WO2005044885A1 - Polyurethandispersion mit siloxangruppen - Google Patents
Polyurethandispersion mit siloxangruppen Download PDFInfo
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- WO2005044885A1 WO2005044885A1 PCT/EP2004/012340 EP2004012340W WO2005044885A1 WO 2005044885 A1 WO2005044885 A1 WO 2005044885A1 EP 2004012340 W EP2004012340 W EP 2004012340W WO 2005044885 A1 WO2005044885 A1 WO 2005044885A1
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- Prior art keywords
- group
- polyurethane
- compounds
- isocyanate
- reactive
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- CEYNAJISLOHGHO-UHFFFAOYSA-N C[N](C)(OC)O[N](C)(C)O[N](C)(C)OC Chemical compound C[N](C)(OC)O[N](C)(C)O[N](C)(C)OC CEYNAJISLOHGHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
Definitions
- the invention relates to an aqueous dispersion of a polyurethane obtainable by reacting polyisocyanates and isocyanate-reactive compounds in a miniemulsion, characterized in that the isocyanate-reactive compounds are at least partly polysiloxanes of the formula I.
- R 1 and R 2 independently of one another represent a monovalent hydrocarbon radical with a maximum of 20 carbon atoms, which may also contain heteroatoms such as O or N,
- R 3 and R 4 independently of one another represent a single bond or a divalent hydrocarbon radical with a maximum of 20 carbon atoms, which may optionally also contain heteroatoms such as O or N.
- R 5 and R 6 independently of one another represent a group OH, SH, NH 2 or NHR 7 and R 7 is a monovalent hydrocarbon radical with a maximum of 20 carbon atoms, which may optionally also contain heteroatoms such as O or N.
- n an integer from 1 to 100.
- Polyurethanes are usually produced by reacting their starting compounds (isocyanates and compounds reactive with isocyanates) in an organic solvent.
- a so-called secondary dispersion is obtained by dispersing the polyurethane obtained in water.
- Polyurethane dispersions can also be obtained directly by reacting the starting compounds in the aqueous phase (primary dispersions).
- the starting compounds are emulsified in water in the presence of small amounts of a hydrophobic compound with a water solubility of less than 10 '7 g / l water (at 21 ° C).
- the size of the droplets is adjusted to 50 to 500 nm by known methods. Due to the presence of the hydrophobic substance, the effect of Ostwald ripening (droplet growth up to phase separation) does not occur.
- the starting compounds can be converted into polyurethanes in the droplets with a more or less constant droplet size.
- Primary polyurethane dispersions are obtained in this way.
- Polyurethane dispersions that are as small as possible are desired.
- the polyurethane dispersions should have as few low molecular weight components as possible that can later migrate from the films obtained.
- the polyurethane dispersions should have a high stability and good application properties.
- the object of the present invention was therefore to improve the stability and the performance properties of the polyurethane primary dispersions obtainable in mini-emulsion.
- polyurethane dispersions of the present application are primary dispersions which can be obtained by reacting isocyanates and compounds which are reactive with isocyanate in the aqueous phase in a mini-emulsion, as described in WO 02/064657.
- the isocyanates and the compounds reactive with isocyanate are dissolved in water with the aid of surface-active compounds, e.g. Emulsifiers or protective colloids, emulsified.
- costabilizers have a water solubility of preferably less than 10 "5 , more preferably less than 10 " 6 , very particularly preferably less than 10 "7 g / liter of water at 21 ° C, 1 bar.
- the amount of costabilizers can e.g. 0.1 to 10 parts by weight, in particular 1 to 3 parts by weight per 100 parts by weight of starting compounds.
- Possible costabilizers are e.g. Hydrocarbons such as hexadecane, halogenated hydrocarbons, silanes, siloxanes, hydrophobic oils (olive oil) or starting compounds for the polyurethane, provided that they have the necessary hydrophobicity.
- Hydrocarbons such as hexadecane, halogenated hydrocarbons, silanes, siloxanes, hydrophobic oils (olive oil) or starting compounds for the polyurethane, provided that they have the necessary hydrophobicity.
