers can be emulsified in water, and b) the reaction with bisulphites is carried out in the aqueous phase in the absence of organic solvents.
PRODUCTS OF POLYISOCYANATE PREPOLYMERS IN WATER
ABSTRACT OF THE DISCLOSURE
The instant invention relates to a new process for the production of bisulphite addition compounds of poly-isocyanate prepolymers containing free isocyanate groups which is carried out in the absence of organic solvents.
In general, the process is characterized by reacting the polyisocyanate prepolymers with water-soluble bisulphites, wherein, a) The polyisocyanate prepolymers used are isocyanate group containing reaction products of low molecular weight organic polyisocyanates with deficits of organic polyhydroxyl compounds which have been modified by the incorporation of non-ionic hydrophilic groups in such a way that the polyisocyanate prepolymers can be emulsified in water, and b) the reaction with bisulphites is carried out in the aqueous phase in the absence of organic solvents.
Description
Mo-1631-G
LeA 16,670-G
~797 L~ 4 A PROCESS FOR THE PRODUCTION OF BISULPHITE ADDITION
PRODUCTS OF POLYISOCYANATE PREPO~YMERS IN WATER
sack~round of the Invention The production of addition products from isocyanates and acid salts of sulphurous acid in the aqueous phase is - already known (German Patent No. 859,156~. This process is based on the reaction of relatively low molecular weight mono-and poly-isocyanates.
It is also generally known (see e. g. German Offen-legungsschrift 2,307,563) that bisulphite adducts of relatively high molecular weight polyisocyanate prepolymers cannot be produced under these conditions. The conversion oE relatively high molecular weight polyisocyanate prepolymers into the bisulphite addition products only takes place when relatively large quantities of organic water-miscible solvents are added to the aqueous phase. Unfortunately, this complicates the -process in terms of practical working because the use of organic solvents involves a number of disadvantages, including, or example, the costs of the solvent, the outlay involved in its recovery, the in1ammability o~ the solvent and the toxicity of the solvent vapors. The volume-time yield of this process and, hence, itseconomy is extremely unsatisfactory.
DESCRIPTION OF THE INVENTION
It has now surprisingly been found that these dis-advantages can be eliminated by using non-ionically hydro-philised prepolymers for the productio;n of the bisulphite adducts of polyisocyanate prepolymers. The reaction between the prepolymers thu5 modified and the salt-like bis1ulphites takes place in water at room temperature in the abslence of LeA 16,670-G
~797~
organic solvents, giving aqueous homogeneous solutions of the bisulphite addition products of polyisocyana-te prepolymers.
~ccordingly, this new process enables bisu:Lphite addition products of polyisocyanate prepolymers to be obtained in an extremely simple manner.
Accordingly, the present invention is directed to a process for the production of bisulphite addition products o~
polyioscyanate prepolymers by reacting the polyisocyanate prepolymers with water-soluble bisulphites, wherein a) the polyisocyanate prepolymers used are isocyanate group containing reaction products of (i) low molecular weight, organic pol~isocy~nates with (ii) less than stoichiometric amounts of organic polyhydroxyl compounds which have been modified by the incorporation of non-ionic hydrophilic groups in such a way that the polyisocyanate prepolymers can be emulsified in water, and b) reaction with the bisulphites is carried out in the aqueous phase in the absence of organic solvents.
The polyisocyanate prepolymers used in the process according to the invention are reaction products containing terminal isocyanate groups o~ excess quantities of diisocyanates corresponding to the formula;
R(NCO)2 :
with polyether polyols corresponding to the formula A(OH)n ~eA 16,670-G - 2 -~L~i7974~
These reaction products, in general, correspond to the ~;
formula: :
A-(0-C-NH-R-NCO)n O " ' :' In the above formu~a:
A represents a radical of the type obtained by removing ~ ~:
the hydroxyl groups from an _-functional polyalkylene oxide polyol which has a molecular weight of from 500 to 8000, preferably from 1000 to 6000, and 8 to 70%, preferably 8 to 30 %
of whose alkylene oxide segments consist of ethylene oxide segments and whose remaining alkylene oxide segments are propylene oxide, butylene oxide or styrene oxide segments, and preferably propylene ~.
oxide segments; .
R represents a radical of the type obtained by removing the isocyanate groups from an organic diisocyanate which has a molecular weight in the range from 112 to 1000, preferably an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydro-carbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms, and with particular preference - :~
a hydrocarbon radical of the type obtained by removing ~ ;
the isocyanate groups from hexamethylene diisocyanate or 2,4- and 2,6-diisocyanatotoluene;
- n is an integer from 2 to 4, preferably 2 or 3, mo~t prefer-ably 3.
LeA 16,670-G - 3 -.
4~
The polyether polyols AtOH)n are preferably produced by the alkoxylation known per se of a starter molecule of n-functionality, in the context of the alkylene oxide addition reaction, in the presence of ethylene oxide and, optionally, propylene oxide, isomeric butylene oxides, styrene oxide, and preferably propylene oxide, the aEorementioned alkylene oxides being used in any order or even in admixture with one another.
It is preferred to use ethylene oxide and propylene oxide in any order or in admixture in such quantities that the alkylene oxide segments of the polyether polyol correspond to the com-position gi~en above. Particularly preferred polyether polyolsare those which contain terminal polyethylene oxide segments in a quantity which corresponds to between 8 and 30 ~ of the total number o~ alkylene oxide units. In addition to the aforementioned alkylene oxides, it is also possible to use tetrahydrofuran for the production of the polyethers.
