CA2047920C - Low-temperature-stable titanium chelates - Google Patents
Low-temperature-stable titanium chelates Download PDFInfo
- Publication number
- CA2047920C CA2047920C CA002047920A CA2047920A CA2047920C CA 2047920 C CA2047920 C CA 2047920C CA 002047920 A CA002047920 A CA 002047920A CA 2047920 A CA2047920 A CA 2047920A CA 2047920 C CA2047920 C CA 2047920C
- Authority
- CA
- Canada
- Prior art keywords
- 2tix2
- butyl
- titanium
- temperature
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010936 titanium Substances 0.000 title abstract description 23
- 229910052719 titanium Inorganic materials 0.000 title abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- OVSGBKZKXUMMHS-VGKOASNMSA-L (z)-4-oxopent-2-en-2-olate;propan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CC(C)[O-].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O OVSGBKZKXUMMHS-VGKOASNMSA-L 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000005357 flat glass Substances 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract description 2
- 239000000976 ink Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000002318 adhesion promoter Substances 0.000 abstract 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004922 lacquer Substances 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 titanium ortho esters Chemical class 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000020 Nitrocellulose Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YAVVXGZJLQNDOP-UHFFFAOYSA-N CCCCO[Ti]OC(C)C Chemical compound CCCCO[Ti]OC(C)C YAVVXGZJLQNDOP-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- WVAFBJDECCWPPT-UHFFFAOYSA-N CCO[Ti]OC(C)C Chemical compound CCO[Ti]OC(C)C WVAFBJDECCWPPT-UHFFFAOYSA-N 0.000 description 1
- MBMKFKOVXPKXCV-UHFFFAOYSA-N CCO[Ti]OCC Chemical compound CCO[Ti]OCC MBMKFKOVXPKXCV-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTKOCRSQUPLVTD-UHFFFAOYSA-N butan-1-olate;titanium(2+) Chemical compound CCCCO[Ti]OCCCC MTKOCRSQUPLVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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 Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Surface Treatment Of Glass (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Titanium chelates of the formula (see formula I) in which X represents (see formula II) and It is selected from the group consisting of ethyl, n-propyl, n-butyl, i-butyl and t-butyl, and mixtures thereof are disclosed.
The compounds are prepared by mixing diisopropoxytitanium bis-(acetylacetonate) (i-PrO)2TiX2 with dialkoxytitanium bis(acetyl-acetonate) (RO)2TiX2 and allowing the mixture to react at a temperature of from 1 to 100°C above the melting point of the higher melting component of the mixture for 0 to 60 minutes.
The compounds are useful as adhesion promoters between inorganic and organic surfaces and printing inks and for coating sheet glass, hollow glassware and glass fibres to improve mechanical and optical properties thereof.
The compounds are prepared by mixing diisopropoxytitanium bis-(acetylacetonate) (i-PrO)2TiX2 with dialkoxytitanium bis(acetyl-acetonate) (RO)2TiX2 and allowing the mixture to react at a temperature of from 1 to 100°C above the melting point of the higher melting component of the mixture for 0 to 60 minutes.
The compounds are useful as adhesion promoters between inorganic and organic surfaces and printing inks and for coating sheet glass, hollow glassware and glass fibres to improve mechanical and optical properties thereof.
Description
The invention relates to novel titanium chelates, in particular to novel titanium acetylacetone chelates and mixtures thereof and to a method for preparing these compounds.
The preparation of titanium chelates of the formula (RO)2TiX2, in which X is an acetylacetonate radical and R is a C2-4-alkyl radical either branched or unbranched, is in general carried out by reaction of titanium ortho esters of the formula Ti(OR)4 with two equivalents of the chelating agent acetylacetone with the elimination of two equivalents of the alcohol ROH. The titanium chelates so prepared are usually left in the reaction solution and the alcohol formed in the reaction is not separated off. This was the only known manner to achieve moderate low-temperature stability of these substances. When such acetyl-acetonate solutions are used in industry, very low flash points due to the alcohol content have to be accepted. Also the effects achieved often vary substantially and are therefore not satisfactory. Moreover, the alcohol present in the solution enters the waste air and/or the waste water and has to be removed therefrom by expensive procedures. The separation by distillation of the alcohols formed in the reaction results in viscous liquids whose setting points are above -18°C or which crystallise spontaneously over a short period of time even at room temperature and thus become unusable.
