Classifications

• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0834—Compounds having one or more O-Si linkage
  • C07F7/0838—Compounds with one or more Si-O-Si sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B69/00—Dyes not provided for by a single group of this subclass
  • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds

Definitions

• the invention relates to functionalized silicone compounds to which additional coloring molecules are covalently attached, processes for their preparation and the use of these colored silicone compounds.
• the present invention relates to organopolysiloxanes containing dye residues containing units of the general formula
• R can be the same or different and represents a hydrogen atom or a monovalent optionally substituted hydrocarbon radical
• R 1 can be the same or different and means hydrogen atom or monovalent, SiC-bonded hydrocarbon radical
• R can be the same or different and means substituted monovalent, SiC-bonded hydrocarbon radical
• A can be the same or different and means sulfonic acid and / or sulfonate group-containing, water-soluble, organic dye residue and / or their complex compound with metals
• a is 0, 1, 2 or 3
• b is 0, 1, 2 or 3
• d is 0, 1, 2 or 3, preferably 0 or 1
• c is 0, 1 or 2, preferably 0 or 1, with the proviso that the sum of a, b, c and d is less than or equal to 3, the organopolysiloxanes have at least one radical A per molecule and in the units of the formula (I) with c different from 0 d is 0.
• organopolysiloxanes is intended to include both polymeric and dimeric and oligomeric siloxanes.
• the radical R is preferably hydrogen atom and hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably hydrocarbon radicals having 1 to 6 carbon atoms, in particular the methyl radical.
• radical R examples include alkyl radicals, such as the methyl,
• the radical R is preferably a hydrogen atom or optionally substituted alkyl radicals having 1 to 12 carbon atoms, which can be interrupted by oxygen atoms, particularly preferably the hydrogen atom, the methyl and the ethyl radical.
• radical R examples are the examples given for R.
• the radical R is preferably substituted hydrocarbon radicals having 1 to 18 carbon atoms, particularly preferably hydrocarbon radicals having 1 to 18 carbon atoms which are substituted by amino groups and / or their derivatives, mercapto groups and carboxylic acid groups and / or their derivatives.
• radical R examples include hydrocarbon radicals substituted with amino groups and their derivatives, such as, for example, aminopropyl, aminopropylaminoethyl, cyclohexylaminopropyl or acetylated aminopropyl radicals, hydrocarbon radicals substituted with mercapto groups, such as, for example, the mercapto-n-propyl radical, hydrocarbon radicals substituted with epoxy groups, for example Propyglycidetherrest, hydrocarbon residues substituted with acrylate or methacrylate groups, such as n-propylacrylic acid ester residue and n-propyl-methacrylic acid ester residue, hydrocarbon residues substituted with carboxylic acid groups or their derivatives, such as with alkanoic acid residues, such as the acetic acid residue, the butyric acid residue, the undecenoic acid residue with acid anhydrides, such as the succinic anhydride residue, with esters, such as the undecensilyl ester residue, hydrocarbon radical
• Residue A is preferably water-soluble organic dye residues containing sulfonic acid groups or sulfonate groups with azo groups or quinone groups and / or their complex compound with metals.
• the radical A can be monovalent or polyvalent radicals, so that radical A can also link several sil (oxan) yl radicals to one another.
• X is a divalent radical of the formula -YR -, where Y is a radical -0-, -S-, -NH- or -NR -, R 4 is a divalent optionally substituted hydrocarbon radical and R is a monovalent optionally substituted hydrocarbon radical, with the proviso that in the compound according to the invention Y is connected to the dye residue and R to the silicon atom in question.
• the radical R is preferably divalent optionally substituted linear hydrocarbon radicals having 1 to 30 carbon atoms which can be interrupted by heteroatoms, such as nitrogen, sulfur or oxygen, optionally substituted alkylene radicals having 1 to 10 carbon atoms being particularly preferred, such as e.g. Methylene, ethylene, propylene and butylene residue, aminopropylaminoethyl residue, ethylene oxide residue and alkylene groups substituted with a maximum of 4 sugar residues.
• the radical R is preferably monovalent, optionally substituted hydrocarbon radicals, optionally substituted alkyl radicals having 1 to 10 carbon atoms being particularly preferred.
• R examples of R are the methyl, ethyl, propyl, butyl,
• V has the meaning of halogen, sulfato or thiosulfate residue
• X stands for halogen, such as fluorine, chlorine or bromine, in particular, chlorine radicals, and R represents hydrogen atom or organic radical.
• dye molecules used according to the invention are:
• the dyes used according to the invention are commercially available products or can be prepared by methods customary in organic chemistry.
• the dyes mentioned as specific examples are commercially available from DYE Stars Darmstadt (Remazol ® series) or from Reactasil.
• the organopolysiloxanes according to the invention are preferably those which consist of units of the formula (I), the sum of all siloxane units in preferably at least 50%, particularly preferably in at least 80%, in particular in at least 90% a + b + c + d is 2, with the proviso that at least one radical A is present per molecule and in units of the formula (I) with c different from 0 d is 0.
• organopolysiloxanes according to the invention are particularly preferably those of the formula (II)
• R, R and A have the meaning given above, f is 0 or 1, preferably 1 j is 0 or 1, preferably 1 m is 0, 1 or 2, preferably 0, e is 0 or an integer of 1 to 100, g is 0 or an integer from 1 to 100, h is 0 or an integer from 1 to 1000 and k is an integer from 1 to 100, with the proviso that (etg) ⁇ (h + k) / 10 and that the units specified in formula (II) can be statistically distributed in the siloxane molecule.