Preferred starter molecules are those corresponding to the formula:
B(OH)m, in which B represents hydrogen or an aliphatic hydrocarbon radical having 2 to 18 carbon atoms and preferably ~ :
having 2 to 6 carbon atoms, and m is identical with _ where B is a hydrocarbon radical, or is the number 1 where B is hydrogen.
In addition to these preferred starter molecules, it is also poss~ble to ~se any other c~mpounds o~ n~$unctional-ity, in the context of the alkylene oxide addition re~ct:ion which are suitable for the addition of alkylene oxides. In LeA 16,670-G - 4 ~
1~797~L
this case, however, the molecular weight of the starter molecule is pre~erably selected in such a way that the proportion of polyalkylene oxide segments in the polyether polyol A(OH)n amounts to at least 80~ by weight, based on the total weight of the polyether polyol.
Starter molecules suitable for producing the poly-ether polyols include, for example, water, ethylene glycol, 1,2-propane diol, trimethylene glycol, 1,2-butane diol, 2,3-butane diol, tetramethylene glycol, blycerol, 1,2,6-hexane triol, trimethylol propane, trimethylol ethane, pentaerythritol or even nitrogen-containing starter molecules such ~s tri-ethanolamine, ethylene diamine, aniline or aminoethanol. ..
Generally, it is also possible to use aromatir starter mole-cules such as resorcinol or bispheno.l A.
Suitable isocyanates R(NCO)2 include, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexa-methylene diisocyanate, 1,12-dodecane diiRocyanate, cyclo-butane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate and -1,4-diisocyanate, also mixtures of these isomers, l-isocyanato-3,35-trimethyl-5-isocyanatomethyl cyclohexane, 2,4- and
LeA 16,670-G
~797 L~ 4 A PROCESS FOR THE PRODUCTION OF BISULPHITE ADDITION
PRODUCTS OF POLYISOCYANATE PREPO~YMERS IN WATER
sack~round of the Invention The production of addition products from isocyanates and acid salts of sulphurous acid in the aqueous phase is - already known (German Patent No. 859,156~. This process is based on the reaction of relatively low molecular weight mono-and poly-isocyanates.
It is also generally known (see e. g. German Offen-legungsschrift 2,307,563) that bisulphite adducts of relatively high molecular weight polyisocyanate prepolymers cannot be produced under these conditions. The conversion oE relatively high molecular weight polyisocyanate prepolymers into the bisulphite addition products only takes place when relatively large quantities of organic water-miscible solvents are added to the aqueous phase. Unfortunately, this complicates the -process in terms of practical working because the use of organic solvents involves a number of disadvantages, including, or example, the costs of the solvent, the outlay involved in its recovery, the in1ammability o~ the solvent and the toxicity of the solvent vapors. The volume-time yield of this process and, hence, itseconomy is extremely unsatisfactory.
DESCRIPTION OF THE INVENTION
It has now surprisingly been found that these dis-advantages can be eliminated by using non-ionically hydro-philised prepolymers for the productio;n of the bisulphite adducts of polyisocyanate prepolymers. The reaction between the prepolymers thu5 modified and the salt-like bis1ulphites takes place in water at room temperature in the abslence of LeA 16,670-G
~797~
organic solvents, giving aqueous homogeneous solutions of the bisulphite addition products of polyisocyana-te prepolymers.
~ccordingly, this new process enables bisu:Lphite addition products of polyisocyanate prepolymers to be obtained in an extremely simple manner.
Accordingly, the present invention is directed to a process for the production of bisulphite addition products o~
polyioscyanate prepolymers by reacting the polyisocyanate prepolymers with water-soluble bisulphites, wherein a) the polyisocyanate prepolymers used are isocyanate group containing reaction products of (i) low molecular weight, organic pol~isocy~nates with (ii) less than stoichiometric amounts of organic polyhydroxyl compounds which have been modified by the incorporation of non-ionic hydrophilic groups in such a way that the polyisocyanate prepolymers can be emulsified in water, and b) reaction with the bisulphites is carried out in the aqueous phase in the absence of organic solvents.
The polyisocyanate prepolymers used in the process according to the invention are reaction products containing terminal isocyanate groups o~ excess quantities of diisocyanates corresponding to the formula;
R(NCO)2 :
with polyether polyols corresponding to the formula A(OH)n ~eA 16,670-G - 2 -~L~i7974~
These reaction products, in general, correspond to the ~;
formula: :
A-(0-C-NH-R-NCO)n O " ' :' In the above formu~a:
A represents a radical of the type obtained by removing ~ ~:
the hydroxyl groups from an _-functional polyalkylene oxide polyol which has a molecular weight of from 500 to 8000, preferably from 1000 to 6000, and 8 to 70%, preferably 8 to 30 %
of whose alkylene oxide segments consist of ethylene oxide segments and whose remaining alkylene oxide segments are propylene oxide, butylene oxide or styrene oxide segments, and preferably propylene ~.
oxide segments; .