One aspect of the present invention is to develop products which allow easy and low-risk handling and have a reliably good effect, especially in the treatment of surfaces. A further aspect is to lower the solvent content of the product to reduce the environmental pollution.
The preparation of titanium chelates of the formula (RO)2TiX2, in which X is an acetylacetonate radical and R is a C2-4-alkyl radical either branched or unbranched, is in general carried out by reaction of titanium ortho esters of the formula Ti(OR)4 with two equivalents of the chelating agent acetylacetone with the elimination of two equivalents of the alcohol ROH. The titanium chelates so prepared are usually left in the reaction solution and the alcohol formed in the reaction is not separated off. This was the only known manner to achieve moderate low-temperature stability of these substances. When such acetyl-acetonate solutions are used in industry, very low flash points due to the alcohol content have to be accepted. Also the effects achieved often vary substantially and are therefore not satisfactory. Moreover, the alcohol present in the solution enters the waste air and/or the waste water and has to be removed therefrom by expensive procedures. The separation by distillation of the alcohols formed in the reaction results in viscous liquids whose setting points are above -18°C or which crystallise spontaneously over a short period of time even at room temperature and thus become unusable.
One aspect of the present invention is to develop products which allow easy and low-risk handling and have a reliably good effect, especially in the treatment of surfaces. A further aspect is to lower the solvent content of the product to reduce the environmental pollution.
According to one aspect, the invention provides for a process for producing a compound of the formula H C X
HC-O- Ti- 0-R
comprising contacting (i-Pr0)2-TiX2 with (RO)2TiX2 wherein X is ~H3 IH3 O-C- CH-C= 0 R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-butyl and t-butyl, and mixtures thereof; the molar ratio of (i-Pr0) 2-TiX2 to (RO) 2TiX2 is in the range of from 1 : 0 . 1 to 1:1.9; said process is carried out at a temperature between 20°C and 100°C above the melting point of the higher melting component of (i-Pr0)2-TiXz or (RO)2TiXz.
The invention further relates to a process for the preparation of titanium chelates (i-Pr0) (RO)TiX2 and to applica-tions of these titanium chelates for increasing the adhesiveness of printing inks on inorganic and organic surfaces and for coating sheet glass, hollow glassware and glass fibres for improving mechanical and optical properties thereof.
The titanium chelates according to the invention have never been prepared in pure form.
The previously used processes for the preparation of titanium acetylacetonates having different alkoxy radicals on the central atom, such as, for example, mixing the titanium ortho esters (i-Pr0)4Ti and (RO)4Ti, reacting this mixture with the chelating agent acetylacetone and removing the alcohols formed in ~ ._ ~C94'~ ~~t~
the reaction by distillation or mixing one of the starting che~.ates (R'O)2TiX2 with the titanium ortho ester (R"0)4Ti, where R' is R or i-Pr, R" is R or i--Pr, and R' ~ R", reacting the mixture with the chelating agent and removing the alcohols formed in the reaction by distillation, do not lead to the uniform final products having the stoichiometry predetermined by the ratio of the titanium compounds used. These processes merely lead to non-uniform solutions of mixed titanium chelates having variable compositions and the disadvantageous properties resulting ZO therefrom.
'L'he t:Ltanium chelates (R'O)2TiX2 which are suitable as starting materials for the process according to the invention are prepared separately in a preceding reactian in a manner known per se by mixing the corresponding titanium ortho esters Ti(OR')4 with the chelating agent acetylacetone and distilling off the alcokrol R'OH formed in the reaction. The components are then reacted with one another at temperatures between 1°C to 100°C, preferably 1°C to 30°C, above the melting poa.nt of the higher melting component, for .From about 0 to athaoi t: E;0 minutes, prefer-20 ably for about 30 minutes.
Spectroscopic and chromatographic analyses clearly show that thc: starting chelates are no longer present in the reaction products obtained and the compounds according to the invention have been :Formed:
(i-Pr0) 2TiX2 -I- (RO) 2TiX2 _-_->
2 (i-Pr0)(RO)TiX2 , - 4 - 2~1~4'~~~~
If it is desired that the final product with respect to the alkyl groups R and i-propyl present has a composition which differs from the 1 : 1 ratio, one of the components can be used in the appropriate excess amount in the reaction described above. The molar ratio of components can vary in a broad range, typically from 1:0.1 to 1:1.9. This gives the mixtures of the titanium chelate (i-Pr0) (RO)TiX2 with excess titanium chelate (R'0)TiX2, which can be also obtained by mixing the mixed titanium chelate (i-~PrO)(RO)TiX2 with further starting chelate (R'0)2TiX2.