• the viscosities of the organopolysiloxanes according to the invention range from preferably 100 mm / s to wax-like substances which are solid at room temperature.
• the viscosity range between 1,000 mm / s and 20,000 mm / s and the range of the organopolysiloxanes which are wax-like at room temperature are particularly preferred.
• the dye content of the organopolysiloxanes according to the invention is preferably 0.1 to 80 percent by weight (based on the total weight), particularly preferably 1 to 15 percent by weight, in particular 5 to 10 percent by weight.
• organopolysiloxanes according to the invention are, where Me is methyl:
• the colored organopolysiloxanes according to the invention have the advantage that, in addition to the covalently bound dye residues, they can have other functional groups which, in addition to the color, give the compound further properties, such as e.g. Substantivity and hydrophobicity.
• the colored organopolysiloxanes according to the invention have the further advantage that they are stable, i.e. at room temperature and under the pressure of the surrounding atmosphere are stable for at least 1 year.
• Another advantage of the colored organopolysiloxanes according to the invention is that hydrophobic systems, such as silicone rubber compositions, can be colored in a very simple manner.
• the colored organopolysiloxanes according to the invention containing units of the general formula (I) can now be prepared in different ways depending on the functional groups of the dye molecules.
• Another object of the present invention is a process for the preparation of organopolysiloxanes containing dye residues, characterized in that water-soluble organic dyes containing sulfonic acids and / or sulfonate groups and / or their complex compound with metals having reactive groups covalently attached to the dye molecule are selected from the group consisting of halogenated triazine radicals or radicals of the formula -S0 2 - (CH 2 ) 2 -V with V equal to the meaning given above and any intermediates which may be formed during the reaction with amino, carboxy, mercapto, anhydride , organopolysiloxanes having prim, sec, tert-carbinol, glycosido, phenol, epoxy, aldehyde, polyglycol, phosphonato, silalactone, acrylate and / or methacrylate groups.
• organopolysiloxanes used according to the invention can be any organopolysiloxanes known to date, such as those composed of units of the formula
• R can be identical or different and an amino, carboxy, mercapto, anhydride, prim, sec, tert-carbinol, glycosido -, phenol, epoxy, aldehyde, polyglycol, phosphonato, silalactone, acrylate or methacrylate and c "has a meaning given for c, with the proviso that the sum of a, b, c "and d is less than or equal to 3, the organopolysiloxanes have at least one radical R" per molecule and in the units of the formula (I ") with c" different from 0 d is 0.
• radicals R are the radicals mentioned above for the radical R, hydrocarbon radicals substituted with amino groups and their derivatives, such as aminopropyl, aminopropylaminoethyl radical and cyclohexylaminopropyl radical, and hydrocarbon radicals substituted with carboxylic acid groups or their derivatives, such as e.g.
• alkanoic acid residues such as the acetic acid residue, the butyric acid residue, the undecenoic acid residue
• acid anhydrides such as the succinic anhydride residue
• esters such as the undecensilyl ester residue
• hydrocarbon residues substituted with amino groups and their derivatives such as aminopropyl-, aminopropylhexinoaminoethyl and cyclo are particularly preferred.
• the preferred and particularly preferred species of the organopolysiloxanes used according to the invention are of course analogous structures as described above in connection with the organopolysiloxanes according to the invention.
• the organopolysiloxanes used according to the invention have a viscosity of preferably 50 to 50,000 mm / s, particularly preferably 200 to 15,000 mm / s, in each case at 25 ° C.
• organopolysiloxanes used with particular preference according to the invention are in particular those with an amine number of 0.01 to 10.0, the amine number being the number corresponds to the ml of 1-n-HCl required to neutralize 1 g of substance.
• organosilicon compounds used according to the invention are commercially available products or can be prepared by methods customary in silicon chemistry.
• reaction according to the invention can be a nucleophilic addition reaction, nucleophilic substitution on the aromatic heterocycle and the sulfoimide formation, which should be specified in the following examples:
• dye is used in amounts of preferably 0.1 to 80 percent by weight, particularly preferably 0.1 to 10 percent by weight, in particular 2 to 5 percent by weight, in each case based on the total weight of organopolysiloxane used, the molar amount of dye being at most 95 mol% of those described above functional groups in the organopolysiloxane used according to the invention may be.
• reaction according to the invention can be carried out in the presence or absence of catalysts, the former being preferred.
• catalyst it can be acidic as well as basic catalysts, with acidic catalysts being preferred.
• bases which can be used as a catalyst in the reaction according to the invention are primary and secondary amines, alkali metal alkoxides in aqueous solution and alkaline earth metal hydroxides and oxides in aqueous solution.
• acids that can be used as a catalyst in the reaction according to the invention are mineral acids and carboxylic acids, preferably carboxylic acids with C Q to Cg alkyl radical, particularly preferably formic acid and acetic acid.
• the acids can be used in bulk or in solution. If they are used in solution, water is particularly preferably the solvent.
• the catalyst can also be covalently bound to the organopolysiloxane used according to the invention, such as carboxylic acids or carboxylic anhydrides, succinic anhydride being particularly preferred.
• the acidic catalyst which is covalently bound to the organopolysiloxane, can also act as a reaction partner of the reactive dye, such as. B. carboxylic acids or their anhydrides, e.g. succinic anhydride.