R represents a radical of the type obtained by removing the isocyanate groups from an organic diisocyanate which has a molecular weight in the range from 112 to 1000, preferably an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydro-carbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms, and with particular preference - :~
a hydrocarbon radical of the type obtained by removing ~ ;
the isocyanate groups from hexamethylene diisocyanate or 2,4- and 2,6-diisocyanatotoluene;
- n is an integer from 2 to 4, preferably 2 or 3, mo~t prefer-ably 3.
LeA 16,670-G - 3 -.
4~
The polyether polyols AtOH)n are preferably produced by the alkoxylation known per se of a starter molecule of n-functionality, in the context of the alkylene oxide addition reaction, in the presence of ethylene oxide and, optionally, propylene oxide, isomeric butylene oxides, styrene oxide, and preferably propylene oxide, the aEorementioned alkylene oxides being used in any order or even in admixture with one another.
It is preferred to use ethylene oxide and propylene oxide in any order or in admixture in such quantities that the alkylene oxide segments of the polyether polyol correspond to the com-position gi~en above. Particularly preferred polyether polyolsare those which contain terminal polyethylene oxide segments in a quantity which corresponds to between 8 and 30 ~ of the total number o~ alkylene oxide units. In addition to the aforementioned alkylene oxides, it is also possible to use tetrahydrofuran for the production of the polyethers.
Preferred starter molecules are those corresponding to the formula:
B(OH)m, in which B represents hydrogen or an aliphatic hydrocarbon radical having 2 to 18 carbon atoms and preferably ~ :
having 2 to 6 carbon atoms, and m is identical with _ where B is a hydrocarbon radical, or is the number 1 where B is hydrogen.
In addition to these preferred starter molecules, it is also poss~ble to ~se any other c~mpounds o~ n~$unctional-ity, in the context of the alkylene oxide addition re~ct:ion which are suitable for the addition of alkylene oxides. In LeA 16,670-G - 4 ~
1~797~L
this case, however, the molecular weight of the starter molecule is pre~erably selected in such a way that the proportion of polyalkylene oxide segments in the polyether polyol A(OH)n amounts to at least 80~ by weight, based on the total weight of the polyether polyol.
Starter molecules suitable for producing the poly-ether polyols include, for example, water, ethylene glycol, 1,2-propane diol, trimethylene glycol, 1,2-butane diol, 2,3-butane diol, tetramethylene glycol, blycerol, 1,2,6-hexane triol, trimethylol propane, trimethylol ethane, pentaerythritol or even nitrogen-containing starter molecules such ~s tri-ethanolamine, ethylene diamine, aniline or aminoethanol. ..
Generally, it is also possible to use aromatir starter mole-cules such as resorcinol or bispheno.l A.
Suitable isocyanates R(NCO)2 include, for example, ethylene diisocyanate, tetramethylene diisocyanate, hexa-methylene diisocyanate, 1,12-dodecane diiRocyanate, cyclo-butane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate and -1,4-diisocyanate, also mixtures of these isomers, l-isocyanato-3,35-trimethyl-5-isocyanatomethyl cyclohexane, 2,4- and
2,6-hexahydrotolylene diisocyante and mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'-diphenyl methane di.isocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and mixtures of these isomers, diphenyl methane 2,4' and/or -4,4'- diisocyanate and naphthylene-1,5-diisocyanate.
Generally, it is also possible in the process according LeA 16,670-G - 5 -~07~7~
to the invention to us~e polyisocyanate prepoly~ers which have been produced from polyisocyanates of hi~her functionality, for example from triphenyl methane-4,4', 4"-tri-isocyanate or from polyphenyl polymethylene polyisocyanates o~ the type obtained by condensing aniline with formaldehyde, followed by phosgenation, and described for example in British Patents 874,430 or 848,671.
The polyisocyan~te prepolymers suitable for the process according to the invention are obtained by the conven-tional polyisocyanate polyaddition process by reacting anexcess of polyisocyanates with the hydrophilic polyether poly-ol~. Depending upon the purpose Eor which the bisulphite addition product is lnt~nded, it may be of advantage to separate the excess polyisocyanate from the polyisocyanate prepolymer after the reaction, (for example, by high vacuum thin-layer evaporation), in order to obtain a polyisocyanate substantially free from monomers. However, this additional operation is not absolutely essential to the process according to the invention.
As already mentioned, the most pre~erred poly-isocyanate prepolymers are those whose polyether component contains from 8 to 30 % of ethylene oxide segments ~CH2-CH2-O-, based on the total content of alkylene oxide segments~ These highly preferred polyisocyanate prepolymers are insolu~le in water because of their low proportion of hydrophilic chain .
segments, but are largely hydrophobic. Accordingly, it is particularly surprising that, in particular, this minimal hydrophilic modification is sufficient in order to be able to work without solvents in accordance with the inYention~
Le~ 16,670-~ - 6 -1~>79~4 ` ~
The polyisocyanate prepolyme~s ùstëd in the process according to the invention may be reacted wit~ aqueous bisulphite solutions bot~ in the presence and in the absence of emulsifying aids. In this respect, the nature of the cation of the bisulphite used is largely unimportant. The only important factor is that water-soluble bisulphites should be used. It is preferred to use sodium, potassium or ammonium bisulphites in the form of their aqueous solutions. When the reactants are mixed, an emulsion is initially formed. Reaction of the isocyanate groups with the bisulphite anions takes place more quickly the more hydrophilic the starting polyether, the emulsion graclually changing into a clear homogeneous solution. Depending upon the polyether polyol and poIyisocyan-ate used, it is also possible to obtain turbid solutions.