The procedure according to the invention ensures that the reaction product always has the preselected stoichiometric composition. The procedure according to the invention further ensures that the alcohol R'OH formed in the reaction is separated and thus recovered in the pure form. This alcohol can be recycled into the synthesis of the basic titanates Ti(OR')4 and is not lost in a manner po7.luting the environment.
Example 1 200 g of xcety:Lacetone err-.. addod dropwise with cooling to 284 g of titanium tetrai sopropox9.de. After stirring for a further half an hour, the liberated isopropanol (120 g) is completely distilled oft. A setting point of -18°C is measured for the residue diisopropoxytitanium bis(acetylacetonate). In a second reaction vessel, 340 g of titanium tetra-n-butoxide are reacted in the same way with 200 g of acetylacetone, and 148 g of n-butanol are then distilled off. The reaction product di-n-butoxytitanium bis(acetylacetonate), if not immediately processed further, forms crystals having edges several centimetres in length at room 2~~ ~'~~,~
temperature. The residue from the first distillation is mixed with the residue of the last distillation and the mixture is stirred at room temperature for another 30 minutes. The reaction product isopropoxy-n-butoxytitanium bis(acetylacetonate) has a setting point of -42°C.
Example 2 Solvent-free diisopropoxytitanium bis(acetylacetonate) is prepared from 284 g of titanium tetraisopropoxide and 200 g of acetylacetone as described in Example 1. The second reaction vessel is charged with 228 g of titanium tetraethoxide. 200 g of acetylacetone are added dropwise with cooling, and 92 g of ethanol are then distilled off. The remaining diethoxytitanium bis(acetylacetonate) crystallises, if the bottom temperature in the distillation flask towards the end of the distillation is allowed to drop below 35°C and melts again at 44 to 50°C. The residue from the .first distillation is added to the residue from the second distillation at 60°C, and the reaction mixture is kept at 60°C for a further 30 minutes. A setta.ng point of -33°C is measured for the roaction product ethoxyisopropoxytitanium bis-(acetylacetonate) which is formed quantitatively.
Example 3 which follows demonstrates the adhesion-increasing effect of the substances according to the invention as additives in nitrocellulose lacquers:
Example 3 A nitrocellulose white lacquer containing 25 percent of nitrocellulose is mixed with 1 percent of isopropoxy-n-butoxy-titanium b:is(acetylacetonate). The untreated lacquer is applied by means of a Jcnife to one half of a degreased polypropylene sheet and the lacquer to which the 'titanium chelate according to the invention has been added to the other half. The sheet thus treated is dried in air for 5 minutes. Two adhesive strips are then attached horizontally and pulled off i.n one go, beginning in each case from opposite ends. Comparison of the two sheet halves shows that more than 95 percent of the untreated lacquer was removed from the sheet but only about 50 percent of the lacquer treated according to the invention.
Comparative Example The comparative example which follows does not form part of the present invention:
284 g of titanium tetraiospropoxide and 340 g of titanium tetra-n-butoxide are mixed. 400 g of acetylacetone are added dropwise, and the alcohol mixture liberated is distilled off.
This mixture of isopropanol and n-butanol cannot be separated into the components in a cost-effective manner and has to be disgarded. Furthermore, the composition of the alcohol mixture is dependent on the chancJe in press;u.r,e dur:i.ncJ t:h<a distill.at:~o.n and is there:f.ore: di.E:Eicu:J_i~ to r.oC~roducc. 't'h:Ls al4:o has an ef:t'ect on the composition of the product, as evidenced by the Ti02 contents varying between 19.5 and 22.5 percent in several experiments .
HC-O- Ti- 0-R
comprising contacting (i-Pr0)2-TiX2 with (RO)2TiX2 wherein X is ~H3 IH3 O-C- CH-C= 0 R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-butyl and t-butyl, and mixtures thereof; the molar ratio of (i-Pr0) 2-TiX2 to (RO) 2TiX2 is in the range of from 1 : 0 . 1 to 1:1.9; said process is carried out at a temperature between 20°C and 100°C above the melting point of the higher melting component of (i-Pr0)2-TiXz or (RO)2TiXz.