- the polysiloxanes of the formula I are also suitable.
- Preferred polysiloxanes of the formula I therefore have the solubilities of the costabilizers given above.
- Other costabilizers can then be dispensed with.
- the polyurethane then contains no costabilizers that can migrate from the coatings obtained.
- At least 50% by weight of the costabilizers can be those of the formula I.
- the particle size of the emulsified droplets of the starting compounds is preferably 50 to 500 nm.
- the particle size can be determined by known methods such as homogenization
- High pressure homogenizers or application of ultrasound can be set.
- the reaction of the starting compounds to the polyurethane can be carried out in a known manner at elevated temperature, e.g. from 20 to 120 ° C, preferably 60 to 100 ° C.
- the polyurethane dispersion obtained has a droplet size of preferably 50 to 500 nm, particularly preferably 100 to 300 nm.
- the isocyanate-reactive compounds are at least partially polysiloxanes of the formula I.
- R 1 and R 2 independently of one another represent a monovalent hydrocarbon radical with a maximum of 20 C atoms, which may also contain heteroatoms such as O or N atoms.
- the hydrocarbon radical can contain oxygen atoms, for example as an ether group or hydroxyl group.
- R 1 and R 2 represent an alkyl group, particularly preferably a C do-alkyl group, very particularly preferably a C 1 -C 4 -alkyl group.
- R 1 and R 2 represent a methyl group.
- R 3 and R 4 in the formula I can independently of one another stand for a single bond or a divalent hydrocarbon radical with a maximum of 20 carbon atoms, which may optionally also contain heteroatoms such as O or N.
- R 3 and R 4 stand for a single bond is to be understood in such a way that R 3 and R 4 in formula I above are eliminated and R 5 and R 6 are bound directly to the respective silicon atom.
- R 3 and R 4 represent a hydrocarbon radical, this can contain heteroatoms, for example, as an ether group, hydroxyl group or primary or secondary amino groups.
- R 3 and R 4 are preferably independently of one another a single bond or a CC 2 o -alkyl group, in particular a CrC 10 alkylene group.
- R 3 and R 4 are particularly preferably, independently of one another, a single bond or a CrC- 6 alkylene group.
- R 5 and R 6 independently of one another represent a group OH, SH, NH 2 or NHR 7 .
- R 7 has the meaning of R 1 .
- R 7 represents an alkyl group, particularly preferably a CC 10 alkyl group, very particularly preferably a CC 4 alkyl group.
- R 5 and R 6 preferably represent a hydroxyl group (OH).
- variable n stands for an integer from 1 to 100, preferably from 1 to 50, particularly preferably from 5 to 50 and very particularly preferably from 5 to 40.
- Examples of preferred compounds of the formula I are compounds of the formula II mentioned, in which R 6 and R 5 represent a hydroxyl group and R 1 and R 2 represent a CC 4 alkyl group.
- Preferred compounds of the formula I are also those in which R 6 and R 5 represent a hydroxyl group, R 1 and R 2 represent a CC alkyl group and R 3 and R 4 represent a d-Ce alkylene group.
- Such compounds are, for example under the name Tegomer® ® by Goldschmidt Avail- borrowed.
- the polyurethane is preferably composed of:
- monomers (a) are diisocyanates X (NCO) 2 , where X is an aliphatic hydrocarbon radical with 4 to 15 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical with 6 to 15 carbon atoms or an aromatic phosphate radical with 7 to 15 Carbon atoms.
- diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclo
- Such diisocyanates are commercially available.
- the mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane are particularly important; the mixture of 80 mol% 2,4-diisocyanatotoluene and 20 mol% 2,6-diisocyanatotoluene is particularly suitable.
- mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocyanates such as hexamethylene diisocyanate or IPDI are particularly advantageous, the preferred mixing ratio of the aliphatic to aromatic isocyanates being 4: 1 to 1: 4 is.
- Polyisocyanates with more than 2 isocyanate groups can also be used.