Homogeneous bisulphite adduct solutions, which can be further `
diluted with water as required, are thus obtained.
Emulsifiers suitable for use in the process according to the invention include any standard, commercial-grade surface-active substances of the type known and used for the preparation of oil-in-water emulsions. For example, it is possible to use non-ionic compounds containing hydrophobic hydrocarbon units and hydrophilic polyethylene ether glycol units such as, for example, 3-benzyl-4-hydroxy ~iphenyl poly-glycol ethers, or even ionic emulsifiers such as, for example, the sodium salt of a standard commercial-grade paraffin sulphate or mixtures of these emulsifying aids~ The emul- ;
sifiers can be used in quantities of from 0 to 20 % by weight and prefer~bly in quantitles of from 0 to lO ~ by weight~
based on the quantity of the p~ep~l~mer~
LeA 16,670~G ~ 7 1~7979~4 For the purpos~s of the invention r the total con-centration of ~isulphite anions should be sufficient to react with all the isocyanate groups present. Preferably a slight excess should be present. A ratio of moles of bisulphite anions to NCO~equivalents of 1,01 to 1,5:1 is particularly preferred. However, it is,of course, also possible to react only part, for example 60 to 90 %, of the NC0-groups with bisulphite, especially in cases where the presence of excess salt is to be avoided.
The solids content, expressed as bisulphite addition products, of the solutions obtained by the proce3s according to the invention generally amounts to between 1 and 80%, and preerably to between 20 and 60~ In this concentration range, the corresponding polyisocyanate prepolymers may be reacted with aqueous bisulphite anion solutions to form their bisulphite adducts in the absence of organic solvents.
Depending upon requirements and intended application, additives soluble or emulsifiable in water may be stirred into these bisulphite adduct solutions in order to improve their storage properties or to adjust pH, vi~c09ity, clarity, pourability and the like, For example, it is generally advisable to adjust the pH-value of the bisulphite adduct solutions in the acid range, i,e. to pH~ 3, in order to obtain adequate storage stability. This result can be obtained for example, by adding from 0,5 to 5~ by weight, based on the total weight, o~ strong inorganic or organic acids such as, for example, sulphuric acid or paratoluene sulphonic acid.
However, adjustment of the pH-value in the strongly acid range may also be obtained by the addition of hydrogen peroxide, in which case the bisulphite anions present in LeA 16,670~G - 8 -97~
excess are oxidized into the corresponding s~rongly acid bisulphate anions, The bisulphite adduct solutions thus stabilized may be stored almost indefinitely at room temperature.
The aqueous solutions of the bisulphite addition proaucts of polyisocyanate prepolymers obtaIned by the process according to the invention may be used for applications where water~soluble masked polyisocyanate prepolymers are employed.
By virtue of the fact that these bisulphite adducts are readily and economically available, these applications are particularly attractive. ~hus, the bisulphite adduct solutions may be used or example as binders ~or chipboard, as adhesives, impregnating agents Eor plastics, crosslinking agents ~or emul-sions, dispersions or aqueous solutions of isocyanate~reactive precondensates, hardening taking place under heat or steam.
The bisulphite adduct solutions obtained by the pro-cess according to the invention are particularly suitable for use as finishing preparations or sheet-form textiles of nat-ural fibers or synthetics and mixtures thereof. They produce an improvement in the wearing properties, feel, surEace stability, crease resistance~ elasticity and, hence, recovery.
They also improve the scuffing resistance of the articles pro--duced from the sheet-form textiles, and reduce their tendency towards pilling and snagging. The treated textiles obtained show a high level of resistance to washing and dry cleaningt As already known (DOS 2,307~563), the bisulphite adduct solutions can be used ~or improving the dimensional st~bility and also ~or the non-matt finishing of w~Ven ~nd knitted ~abrics of wool or wool mixtures. The bisulphite adducts ohtained by the new process described herein are LeA 16,607-G - 9 -~)79744 distinguished ~y non-matting effects in the finishing of wool comparable with those of, for example, conventional hydro-phobic bisulphite adducts~
To obtain special effects, the bisulphite adducts may be combined with other inishes such as, for example, plastics dispersions (acrylate-based or polyurethane-based, etc.), with plasticizers, crease-proofing agents, nonslip agents, antielectrostatic agents, hydrophilizing agents, hydrophobizing agents, and the like. The resistance to washing and dry cleaning o the textiles obtainable with aerylate and polyurethane dispersions are diskinetly inereased by the addition of the bisulphite adduet solution.
By virtue of their low proportion of hydrophilie eomponents, the preferred produets o~ the proeess aeeording ~: ~
to the invention obtained from the preferred starting materials ~ ;.
referred to above are suffieiently hydrophobie to guarantee favorable finishing effeets, even after repeated washing.