The invention further relates to a process for the preparation of titanium chelates (i-Pr0) (RO)TiX2 and to applica-tions of these titanium chelates for increasing the adhesiveness of printing inks on inorganic and organic surfaces and for coating sheet glass, hollow glassware and glass fibres for improving mechanical and optical properties thereof.
The titanium chelates according to the invention have never been prepared in pure form.
The previously used processes for the preparation of titanium acetylacetonates having different alkoxy radicals on the central atom, such as, for example, mixing the titanium ortho esters (i-Pr0)4Ti and (RO)4Ti, reacting this mixture with the chelating agent acetylacetone and removing the alcohols formed in ~ ._ ~C94'~ ~~t~
the reaction by distillation or mixing one of the starting che~.ates (R'O)2TiX2 with the titanium ortho ester (R"0)4Ti, where R' is R or i-Pr, R" is R or i--Pr, and R' ~ R", reacting the mixture with the chelating agent and removing the alcohols formed in the reaction by distillation, do not lead to the uniform final products having the stoichiometry predetermined by the ratio of the titanium compounds used. These processes merely lead to non-uniform solutions of mixed titanium chelates having variable compositions and the disadvantageous properties resulting ZO therefrom.
'L'he t:Ltanium chelates (R'O)2TiX2 which are suitable as starting materials for the process according to the invention are prepared separately in a preceding reactian in a manner known per se by mixing the corresponding titanium ortho esters Ti(OR')4 with the chelating agent acetylacetone and distilling off the alcokrol R'OH formed in the reaction. The components are then reacted with one another at temperatures between 1°C to 100°C, preferably 1°C to 30°C, above the melting poa.nt of the higher melting component, for .From about 0 to athaoi t: E;0 minutes, prefer-20 ably for about 30 minutes.
Spectroscopic and chromatographic analyses clearly show that thc: starting chelates are no longer present in the reaction products obtained and the compounds according to the invention have been :Formed:
(i-Pr0) 2TiX2 -I- (RO) 2TiX2 _-_->
2 (i-Pr0)(RO)TiX2 , - 4 - 2~1~4'~~~~
If it is desired that the final product with respect to the alkyl groups R and i-propyl present has a composition which differs from the 1 : 1 ratio, one of the components can be used in the appropriate excess amount in the reaction described above. The molar ratio of components can vary in a broad range, typically from 1:0.1 to 1:1.9. This gives the mixtures of the titanium chelate (i-Pr0) (RO)TiX2 with excess titanium chelate (R'0)TiX2, which can be also obtained by mixing the mixed titanium chelate (i-~PrO)(RO)TiX2 with further starting chelate (R'0)2TiX2.
The procedure according to the invention ensures that the reaction product always has the preselected stoichiometric composition. The procedure according to the invention further ensures that the alcohol R'OH formed in the reaction is separated and thus recovered in the pure form. This alcohol can be recycled into the synthesis of the basic titanates Ti(OR')4 and is not lost in a manner po7.luting the environment.
Example 1 200 g of xcety:Lacetone err-.. addod dropwise with cooling to 284 g of titanium tetrai sopropox9.de. After stirring for a further half an hour, the liberated isopropanol (120 g) is completely distilled oft. A setting point of -18°C is measured for the residue diisopropoxytitanium bis(acetylacetonate). In a second reaction vessel, 340 g of titanium tetra-n-butoxide are reacted in the same way with 200 g of acetylacetone, and 148 g of n-butanol are then distilled off. The reaction product di-n-butoxytitanium bis(acetylacetonate), if not immediately processed further, forms crystals having edges several centimetres in length at room 2~~ ~'~~,~
temperature. The residue from the first distillation is mixed with the residue of the last distillation and the mixture is stirred at room temperature for another 30 minutes. The reaction product isopropoxy-n-butoxytitanium bis(acetylacetonate) has a setting point of -42°C.
Example 2 Solvent-free diisopropoxytitanium bis(acetylacetonate) is prepared from 284 g of titanium tetraisopropoxide and 200 g of acetylacetone as described in Example 1. The second reaction vessel is charged with 228 g of titanium tetraethoxide. 200 g of acetylacetone are added dropwise with cooling, and 92 g of ethanol are then distilled off. The remaining diethoxytitanium bis(acetylacetonate) crystallises, if the bottom temperature in the distillation flask towards the end of the distillation is allowed to drop below 35°C and melts again at 44 to 50°C. The residue from the .first distillation is added to the residue from the second distillation at 60°C, and the reaction mixture is kept at 60°C for a further 30 minutes. A setta.ng point of -33°C is measured for the roaction product ethoxyisopropoxytitanium bis-(acetylacetonate) which is formed quantitatively.