• the amounts are preferably 0.1 to 1 percent by weight, based on the total weight of the starting materials.
• the reaction according to the invention can now be carried out as a one-phase reaction or as a two-phase reaction, the latter also being emulsions.
• reaction of dye with organopolysiloxane is carried out using immiscible solvents for one or both reactants, so that two phases are formed by means of suitable mixing methods without catalyst or with basic or acid catalysis, acid catalysis being particularly preferred.
• the reaction according to method A according to the invention is carried out at a temperature of preferably 0 to 200 ° C., particularly preferably 50 to 160 ° C., in particular 80 to 130 ° C., and preferably at a pressure of the surrounding atmosphere, that is to say at 900 to 1100 hPa .
• the reaction times are preferably between 5 minutes and 2 hours, particularly preferably between 5 and 15 minutes.
• Suitable solvents for the dye used according to the invention are organic aprotic solvents, water, aqueous electrolyte solutions, aqueous alkalis, aqueous acids or organic-aqueous mixtures of the aforementioned aromatic organic solvents with aqueous Systems.
• Preferred aprotic, organic solvents are dimethylformamide and dimethyl sulfoxide.
• Preferred aqueous systems are aqueous alkalis and aqueous acids, with aqueous acids being particularly preferred.
• the solvent in which the dye used according to the invention is dissolved is preferably water, aqueous bases and aqueous acids, with aqueous acids, such as, for example, an aqueous 1-30% by weight formic acid solution, being particularly preferred.
• Suitable solvents for the organopolysiloxane used according to the invention are organic, aprotic solvents which are inert to the reactants, such as toluene, hexane, cyclohexane or dimeric, oligomeric or polymeric siloxanes, such as hexamethyldisiloxane, which do not mix with the solvent or the solvent mixture of the reactive dye used according to the invention are miscible.
• immiscibility of solvents is understood to mean a miscibility of up to 1% by weight at 25 ° C. and the pressure of the surrounding atmosphere.
• process A it is possible to use all known, also continuous, mixing methods which homogenize the two immiscible phases as much as possible and thus create a large internal reaction area.
• Suitable methods for dispersing the phases are agitators of all kinds, preferably ultrasound probes or baths and high-speed agitators, high-speed agitators such as e.g. Ultra-Turrax stirrer (Janke
• Process A according to the invention has the advantage that the colored organopolysiloxanes obtained according to the invention no longer have to be worked up.
• Process A also has the advantage that it can be carried out without a solubilizer, such as primary alcohol, and without surface-active substances, such as surfactants.
• Two-phase reaction with reactions of dispersions such as emulsions or microemulsions
• the conversion of the starting compounds into the organopolysiloxanes according to the invention can also be carried out in emulsion or microemulsion, the organopolysiloxane used according to the invention being the dispersed phase in the aqueous liquor and being stabilized in a known manner, for example by means of suitable emulsifiers.
• the reactive dye used according to the invention is dissolved in a suitable solvent, preferably water or aqueous, dilute electrolyte solutions, and added to the dispersion or vice versa.
• the reaction also proceeds either without a catalyst, or with basic or acid catalysis. The above applies to the catalysts.
• the reaction according to method B according to the invention is carried out at a temperature of preferably 0 to 100 ° C., particularly preferably at 10 to 50 ° C., in particular at 20 to 35 ° C., and preferably at a pressure of the surrounding atmosphere, that is to say at 900 to 1100 hPa , carried out.
• the reaction times are preferably between one and 200 hours, and the dispersion can be mixed.
• the dispersion containing the organopolysiloxane used according to the invention can be prepared in any desired and previously known manner.
• all emulsifiers that have hitherto been used to prepare dispersions such as nonionic, anionic, cationic or amphoteric emulsifiers, can be used.
• the dispersions used according to the invention preferably have a siloxane content of 1 to 30 percent by weight.
• Organosiloxane oils containing aminoalkyl groups and having a viscosity between 100 and 10000 mm / s and an amine number between 0.2 and 2 are particularly suitable as the dispersed siloxane phase.
• the dispersion containing the organopolysiloxanes according to the invention can be worked up by methods known per se, for example by breaking the dispersion with concentrated electrolyte solutions or by adding water-soluble, polar solvents such as acetone.
• the oil phase is then preferably separated off and then purified by repeated shaking with concentrated electrolyte solutions, such as, for example, with 20% by weight sodium chloride solution.
• concentrated electrolyte solutions such as, for example, with 20% by weight sodium chloride solution.
• the organopolysiloxanes according to the invention thus obtained are then preferably dried.
• Process B according to the invention has the advantage that the colored organopolysiloxanes produced according to the invention are obtained directly in the form of emulsions and as such directly, depending on
• the conversion of the starting compounds into the colored organopolysiloxanes according to the invention can also be carried out homogeneously.
• the reactive dye used according to the invention and the organopolysiloxane used according to the invention are dissolved in a common aprotic organic solvent which is inert to the reactants or in aqueous-organic solvent mixtures, preferably in dimethylformamide and dimethyl sulfoxide, particularly preferably dimethyl sulfoxide.
• the reaction also proceeds either without a catalyst, or with basic or acid catalysis, as already described above.
• the reaction according to method C according to the invention is carried out at a temperature of preferably 5 to 100 ° C., particularly preferably at 60 to 80 ° C., and preferably at a pressure of the surrounding atmosphere, that is to say at 900 to 1100 hPa.
• the reaction times are preferably 15 to 300 minutes.
• the colored organopolysiloxanes according to the invention can then e.g. can be isolated by simply distilling off the solvent or the solvent mixture.
• Process C according to the invention has the advantage that it can be carried out in a simple manner using simple apparatus.
• organopolysiloxanes according to the invention are preferably carried out by process A or B, particularly preferably by process A, in each case optionally in combination with an equilibration step.
• organosiloxanes containing dye residues obtained by the process according to the invention can be combined with organopolysiloxanes (1), preferably selected from the group consisting of linear organopolysiloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, cyclic organopolysiloxanes and copolymers of anane polymers from and monoorganosiloxane units can be equilibrated, for example by setting the desired molecular weight and the targeted distribution of the dye groups in the molecule and, if necessary, the introduction of further functionalities is made possible.
• organopolysiloxanes (1) preferably selected from the group consisting of linear organopolysiloxanes containing terminal triorganosiloxy groups, linear organopolysiloxanes containing terminal hydroxyl groups, cyclic organopolysiloxanes and copolymers of anane polymers from and monoorganosilox
• Preferred linear organopolysiloxanes having triorganosiloxy groups are those of the formula
• R can be the same or different and has a meaning given for R, u is 0 or an integer from 1 to 1500, v is 0 or an integer from 1 to 1500 and t is an integer of 3 to 12.
• the quantitative ratios of the organopolysiloxanes (1) used in the equilibration, if any, and organopolysiloxanes containing dye groups prepared according to the invention are determined only by the desired proportion of the dye groups in the organopolysiloxanes produced in the optionally performed equilibration, and by the desired average chain length.
• basic catalysts which promote the equilibration are preferably used. Examples of such catalysts are benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, alkali hydroxide and alkaline earth hydroxide in methanolic solution, and silanolates.
• Alkali metal hydroxides are preferred, which are used in amounts of preferably 50 to 10,000 ppm by weight (parts per million), in particular 500 to 2000 ppm by weight, in each case based on the total weight of the organosilicon compounds used.
• the equilibration which is carried out is preferably carried out at 50 to 150 ° C., particularly preferably 70 to 120 ° C., in particular 80 to 100 ° C., and preferably at the pressure of the surrounding atmosphere, that is to say between 900 and 1100 hPa. However, it can also be carried out at higher or lower pressures.
• the equilibration can, if desired, be carried out in a water-immiscible solvent such as toluene, but this is not preferred. However, if such organic solvents are used, amounts of 5 to 20 percent by weight, based on the total weight of the organosilicon compounds used, are preferred.
• the catalyst Before working up the mixture obtained in the equilibration according to the invention, the catalyst can be rendered ineffective.
• organopolysiloxanes according to the invention with covalently bound dye molecules in bulk, in solution or in the form of dispersions can be used wherever at the same time the properties of organopolysiloxanes, such as Hydrophobization, dirt repellency, protection, soft feel, etc., combined with coloring are required, such as in the field of cosmetic applications, in particular in hair care, when finishing, dyeing and caring for textiles, in paint care, such as for car paints.
• organopolysiloxanes according to the invention can be used for coloring organosilicon compounds of all kinds, since there is no incompatibility with other organosilicon compounds due to the covalent attachment of the dye to a siloxane molecule.
• silicone oils, crosslinkable silicone rubber compositions can be colored with a homogeneously distributed, molecularly present dye that is no longer extractable.
• Examples lb, lc, le, lf and li a dye containing sulfato-vinylsulfonic acid groups is used, which is commercially available under the trade name Remazol
• Siloxane A Me 3 SiO (Me 2 SiO) 2 oo (MeSiO) 4 SiMe 3
• 100 g of the acidic dispersion used with a pH of 4.5 contain 2% by weight of formic acid, 17% by weight of aminoethylaminopropyl-functionalized organopolysiloxane with trimethylsilyl end groups and an average chain length of approx. 150 and that given in Table 3 Amine number and approx. 10% by weight of ethoxylated fatty acid with a chain length distribution between 12 and 18 carbon atoms.
• the amount of dye given in Table 3, dissolved in 5 g of water, is added to this dispersion at room temperature with stirring.
• the dispersion obtained in each case is then stored for 7 days at room temperature and then with 20% sodium chloride solution Broken.
• the isolated, colored silicone oil thus obtained is washed 10 times with 100 g of 20% NaCl solution.
• the residual dye content of the silicone oils that can no longer be washed out is then determined by UV-Vis measurement.
• ® is available under the name Levafix Brill. -Red, is placed in 9 g of dimethyl sulfoxide.
• 0.128 g of an aqueous 85% formic acid solution are metered in as catalyst.
• the reaction mixture is heated to 80 ° C for one hour. 5
• the solvent is then distilled off at 80 ° C. and under full vacuum. 9.2 g of a red silicone oil with a viscosity of 12300 mm / s are obtained, which is water-soluble.
• 1 g of the reaction product is dissolved in 25 g of an oligomeric siloxane and extracted with 42 g of a 20% by weight sodium chloride solution.
• the washable portion of all samples is no longer detectable by UV spectroscopy, i.e. the extractable dye content is less than 0.1 mg / 1.

Priority Applications (7)

Applications Claiming Priority (2)

Publications (1)

Family

ID=7823290

Family Applications (1)

Country Status (9)

Cited By (1)

Families Citing this family (15)

Citations (6)

Family Cites Families (5)

• 1997
  • 1997-03-13 DE DE19710461A patent/DE19710461A1/de not_active Withdrawn
• 1998
  • 1998-03-12 AT AT98913705T patent/ATE198901T1/de not_active IP Right Cessation
  • 1998-03-12 DE DE59800451T patent/DE59800451D1/de not_active Expired - Lifetime
  • 1998-03-12 JP JP53922298A patent/JP3523272B2/ja not_active Expired - Fee Related
  • 1998-03-12 ES ES98913705T patent/ES2154493T3/es not_active Expired - Lifetime
  • 1998-03-12 EP EP98913705A patent/EP0960153B1/de not_active Expired - Lifetime
  • 1998-03-12 CA CA002283582A patent/CA2283582C/en not_active Expired - Fee Related
  • 1998-03-12 US US09/380,977 patent/US6194534B1/en not_active Expired - Lifetime
  • 1998-03-12 WO PCT/EP1998/001413 patent/WO1998040429A1/de active IP Right Grant
  • 1998-03-12 AU AU68305/98A patent/AU6830598A/en not_active Abandoned

Patent Citations (6)

Also Published As

Similar Documents

Legal Events