- Isocyanates and biurets e.g. of hexamethylene diisocyanate.
- isocyanates which, in addition to the free isocyanate groups, have other blocked isocyanate groups, e.g. Wear uretdione groups.
- the polyols (b) which can be considered are primarily higher molecular weight polyols (b1) which have a molecular weight of about 500 to 5000, preferably of about 1000 to 3000 g / mol. It is the number average molecular weight Mn. Mn is obtained by determining the number of end groups (OH number).
- the polyols (b1) can be polyester polyols which, for example, from Ulimann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 62 to 65 are known. Polyester polyols are preferably used which are obtained by reacting dihydric alcohols with dihydric carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to prepare the polyester polyols.
- the polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally substituted, for example by halogen atoms, and / or unsaturated.
- Examples include: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydrophthalic anhydride, glutaric acid, malefic acid, malefic acid, malefic acid, malic acid.
- Dicarboxylic acids of the general formula HOOC- (CH 2 ) y - COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
- polyhydric alcohols examples include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1 , 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-dioI, methylpentanediols, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol , Dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
- Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
- Examples include ethylene glycol, butane-1,4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Neopentyl glycol is also preferred.
- polycarbonate diols such as those e.g. can be obtained by reacting phosgene with an excess of the low molecular weight alcohols mentioned as synthesis components for the polyester polyols.
- polyester polyols based on lactone can also be used, which are homopolymers or copolymers of lactones, preferably hydroxyl-containing addition products of lactones with suitable difunctional starter molecules.
- Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also by a C to C 4 - Alkyl radical can be substituted. Examples are e-caprolactone, ⁇ -propiolactone, g-butyroIactone and / or methyl e-caprolactone and mixtures thereof.
- Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the structural component for the polyester polyols.
- the corresponding polymers of e-caprolactone are particularly preferred. Even lower ones Polyester diols or polyether diols can be used as starters for the preparation of the lactone polymers.
- the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones can also be used.
- Polyether polyols are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for example in the presence of BF 3 or by addition of these compounds, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-bis (4-hydroxyphenyl) propane or aniline.
- Polypropylene oxide, polytetrahydrofuran with a molecular weight of 240 to 5000, and especially 500 to 4500 are particularly preferred.
- B 1 ⁇ only includes polyether polyols which consist of less than 20% by weight of ethylene oxide.
- Polyether diols with at least 20% by weight are hydrophilic polyether diols which belong to monomers c).
- polyhydroxyolefins can also be used, preferably those with 2 terminal hydroxyl groups, e.g. , -w-Dihydroxypolybutadien, a, - ⁇ -Dihydroxypolymethacrylester or ⁇ , -w-DihydroxypoIyacrylester as monomers (d).
- Suitable polyols are polyacetals, polysiloxanes and alkyd resins.
- the hardness and the modulus of elasticity of the polyurethanes can be increased if, in addition to the diols (b1), low molecular weight diols (b2) with a molecular weight of about 60 to 500, preferably from 62 to 200 g / mol, are used as the diols (b).
- polyester polyols The structural components of the short-chain alkanediols mentioned for the production of polyester polyols are primarily used as monomers (b2), the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms as well as pentane-1, 5-diol and neopentyl glycol to be favoured.
- polyols b 2 > are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol and pentane -1,5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1, 3-diol, methylpentanediols, also diethylene glycol, triethylene glycol, tetraethylene glycol , Polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
- Alcohols of the general formula HO- (CH 2 ) x -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
- Examples include ethylene glycol, butane-1,4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Neopentyl glycol is also preferred.
- the proportion of the polyols (bi), based on the total amount of the diols (b), is preferably 10 to 100 mol% and the proportion of the monomers (b 2 ), based on the total amount of the diols (b), 0 to 90 mol% ,
- the ratio of the diols (b1) to the monomers (b2) is particularly preferably 0.1: 1 to 5: 1, particularly preferably 0.2: 1 to 2: 1.
- the polyurethanes can comprise monomers (c) which differ from components (a), (b) and (d), the at least one isocyanate group or at least one group which is reactive toward isocyanate groups and moreover at least one hydrophilic group Group or a group that can be converted into a hydrophilic group, included as a structural component.
- hydrophilic monomers can be used, but are not necessary for a stable mini emulsion.
- the content of ionic groups is preferably less than 100 mmol per 1000 g of polyurethane, particularly preferably the polyurethane contains no monomers c).
- the monomers (d), which differ from the monomers (a) to (c) and which may also be constituents of the polyurethane, are generally used for crosslinking or chain extension.
- Degree of branching or networking can serve, e.g. Trimethylolpropane, glycerin or sugar.
- monoalcohols which, in addition to the hydroxyl group, carry a further group which is reactive toward isocyanates, such as monoalcohols with one or more primary and / or secondary amino groups, e.g. Monoethanolamine.
- Polyamines with 2 or more primary and / or secondary amino groups are used above all if the chain extension or crosslinking is to take place in the presence of water, since amines generally react with isocyanates faster than alcohols or water. This is often necessary when aqueous dispersions of cross-linked polyurethanes or high molecular weight polyurethanes are desired.
- Amines suitable for this purpose are generally polyfunctional amines in the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which are at least at least two amino groups selected from the group of primary and secondary amino groups.
- Examples include diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane , 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane.
- diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine
- the amines can also be in blocked form, e.g. in the form of the corresponding ketimines (see e.g. CA-A 1 129 128), ketazines (see e.g. US-A 4269748) or amine salts (see US-A 4 292226).
- Oxazolidines as are used, for example, in US Pat. No. 4,192,937, are masked polyamines which can be used for the production of the polyurethanes according to the invention for chain extension of the prepolymers.
- Monomers (e) which may be used are monoisocyanates, monoalcohols and monoprimary and secondary amines. In general, their proportion is at most 10 mol%, based on the total molar amount of the monomers. These monofunctional compounds usually carry further functional groups such as olefinic groups or carbonyl groups and are used to introduce functional groups into the polyurethane which enable the polyurethane to be dispersed or crosslinked or further polymer-analogously converted. Monomers such as isopropenyl-a, a-dimethylbenzyl isocyanate (TMI) and esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate are suitable for this.
- TMI isopropenyl-a
- TMI a-dimethylbenzyl isocyanate
- esters of acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate
- Coatings with a particularly good property profile are obtained above all if essentially only aliphatic diisocyanates, cycloaliphatic diisocyanates or araliphatic diisocyanates are used as monomers (a).
- the polysiloxanes can be monomers b) or d).
- the content of polysiloxanes improves the stability of the mini emulsion.
- the dispersions obtained are very finely divided.
- the total content of polysiloxanes of the formula I can be up to 90% by weight, in particular up to 70% by weight, particularly preferably up to 50% by weight.
- the content is preferably, for example, 1 to 70% by weight or 2 to 50% by weight, in particular 5 to 30% by weight, based on the polyurethane.
- A is the molar amount of isocyanate groups
- the ratio A: B is very particularly preferably as close as possible to 1: 1.
- the monomers (a) to (e) used usually carry on average 1.5 to 5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or functional groups which can react with isocyanates in an addition reaction.
- the polyaddition of components (a) to (e) to produce the polyurethane is preferably carried out at reaction temperatures of up to 180 ° C, preferably up to 100 ° C under normal pressure, under autogenous pressure or under excess pressure of a foreign gas, e.g. Nitrogen or carbon dioxide.
- a foreign gas e.g. Nitrogen or carbon dioxide.
- the polysiloxanes of the formula I can be prepared from their starting compounds in the same aqueous phase in which the miniemulsion is formed (in situ).
- the preparation can take place before, during or after the production of the mini-emulsion.
- a miniemulsion can be prepared from the starting compounds of the polyurethanes and the conversion to the polysiloxanes and polyurethanes can take place in this miniemulsion.
- the aqueous dispersions can contain further polymers, in particular polymers obtainable by free-radical polymerization. They are preferably so-called hybrid systems.
- the polyurethane and polymer are present in a mixture in the dispersed particles and are preferably partially bound to one another.
- the starting compounds of the polyurethane and the monomers of the polymer obtainable by free-radical polymerization can be polymerized in the same mini-emulsion as, for example, is described in DE-A 10241294 (PF 53898).
- the hybrid systems are then obtained directly by polymerization in mini-emulsion.
- the polymer obtainable by radical polymerization preferably consists of at least 60% by weight of C 1 -C 2 o-alkyl (meth) acrylates.
- the proportion of polyurethane in the hybrid systems can be, for example, 5 to 95% by weight.
- the proportion of the other polymer complements 100% accordingly and can likewise be 5 to 95% by weight.
- the dispersions of the polyurethane (or else hybrid system) according to the invention have good stability.
- the dispersion particles obtained are more finely divided compared to polyurethanes without these polysiloxanes.
- the dispersions have good application properties, in particular good adhesion to customary substances made of metal, plastic or wood.
- the dispersions are well suited as binders for adhesives, sealants or coatings.
- the dispersions are also suitable as binders for cosmetic preparations, for example hairspray, styling gel, nail polish, make-up or shampoo.
- the content of the polysiloxanes of the formula I is preferably 0.1 to 20% by weight, particularly preferably at least 0.5 to 10% by weight,
- foam stabilizers for example for polyurethane foams.
- a content of at least 10% by weight, particularly preferably at least 20% by weight and a maximum of 80% by weight, particularly preferably a maximum of 60% by weight, of polysiloxane of the formula I in the polyurethane is advantageous.
- IPDI isophorone diisocyanate
- the monomer mixture consists of 1.3456 g IPDI and 4.6544 g Tegomer 2111.
- 2,842 g PDMS, 0.158 g IPDI and 3 g styrene are used to produce the mini emulsion.
- 25 mg of dioctyltin dilaurate are added as a catalyst, then the miniemulsion is produced by ultrasound for two minutes (Branson Sonifier W450 Digital) at an amplitude of 90% (Branson sonifier W450) with ice cooling.
- the temperature is then raised to 60 ° C.
- the temperature is raised to 72 ° C and 40 mg of KPS are added.
- the reaction is complete after 4 hours.
- Particle size 75 nm
- Example 11 comparative example: PolyTHF1000 instead of Tegomer H-Si 2111: 2.85 g PolyTHF1000, 2.06 g melted cyclohexanedimethanol, 2.99 g polyetherol Lupranol VP 9343 and 3.96 g IPDI are mixed and with 26.9 g Demineralized water containing 1.6 g Steinapol NLS stirred with a magnetic stirrer. Then sonicate with a Branson Sonifier W 450 for 90 s at 100% amplitude and 50% pulse while cooling with ice. The sample is mixed with 2 drops of DBTL and heated to 60 ° C for 4 h. After filtration over 40 my, the solids content is 28.6%, particle size: 217 nm
- polyester diol (OHZ 105 mg KOH / g), 11.6 g 3-methyl-pentanediol-1.5; 1.6 g of hexadecane and 27.5 g of IPDI are mixed and stirred with 108.4 g of demineralized water and 17.4 g of Steinapol NLS at RT using a magnetic stirrer. Then sonicate with a Branson Sonifier W 450 for 4 min at 100% amplitude and 50% pulse while cooling with ice. 6 drops of DBTL are added to the sample and the mixture is heated to 60 ° C. for 5 h. After filtration over 40 my, the solids content is 31% particle size: 294 nm