Example 3 which follows demonstrates the adhesion-increasing effect of the substances according to the invention as additives in nitrocellulose lacquers:
Example 3 A nitrocellulose white lacquer containing 25 percent of nitrocellulose is mixed with 1 percent of isopropoxy-n-butoxy-titanium b:is(acetylacetonate). The untreated lacquer is applied by means of a Jcnife to one half of a degreased polypropylene sheet and the lacquer to which the 'titanium chelate according to the invention has been added to the other half. The sheet thus treated is dried in air for 5 minutes. Two adhesive strips are then attached horizontally and pulled off i.n one go, beginning in each case from opposite ends. Comparison of the two sheet halves shows that more than 95 percent of the untreated lacquer was removed from the sheet but only about 50 percent of the lacquer treated according to the invention.
Comparative Example The comparative example which follows does not form part of the present invention:
284 g of titanium tetraiospropoxide and 340 g of titanium tetra-n-butoxide are mixed. 400 g of acetylacetone are added dropwise, and the alcohol mixture liberated is distilled off.
This mixture of isopropanol and n-butanol cannot be separated into the components in a cost-effective manner and has to be disgarded. Furthermore, the composition of the alcohol mixture is dependent on the chancJe in press;u.r,e dur:i.ncJ t:h<a distill.at:~o.n and is there:f.ore: di.E:Eicu:J_i~ to r.oC~roducc. 't'h:Ls al4:o has an ef:t'ect on the composition of the product, as evidenced by the Ti02 contents varying between 19.5 and 22.5 percent in several experiments .
Claims (4)
1. A process for producing a compound of the formula comprising contacting (i-PrO)2-TiX2 with (RO)2TiX2 wherein X is R is selected from the group consisting of ethyl, n-propyl, n-butyl, n-butyl and t-butyl, and mixtures thereof;
the molar ratio of (i-PrO)2-TiX2 to (RO)2TiX2 is in the range of from 1:0.1 to 1:1.9;
said process is carried out at a temperature between 20°C and 100°C above the melting point of the higher melting component of (i-PrO)2-TiX2 or (RO)2TiX2.
the molar ratio of (i-PrO)2-TiX2 to (RO)2TiX2 is in the range of from 1:0.1 to 1:1.9;
said process is carried out at a temperature between 20°C and 100°C above the melting point of the higher melting component of (i-PrO)2-TiX2 or (RO)2TiX2.
2. A process according to claim 1, wherein said process is carried out at a temperature between 1°C and 30°C above the melting point of the higher melting component of (i-PrO)2-TiX2 or (RO)2TiX2.