~eA 16,670~G - 10 -~079~
A hydrophilized polyisocyanate prepolymer is prepared by reacting 2500 g of a trimethylol-propane!-started trifunc-tional polyether polyol having an OH-number of 56.8, 17% of whose alkylene oxide segments consist of terminally arranged ethylene oxide segments and 83% consist of propylene oxide segments, with 1270 g of hexamethylene diisocyanate over a period of 2 hours at a temperature of 120C, The excess hexamethylene diisocyanate is substantially separated off by thin layer distillation n vacuo, leaving a polyisocyanate propolymer having an NCO-content of 3.64 ~, 275 g of this NCO-prepolymer are mixed for 10 minutes at 2800 rpm with 28 g o~ a s~and~rd commercial-grade emul~ifier ~olution (50 s~lium aqueous solution of a mixture of equal parts o ~(parain sulfona~e and oxyeth~la~ed ~ony~-pheno~ 28 g of sodium bisulphite and 640 g o water. A stable emulsion is initially formed, gradually changing into a homogeneous solu-tion over a period o 4 hours. A 30 %, slightly turbid com-pletely water-dilutable bisulphite adduct solution is obtained.
A 50 ~ bisulphite adduct solution is prepared by mixing 458 g o the polyisocyanate prepolymer prepared in accordance with Example 1 with 46 g of the emulsifier solution mentioned in Example 1, 46 g of sodium bisulphite and 420 g o water. Ater standing overnight, a clear aqueous bisulphite adduct solution is obtained. It can be diluted with water in any ratio. This solution can be stored indefinitely after 30 g o$ paratoluene sulphonic acid h~ve been stirred in .
Le A 16,670-G
~7~
A 50 % bisulphite adduct solution o~ the same poly-isocy~nate prepolymer as in Example 1 is prepared by reacting 230 g of this prepolymer with 23 g o~ sodium bisulphite in 232 g of w~ter in the absence of an emulsi~:ier. After standing overnight, a turbid, but homogeneous bisulphite adduct solution is obtained.
EXAMPLE 4 ~-Polyisocyanate prepolymers based on the following polyol polyethers and freed from excess hexamethylene diiso-cyanate are produced in accordance with Example 1.
Polyol polyether Prepolymer Functionality OH- Number of ethylene number oxide segments in % based on the to-tal number of alky-lene oxide segments _ , A 3 56.3 20 B 4 56.9 20 E 4 59.~ 25 F 3 56.5 30 G 3 57,6 55 LeA 16,670-G ~ 12 -~079744 Prepolymers A, D, F and G were based on alkoxylated trimethylol-propane; prepolymers B and E were based on a:lkoxylated penta-erythritol; prepolymer C was based on alkoxylated 1,2-propane diol. In all polyetherpolyols the ethylen~oxide segments were terminal. Besides ethylenoxide segment~ all polyetherpolyol~
contained propylene oxide segments exclusively.
The prepolymers A to G may be reacted with sodium bisulphite in accordance with Example 2 and ~ to ~orm corresponding ~0 %
bisulphite adduct solutions.
Le A16 670 - 12 a -~797~
E~AMPLE 5 In order to make cleax the adequately hydrvphilic character of the polyisocyanate prepolymers used, as required in accordance with the invention, the following NCO-prepolymers were prepared on the basis of propoxylated trimethylolprop~m~
with 5 % of terminal ethylene oxide unit~ in the case K and hexamethylene diisocyanate:
Polyol polyether __ _ PrepolymerFunctionality OH- Number of ethylene number oxide segments in %
based on the total number of alkylene oxide segments K 3 55.5 5 These two NCO-prepolymers cannot be con~erted into their bisulphite adducts by the process according to the invention. The reaction mixture undergoes phase separation, the organic phase representing a swollen mass which is totally insoluble in water after only a few hours.
290 g ~0.1 mol) of a trifunctional trimethylol-propane-started polyether polyol having an OH-numbe~ of 58, 25 % of whose alkylene oxide segments consist of ethylene oxide segments and 75 % consist of propylene oxide segments, are reacted for 3 hours at 110C with 100 g (0.6 mol) of hexamethylene diisocyanate. The reaction mixture obtained then has an NCO-value of 9.25 %. 195 g of this untreated polyisocyanate prepolymer axe emulsi~ied with 19.5 g of the emulsi~ier solution mentioned in Example 1~ 57 g of sodium bisulphite in 233 g of water. ~ somewhat turbid~ hon~ogeneou~
3Q aqueous solution of the bisulphite adduct mixture of the - NCO-prepolymer and the excess hexamethylene diisocyanate is LeA 16,670-G -13-., .
; , . ,, ~ .
~:9'7974~
formed after st~,nding ove~ni~ht ,, LeP., 16~670.-~G - 14 -
Generally, it is also possible in the process according LeA 16,670-G - 5 -~07~7~
to the invention to us~e polyisocyanate prepoly~ers which have been produced from polyisocyanates of hi~her functionality, for example from triphenyl methane-4,4', 4"-tri-isocyanate or from polyphenyl polymethylene polyisocyanates o~ the type obtained by condensing aniline with formaldehyde, followed by phosgenation, and described for example in British Patents 874,430 or 848,671.
The polyisocyan~te prepolymers suitable for the process according to the invention are obtained by the conven-tional polyisocyanate polyaddition process by reacting anexcess of polyisocyanates with the hydrophilic polyether poly-ol~. Depending upon the purpose Eor which the bisulphite addition product is lnt~nded, it may be of advantage to separate the excess polyisocyanate from the polyisocyanate prepolymer after the reaction, (for example, by high vacuum thin-layer evaporation), in order to obtain a polyisocyanate substantially free from monomers. However, this additional operation is not absolutely essential to the process according to the invention.
As already mentioned, the most pre~erred poly-isocyanate prepolymers are those whose polyether component contains from 8 to 30 % of ethylene oxide segments ~CH2-CH2-O-, based on the total content of alkylene oxide segments~ These highly preferred polyisocyanate prepolymers are insolu~le in water because of their low proportion of hydrophilic chain .
segments, but are largely hydrophobic. Accordingly, it is particularly surprising that, in particular, this minimal hydrophilic modification is sufficient in order to be able to work without solvents in accordance with the inYention~
Le~ 16,670-~ - 6 -1~>79~4 ` ~
The polyisocyanate prepolyme~s ùstëd in the process according to the invention may be reacted wit~ aqueous bisulphite solutions bot~ in the presence and in the absence of emulsifying aids. In this respect, the nature of the cation of the bisulphite used is largely unimportant. The only important factor is that water-soluble bisulphites should be used. It is preferred to use sodium, potassium or ammonium bisulphites in the form of their aqueous solutions. When the reactants are mixed, an emulsion is initially formed. Reaction of the isocyanate groups with the bisulphite anions takes place more quickly the more hydrophilic the starting polyether, the emulsion graclually changing into a clear homogeneous solution. Depending upon the polyether polyol and poIyisocyan-ate used, it is also possible to obtain turbid solutions.
Homogeneous bisulphite adduct solutions, which can be further `
diluted with water as required, are thus obtained.
Emulsifiers suitable for use in the process according to the invention include any standard, commercial-grade surface-active substances of the type known and used for the preparation of oil-in-water emulsions. For example, it is possible to use non-ionic compounds containing hydrophobic hydrocarbon units and hydrophilic polyethylene ether glycol units such as, for example, 3-benzyl-4-hydroxy ~iphenyl poly-glycol ethers, or even ionic emulsifiers such as, for example, the sodium salt of a standard commercial-grade paraffin sulphate or mixtures of these emulsifying aids~ The emul- ;
sifiers can be used in quantities of from 0 to 20 % by weight and prefer~bly in quantitles of from 0 to lO ~ by weight~
based on the quantity of the p~ep~l~mer~
LeA 16,670~G ~ 7 1~7979~4 For the purpos~s of the invention r the total con-centration of ~isulphite anions should be sufficient to react with all the isocyanate groups present. Preferably a slight excess should be present. A ratio of moles of bisulphite anions to NCO~equivalents of 1,01 to 1,5:1 is particularly preferred. However, it is,of course, also possible to react only part, for example 60 to 90 %, of the NC0-groups with bisulphite, especially in cases where the presence of excess salt is to be avoided.
The solids content, expressed as bisulphite addition products, of the solutions obtained by the proce3s according to the invention generally amounts to between 1 and 80%, and preerably to between 20 and 60~ In this concentration range, the corresponding polyisocyanate prepolymers may be reacted with aqueous bisulphite anion solutions to form their bisulphite adducts in the absence of organic solvents.
Depending upon requirements and intended application, additives soluble or emulsifiable in water may be stirred into these bisulphite adduct solutions in order to improve their storage properties or to adjust pH, vi~c09ity, clarity, pourability and the like, For example, it is generally advisable to adjust the pH-value of the bisulphite adduct solutions in the acid range, i,e. to pH~ 3, in order to obtain adequate storage stability. This result can be obtained for example, by adding from 0,5 to 5~ by weight, based on the total weight, o~ strong inorganic or organic acids such as, for example, sulphuric acid or paratoluene sulphonic acid.
However, adjustment of the pH-value in the strongly acid range may also be obtained by the addition of hydrogen peroxide, in which case the bisulphite anions present in LeA 16,670~G - 8 -97~
excess are oxidized into the corresponding s~rongly acid bisulphate anions, The bisulphite adduct solutions thus stabilized may be stored almost indefinitely at room temperature.
The aqueous solutions of the bisulphite addition proaucts of polyisocyanate prepolymers obtaIned by the process according to the invention may be used for applications where water~soluble masked polyisocyanate prepolymers are employed.
By virtue of the fact that these bisulphite adducts are readily and economically available, these applications are particularly attractive. ~hus, the bisulphite adduct solutions may be used or example as binders ~or chipboard, as adhesives, impregnating agents Eor plastics, crosslinking agents ~or emul-sions, dispersions or aqueous solutions of isocyanate~reactive precondensates, hardening taking place under heat or steam.
The bisulphite adduct solutions obtained by the pro-cess according to the invention are particularly suitable for use as finishing preparations or sheet-form textiles of nat-ural fibers or synthetics and mixtures thereof. They produce an improvement in the wearing properties, feel, surEace stability, crease resistance~ elasticity and, hence, recovery.
They also improve the scuffing resistance of the articles pro--duced from the sheet-form textiles, and reduce their tendency towards pilling and snagging. The treated textiles obtained show a high level of resistance to washing and dry cleaningt As already known (DOS 2,307~563), the bisulphite adduct solutions can be used ~or improving the dimensional st~bility and also ~or the non-matt finishing of w~Ven ~nd knitted ~abrics of wool or wool mixtures. The bisulphite adducts ohtained by the new process described herein are LeA 16,607-G - 9 -~)79744 distinguished ~y non-matting effects in the finishing of wool comparable with those of, for example, conventional hydro-phobic bisulphite adducts~
To obtain special effects, the bisulphite adducts may be combined with other inishes such as, for example, plastics dispersions (acrylate-based or polyurethane-based, etc.), with plasticizers, crease-proofing agents, nonslip agents, antielectrostatic agents, hydrophilizing agents, hydrophobizing agents, and the like. The resistance to washing and dry cleaning o the textiles obtainable with aerylate and polyurethane dispersions are diskinetly inereased by the addition of the bisulphite adduet solution.
By virtue of their low proportion of hydrophilie eomponents, the preferred produets o~ the proeess aeeording ~: ~
to the invention obtained from the preferred starting materials ~ ;.
referred to above are suffieiently hydrophobie to guarantee favorable finishing effeets, even after repeated washing.
~eA 16,670~G - 10 -~079~
A hydrophilized polyisocyanate prepolymer is prepared by reacting 2500 g of a trimethylol-propane!-started trifunc-tional polyether polyol having an OH-number of 56.8, 17% of whose alkylene oxide segments consist of terminally arranged ethylene oxide segments and 83% consist of propylene oxide segments, with 1270 g of hexamethylene diisocyanate over a period of 2 hours at a temperature of 120C, The excess hexamethylene diisocyanate is substantially separated off by thin layer distillation n vacuo, leaving a polyisocyanate propolymer having an NCO-content of 3.64 ~, 275 g of this NCO-prepolymer are mixed for 10 minutes at 2800 rpm with 28 g o~ a s~and~rd commercial-grade emul~ifier ~olution (50 s~lium aqueous solution of a mixture of equal parts o ~(parain sulfona~e and oxyeth~la~ed ~ony~-pheno~ 28 g of sodium bisulphite and 640 g o water. A stable emulsion is initially formed, gradually changing into a homogeneous solu-tion over a period o 4 hours. A 30 %, slightly turbid com-pletely water-dilutable bisulphite adduct solution is obtained.
A 50 ~ bisulphite adduct solution is prepared by mixing 458 g o the polyisocyanate prepolymer prepared in accordance with Example 1 with 46 g of the emulsifier solution mentioned in Example 1, 46 g of sodium bisulphite and 420 g o water. Ater standing overnight, a clear aqueous bisulphite adduct solution is obtained. It can be diluted with water in any ratio. This solution can be stored indefinitely after 30 g o$ paratoluene sulphonic acid h~ve been stirred in .
Le A 16,670-G
~7~
A 50 % bisulphite adduct solution o~ the same poly-isocy~nate prepolymer as in Example 1 is prepared by reacting 230 g of this prepolymer with 23 g o~ sodium bisulphite in 232 g of w~ter in the absence of an emulsi~:ier. After standing overnight, a turbid, but homogeneous bisulphite adduct solution is obtained.
EXAMPLE 4 ~-Polyisocyanate prepolymers based on the following polyol polyethers and freed from excess hexamethylene diiso-cyanate are produced in accordance with Example 1.
Polyol polyether Prepolymer Functionality OH- Number of ethylene number oxide segments in % based on the to-tal number of alky-lene oxide segments _ , A 3 56.3 20 B 4 56.9 20 E 4 59.~ 25 F 3 56.5 30 G 3 57,6 55 LeA 16,670-G ~ 12 -~079744 Prepolymers A, D, F and G were based on alkoxylated trimethylol-propane; prepolymers B and E were based on a:lkoxylated penta-erythritol; prepolymer C was based on alkoxylated 1,2-propane diol. In all polyetherpolyols the ethylen~oxide segments were terminal. Besides ethylenoxide segment~ all polyetherpolyol~
contained propylene oxide segments exclusively.
The prepolymers A to G may be reacted with sodium bisulphite in accordance with Example 2 and ~ to ~orm corresponding ~0 %
bisulphite adduct solutions.
Le A16 670 - 12 a -~797~
E~AMPLE 5 In order to make cleax the adequately hydrvphilic character of the polyisocyanate prepolymers used, as required in accordance with the invention, the following NCO-prepolymers were prepared on the basis of propoxylated trimethylolprop~m~
with 5 % of terminal ethylene oxide unit~ in the case K and hexamethylene diisocyanate:
Polyol polyether __ _ PrepolymerFunctionality OH- Number of ethylene number oxide segments in %
based on the total number of alkylene oxide segments K 3 55.5 5 These two NCO-prepolymers cannot be con~erted into their bisulphite adducts by the process according to the invention. The reaction mixture undergoes phase separation, the organic phase representing a swollen mass which is totally insoluble in water after only a few hours.
290 g ~0.1 mol) of a trifunctional trimethylol-propane-started polyether polyol having an OH-numbe~ of 58, 25 % of whose alkylene oxide segments consist of ethylene oxide segments and 75 % consist of propylene oxide segments, are reacted for 3 hours at 110C with 100 g (0.6 mol) of hexamethylene diisocyanate. The reaction mixture obtained then has an NCO-value of 9.25 %. 195 g of this untreated polyisocyanate prepolymer axe emulsi~ied with 19.5 g of the emulsi~ier solution mentioned in Example 1~ 57 g of sodium bisulphite in 233 g of water. ~ somewhat turbid~ hon~ogeneou~
3Q aqueous solution of the bisulphite adduct mixture of the - NCO-prepolymer and the excess hexamethylene diisocyanate is LeA 16,670-G -13-., .
; , . ,, ~ .
~:9'7974~
formed after st~,nding ove~ni~ht ,, LeP., 16~670.-~G - 14 -
Claims (7)
1. A process for the production of bisulphite addition products of polyisocyanate prepolymers comprising reacting polyisocyanate prepolymers with water soluble bisulphites wherein, a) the polyisocyanate prepolymer used corresponds to the general formula in which A represents a radical of the type obtained by removing the hydroxyl groups from an n-functional polyether polyol, which has a molecular weight of 500 to 8000 and from 8 to 70% of whose alkylene oxide segments consist of ethylene oxide segments;
R represents a divalent radical of the type obtained by removing the isocyanate groups from an organic diisocyanate with a molecular weight in the range from 112 to 1000, and is an integer from 2 to 4, and b) the reaction with bisulphites is carried out in the aqueous phase in the absence of organic solvents.
R represents a divalent radical of the type obtained by removing the isocyanate groups from an organic diisocyanate with a molecular weight in the range from 112 to 1000, and is an integer from 2 to 4, and b) the reaction with bisulphites is carried out in the aqueous phase in the absence of organic solvents.
2. The process of Claim 1, wherein A is such that 8 to 30% of the alkylene oxide segments of the polyether polyol consist of ethylene oxide units -CH2-CH2-O- and 92 to 70%
consist of propylene oxide units -CH2-CH(CH3)-O-.
consist of propylene oxide units -CH2-CH(CH3)-O-.
3. The process of Claim 2, wherein 8 to 30% of the alkylene oxide segments of the polyether polyol consist of terminal ethylene oxide units.
4. The process of Claim 3, wherein said polyether polyol has a molecular weight of from 1000 to 6000.
5. The process of Claim 4, wherein R represents an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having 6 to 15 carbon atoms, an aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
6. The process of Claim 5, wherein n is 2 or 3.
7. The process of Claim 1, wherein the ratio of moles of bisulphite anions to NCO-equivalents is from 1.01:1 to 1.5:1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752543093 DE2543093A1 (en) | 1975-09-26 | 1975-09-26 | PROCESS FOR THE PREPARATION OF BISULFITE ADDITION PRODUCTS FROM POLYISOCYANATE PREPOLYMERS IN WATER |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079744A true CA1079744A (en) | 1980-06-17 |
Family
ID=5957580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA260,646A Expired CA1079744A (en) | 1975-09-26 | 1976-09-07 | Process for the production of bisulphite addition products of polyisocyanate prepolymers in water |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5241695A (en) |
| AU (1) | AU499554B2 (en) |
| BE (1) | BE846556A (en) |
| CA (1) | CA1079744A (en) |
| DE (1) | DE2543093A1 (en) |
| ES (1) | ES451818A1 (en) |
| FR (1) | FR2325671A1 (en) |
| GB (1) | GB1491437A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53136978U (en) * | 1977-04-05 | 1978-10-30 | ||
| JPS5427094A (en) * | 1977-08-03 | 1979-03-01 | Teijin Ltd | Production of suede like raised fabric |
| JPS5928670B2 (en) * | 1977-09-06 | 1984-07-14 | 帝人株式会社 | Method for manufacturing leather-like structure |
| JPS5856580B2 (en) * | 1980-04-25 | 1983-12-15 | 第一工業製薬株式会社 | Method for producing thermoreactive polyurethane emulsion |
| JPS6414376A (en) * | 1988-03-29 | 1989-01-18 | Dai Ichi Kogyo Seiyaku Co Ltd | Method for improving abrasion strength of seat belt or sling belt |
| US4956438A (en) * | 1989-02-08 | 1990-09-11 | The Dow Chemical Company | Bulk polyurethane ionomers |
| JP3136354B2 (en) * | 1997-03-26 | 2001-02-19 | 第一工業製薬株式会社 | Treatment agent for keratin fiber and method for treating keratin fiber using the same |
| EP2726522A1 (en) | 2011-06-29 | 2014-05-07 | LANXESS Deutschland GmbH | Composition based on compounds containing carbamoylsulfonate groups |
| EP2540753A1 (en) * | 2011-06-29 | 2013-01-02 | LANXESS Deutschland GmbH | Compound on the basis of compounds containing carbamoylsulfonate groups |
-
1975
- 1975-09-26 DE DE19752543093 patent/DE2543093A1/en not_active Withdrawn
-
1976
- 1976-09-07 CA CA260,646A patent/CA1079744A/en not_active Expired
- 1976-09-21 AU AU17983/76A patent/AU499554B2/en not_active Expired
- 1976-09-23 GB GB39484/76A patent/GB1491437A/en not_active Expired
- 1976-09-24 ES ES451818A patent/ES451818A1/en not_active Expired
- 1976-09-24 JP JP51113819A patent/JPS5241695A/en active Pending
- 1976-09-24 FR FR7628883A patent/FR2325671A1/en active Granted
- 1976-09-24 BE BE170909A patent/BE846556A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2325671A1 (en) | 1977-04-22 |
| FR2325671B1 (en) | 1979-08-31 |
| DE2543093A1 (en) | 1977-04-07 |
| GB1491437A (en) | 1977-11-09 |
| BE846556A (en) | 1977-03-24 |
| JPS5241695A (en) | 1977-03-31 |
| AU499554B2 (en) | 1979-04-26 |
| ES451818A1 (en) | 1977-11-01 |
| AU1798376A (en) | 1978-04-06 |
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