- Example 16 32.9 g of Tegomer H-Si 2111, 7.2 g of butanediol 1, 4 and 26.6 g of IPDI are mixed and mixed with 108.4 g of demineralized water and 17.4 g of Steinapol NLS at RT with a magnetic stirrer touched. Then with a Branson Sonifier W 450 4 min. sonicated at 100% amplitude and 50% pulse under ice cooling. 6 drops of DBTL are added to the sample and the mixture is heated to 60 ° C. for 5 h. After filtration over 40 my, the solids content is 29% particle size: 269 nm
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04791093A EP1682594A1 (de) | 2003-11-04 | 2004-10-30 | Polyurethandispersion mit siloxangruppen |
US10/578,178 US20070112129A1 (en) | 2003-11-04 | 2004-10-30 | Polyurethane dispersion comprising siloxane groups |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10352101A DE10352101A1 (de) | 2003-11-04 | 2003-11-04 | Polyurethandispersion mit Siloxangruppen |
DE10352101.1 | 2003-11-04 |
Publications (1)
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WO2005044885A1 true WO2005044885A1 (de) | 2005-05-19 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2004/012340 WO2005044885A1 (de) | 2003-11-04 | 2004-10-30 | Polyurethandispersion mit siloxangruppen |
Country Status (5)
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US (1) | US20070112129A1 (de) |
EP (1) | EP1682594A1 (de) |
CN (1) | CN1878807A (de) |
DE (1) | DE10352101A1 (de) |
WO (1) | WO2005044885A1 (de) |
Families Citing this family (9)
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CN101307181B (zh) * | 2008-07-02 | 2010-06-02 | 天津大学 | 阴离子聚氨酯与氨基硅油复合的水分散液及其制备和应用 |
US8633292B2 (en) * | 2009-03-26 | 2014-01-21 | Signet Armorlite | Polyurethane-based photochromic optical materials |
WO2010143518A1 (ja) * | 2009-06-12 | 2010-12-16 | Dic株式会社 | インクジェット印刷インク用バインダー、それを含むインクジェット印刷用インク及び印刷物 |
CN102199345B (zh) * | 2011-03-28 | 2012-08-08 | 刘春博 | 可钻滤砂管用聚硅氧烷改性聚氨酯及其制备方法与应用 |
US9303125B2 (en) | 2012-03-01 | 2016-04-05 | Dow Corning Corporation | Method of forming particles from an oil-in-water emulsion |
US8716396B2 (en) * | 2012-04-19 | 2014-05-06 | Arrowstar Llc | Nonfluorinated polyurethanes and methods of making and using thereof |
CN108276551A (zh) * | 2017-12-26 | 2018-07-13 | 合肥科天水性科技有限责任公司 | 一种生物基多重交联改性水性聚氨酯树脂及其制备方法和用途 |
CA3084352A1 (en) * | 2018-04-18 | 2019-10-24 | Encapsys, Llc | Aqueous polyurethane microgel dispersion |
NL2022219B1 (en) | 2018-12-17 | 2020-07-03 | Stahl Int B V | Process to prepare aqueous polyurethane dispersions in which the polyurethane includes polysiloxane as side chain |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1248287B (de) * | 1965-12-18 | 1967-08-24 | Bayer Ag | Verfahren zur Herstellung von Formkoerpern aus waessrigen Polyurethandispersionen |
DE10020195A1 (de) * | 2000-04-25 | 2001-10-31 | Basf Ag | PU-modifizierte Miniemulsionspolymerisate |
WO2002055576A2 (en) * | 2000-11-02 | 2002-07-18 | Dow Global Technologies Inc. | Process for preparing aqueous dispersions of hybrid polyurethane particles |
EP1354902A1 (de) * | 2002-04-17 | 2003-10-22 | Goldschmidt AG | Wässrige Polysiloxan-Polyurethan-Dispersion, ihre Herstellung und Verwendung in Beschichtungsmitteln |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4331555A (en) * | 1980-09-29 | 1982-05-25 | Union Carbide Corporation | Use of organosiloxane compositions as foam stabilizers in flexible polyester polyurethane foam |
AU2877792A (en) * | 1991-10-22 | 1993-05-21 | Dap Products Inc. | Moisture curable silicone-urethane copolymer sealants |
DE4139090A1 (de) * | 1991-11-28 | 1993-06-03 | Stockhausen Chem Fab Gmbh | Verwendung von copolymerisaten mit polysiloxan-einheiten zur behandlung von leder und pelzen |
FR2708199B1 (fr) * | 1993-07-28 | 1995-09-01 | Oreal | Nouvelles compositions cosmétiques et utilisations. |
GB9400663D0 (en) * | 1994-01-14 | 1994-03-09 | Ucb Sa | Aqueous polyurethane resin compositions |
FR2736057B1 (fr) * | 1995-06-27 | 1997-08-01 | Oreal | Polycondensats sequences polyurethanes et/ou polyurees a greffons silicones, compositions cosmetiques les contenant et utilisations |
FR2743297B1 (fr) * | 1996-01-05 | 1998-03-13 | Oreal | Composition cosmetiques a base de polycondensats ionisables multisequences polysiloxane/polyurethane et/ou polyuree en solution et utilisation |
DE19618389A1 (de) * | 1996-05-08 | 1997-11-13 | Basf Ag | Wässrige Dispersionen enthaltend ein Polyurethan, ein Polyisocyanat und ein tertiäres Alkanolamin |
DE19849891A1 (de) * | 1997-12-08 | 1999-06-10 | Basf Ag | Mit Polyurethandispersionen gebundene sterile Vliesstoffe |
DE19838851A1 (de) * | 1998-08-26 | 2000-03-02 | Basf Ag | Kosmetisches Mittel |
US6455140B1 (en) * | 1999-01-13 | 2002-09-24 | 3M Innovative Properties Company | Visible mirror film glitter |
US6737069B1 (en) * | 1999-08-10 | 2004-05-18 | National Starch And Chemical Investment Holding Corporation | Cosmetic compositions containing amphoteric polyurethanes |
US6342094B1 (en) * | 2000-01-31 | 2002-01-29 | Hewlett-Packard Company | Miniemulsion techniques for ink jet inks |
US6617391B2 (en) * | 2000-07-18 | 2003-09-09 | Goldschmidt Ag | Linear polydialkylorganosiloxanes having polyoxyalkylene and amino-functional groups which additionally have terminal alkoxy groups |
DE10107494A1 (de) * | 2001-02-15 | 2002-08-22 | Basf Ag | Wäßrige Polyurethandispersion |
DE10206123A1 (de) * | 2002-02-14 | 2003-09-04 | Wacker Chemie Gmbh | Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymer aufweisende textile Gebilde |
DE10212658A1 (de) * | 2002-03-21 | 2003-10-16 | Consortium Elektrochem Ind | Siliconhaltige Schaumstoffe |
-
2003
- 2003-11-04 DE DE10352101A patent/DE10352101A1/de not_active Withdrawn
-
2004
- 2004-10-30 WO PCT/EP2004/012340 patent/WO2005044885A1/de active Application Filing
- 2004-10-30 EP EP04791093A patent/EP1682594A1/de not_active Withdrawn
- 2004-10-30 CN CNA2004800329136A patent/CN1878807A/zh active Pending
- 2004-10-30 US US10/578,178 patent/US20070112129A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1248287B (de) * | 1965-12-18 | 1967-08-24 | Bayer Ag | Verfahren zur Herstellung von Formkoerpern aus waessrigen Polyurethandispersionen |
DE10020195A1 (de) * | 2000-04-25 | 2001-10-31 | Basf Ag | PU-modifizierte Miniemulsionspolymerisate |
WO2002055576A2 (en) * | 2000-11-02 | 2002-07-18 | Dow Global Technologies Inc. | Process for preparing aqueous dispersions of hybrid polyurethane particles |
EP1354902A1 (de) * | 2002-04-17 | 2003-10-22 | Goldschmidt AG | Wässrige Polysiloxan-Polyurethan-Dispersion, ihre Herstellung und Verwendung in Beschichtungsmitteln |
Also Published As
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US20070112129A1 (en) | 2007-05-17 |
DE10352101A1 (de) | 2005-06-02 |
EP1682594A1 (de) | 2006-07-26 |
CN1878807A (zh) | 2006-12-13 |
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