3. A process according to claim 1, wherein process is carried out for from about 0 to about 60 minutes.
4. A process according to claim 1, wherein the molar ratio is 1:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4023851A DE4023851A1 (en) | 1990-07-27 | 1990-07-27 | NEW COLD-TABLE TITANCHELATES |
| DEP4023851.2 | 1990-07-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2047920A1 CA2047920A1 (en) | 1992-01-28 |
| CA2047920C true CA2047920C (en) | 2001-11-20 |
Family
ID=6411106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002047920A Expired - Fee Related CA2047920C (en) | 1990-07-27 | 1991-07-25 | Low-temperature-stable titanium chelates |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0468161B1 (en) |
| JP (1) | JP3222492B2 (en) |
| AT (1) | ATE136034T1 (en) |
| CA (1) | CA2047920C (en) |
| DE (2) | DE4023851A1 (en) |
| ES (1) | ES2085376T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07254360A (en) * | 1994-03-15 | 1995-10-03 | Futaba Corp | Fluorescent display tube and paste |
| US6402823B1 (en) * | 2000-01-07 | 2002-06-11 | Ferro Corporation | Individual inks and an ink set for use in the color ink jet printing of glazed ceramic tiles and surfaces |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK487783A (en) * | 1982-11-05 | 1984-05-06 | Du Pont | TITANESTER COMPOSITION AND PROCEDURE FOR PREPARING THEREOF |
| US4521461A (en) * | 1984-04-25 | 1985-06-04 | Dow Corning Limited | Siloxane-polyester compositions |
| GB2161164B (en) * | 1984-07-03 | 1987-10-14 | Coates Brothers Plc | Coating compositions |
| DE3733608A1 (en) * | 1987-10-05 | 1989-04-13 | Huels Troisdorf | NEW TITANIUM (IV) CHELESES AND THEIR USE IN PRINTING COLORS |
-
1990
- 1990-07-27 DE DE4023851A patent/DE4023851A1/en not_active Withdrawn
-
1991
- 1991-05-28 ES ES91108625T patent/ES2085376T3/en not_active Expired - Lifetime
- 1991-05-28 DE DE59107605T patent/DE59107605D1/en not_active Expired - Lifetime
- 1991-05-28 EP EP91108625A patent/EP0468161B1/en not_active Expired - Lifetime
- 1991-05-28 AT AT91108625T patent/ATE136034T1/en not_active IP Right Cessation
- 1991-07-24 JP JP18426591A patent/JP3222492B2/en not_active Expired - Fee Related
- 1991-07-25 CA CA002047920A patent/CA2047920C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04243887A (en) | 1992-08-31 |
| DE4023851A1 (en) | 1992-01-30 |
| EP0468161B1 (en) | 1996-03-27 |
| ATE136034T1 (en) | 1996-04-15 |
| JP3222492B2 (en) | 2001-10-29 |
| ES2085376T3 (en) | 1996-06-01 |
| CA2047920A1 (en) | 1992-01-28 |
| EP0468161A1 (en) | 1992-01-29 |
| DE59107605D1 (en) | 1996-05-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0682033B1 (en) | Hydrolysable and polymerisable silanes | |
| EP0832911B1 (en) | Glycidether, acryl- and/ or methacryl-functional waterborne organopolysiloxane-containing compositions, process for their preparation and their use | |
| EP0799832B1 (en) | Hydrolysable fluorinated silanes; process for their preparation and their use in preparing silicic acid polycondensates and silicic acid heteropolycondensates | |
| EP0525392B1 (en) | Hydrolysable and polymerisable silanes | |
| DE69115632T2 (en) | Refractory dielectric coating compositions | |
| GB2041389A (en) | Processes for the preparation of organopoly-siloxanes suitable for use as active compounds for non-stick coating compositions | |
| EP0781290A1 (en) | Hydrolyzable and polymerizable or addition-polymerizable silanes | |
| EP1205505A2 (en) | Continous process for preparing organoalkoxysiloxanes | |
| EP0978525A2 (en) | Acryloxypropyl or methacryloxypropyl group containing siloxane oligomers | |
| EP0085831B1 (en) | Organosilane esters with residues of glycol ethers | |
| DE2200347A1 (en) | ALKANDIOXY TITANCHELATE | |
| EP0512418A1 (en) | Process for preparing coatings bases on silicone resin | |
| EP0280946B1 (en) | Organosilanes containing benzoylthiourea; process for their preparation | |
| DE3789735T2 (en) | MULTIFUNCTIONAL, METAL-ORGANIC AMINO-ZIRCONIUM-ALUMINUM COMPLEXES AS BOND IMPROVERS. | |
| CA1234133A (en) | Water-soluble titaniumacetyl-acetonates | |
| CA2047920C (en) | Low-temperature-stable titanium chelates | |
| EP2838905A1 (en) | Novel, mono-synthesizable, spontaneously water-soluble, substantially voc-free, environmentally friendly (meth)acrylamido-functional siloxanol systems, process for their preparation and use | |
| DE102012206508A1 (en) | New, easy-to-produce, VOC-reduced, environmentally friendly (meth) acrylamido-functional siloxane systems. Processes for their preparation and use | |
| US5349073A (en) | Low-temperature-stable titanium chelates and method for their preparation | |
| EP0151931B1 (en) | Water-soluble esters of zirconic acid | |
| US5796117A (en) | Preparation of waterborne silane/titanium chelates composition | |
| CH661928A5 (en) | METHOD FOR PRODUCING FUNCTIONALLY SUBSTITUTED SILANES. | |
| JPH049795B2 (en) | ||
| EP0193739B1 (en) | Process for the preparation of aminosilanes | |
| JPH11199855A (en) | Metal chelate compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |