CA2084698A1 - Polyisocyanates containing ether and urethane groups, a process for their preparation and their use in the production of polyurethane lacquers - Google Patents
Polyisocyanates containing ether and urethane groups, a process for their preparation and their use in the production of polyurethane lacquersInfo
- Publication number
- CA2084698A1 CA2084698A1 CA002084698A CA2084698A CA2084698A1 CA 2084698 A1 CA2084698 A1 CA 2084698A1 CA 002084698 A CA002084698 A CA 002084698A CA 2084698 A CA2084698 A CA 2084698A CA 2084698 A1 CA2084698 A1 CA 2084698A1
- Authority
- CA
- Canada
- Prior art keywords
- tolylene diisocyanate
- weight
- polyisocyanates
- polyether
- polyhydroxy
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8029—Masked aromatic polyisocyanates
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
Abstract
Mo3816 LeA 28,776 POLYISOCYANATES CONTAINING ETHER AND URETHANE GROUPS, A PROCESS FOR THEIR PREPARATION AND THEIR USE IN THE
PRODUCTION OF POLYURETHANE LACQUERS
ABSTRACT OF THE DISCLOSURE
Polyisocyanates based on polyhydroxy polyethers and tolylene diisocyanate containing ether and urethane groups and having an isocyanate group content of from 11.8 to 14.4% by weight, an average isocyanate functionality of from 3.1 to 4.0 and a free tolylene diisocyanate content of less than 0.1% by weight are produced by reacting a polyhydroxy polyether having a molecular weight in the range of from about 350 to about 500 with excess quantities of tolylene diisocyanate and subsequently distilling the mixture to remove unreacted excess of the starting diisocyanate. These polyisocyanates are particularly useful in the production of polyurethane lacquers Mo3816
PRODUCTION OF POLYURETHANE LACQUERS
ABSTRACT OF THE DISCLOSURE
Polyisocyanates based on polyhydroxy polyethers and tolylene diisocyanate containing ether and urethane groups and having an isocyanate group content of from 11.8 to 14.4% by weight, an average isocyanate functionality of from 3.1 to 4.0 and a free tolylene diisocyanate content of less than 0.1% by weight are produced by reacting a polyhydroxy polyether having a molecular weight in the range of from about 350 to about 500 with excess quantities of tolylene diisocyanate and subsequently distilling the mixture to remove unreacted excess of the starting diisocyanate. These polyisocyanates are particularly useful in the production of polyurethane lacquers Mo3816
Description
Mo381~
LeA 28,776-US
POLYISOCYANATES CONTAINING ETHER AND URETHANE GROUPS, A PROCESS FOR THEIR PREPARATION AND THEIR USE IN THE
PRODUCTION OF POLYURETHANE LACqUERS
BACKGROUND OF THE INVENTION
This invention relates to polyisocyanates based on tolylene diisocyanate which contain ether and urethane groups, to a process for their preparation and to their use as polyisocyanate components in one-component and two-component polyurethane lacquers.
Urethane group-containing polyisocyanates obtained from low molecular weight polyhydric alcohols and tolylene diisocyanate are known and are described, for example, in German Patent Specifications Nos. 870,400, 953,012 and 1,0g0,196. Such products are of great importance in the field of polyurethane lacquers and coatings and for adhesives.
Commercial products are currently produced by reacting polyhydric alcohols with an excess of tolylene diisocyanate of from 5 to 10 times the quantity of alcohol present and then removing the excess starting diisocyanate by distillation, preferably in a thin layer evaporator. Such processes are described, for example, in DE-PS 1,090,186 and U.S. 3,183,112.
The polyisocyanates which are produced by these methods have, however, two basic disadvantages. First, when the polyisocyanate is used in combination with commercial polyols, the products have a relatively short processing time so that they cannot be optimally used in all fields of application.
Secondly, the known products have a very high melt viscosity.
Consequently, removal of the tolylene diisocyanate by distillation can only be carried out down to a residue of about 0.2% by weight. For reasons of hygiene in the work place, however, it is desirable to reduce the monomer content to less than 0.1% by weight.
Numerous chemical after-treatment methods for removing residual monomers have been described in the Patent literature LeA 28 776-US
, , ~ : - -~ , ~
LeA 28,776-US
POLYISOCYANATES CONTAINING ETHER AND URETHANE GROUPS, A PROCESS FOR THEIR PREPARATION AND THEIR USE IN THE
PRODUCTION OF POLYURETHANE LACqUERS
BACKGROUND OF THE INVENTION
This invention relates to polyisocyanates based on tolylene diisocyanate which contain ether and urethane groups, to a process for their preparation and to their use as polyisocyanate components in one-component and two-component polyurethane lacquers.
Urethane group-containing polyisocyanates obtained from low molecular weight polyhydric alcohols and tolylene diisocyanate are known and are described, for example, in German Patent Specifications Nos. 870,400, 953,012 and 1,0g0,196. Such products are of great importance in the field of polyurethane lacquers and coatings and for adhesives.
Commercial products are currently produced by reacting polyhydric alcohols with an excess of tolylene diisocyanate of from 5 to 10 times the quantity of alcohol present and then removing the excess starting diisocyanate by distillation, preferably in a thin layer evaporator. Such processes are described, for example, in DE-PS 1,090,186 and U.S. 3,183,112.
The polyisocyanates which are produced by these methods have, however, two basic disadvantages. First, when the polyisocyanate is used in combination with commercial polyols, the products have a relatively short processing time so that they cannot be optimally used in all fields of application.
Secondly, the known products have a very high melt viscosity.
Consequently, removal of the tolylene diisocyanate by distillation can only be carried out down to a residue of about 0.2% by weight. For reasons of hygiene in the work place, however, it is desirable to reduce the monomer content to less than 0.1% by weight.
Numerous chemical after-treatment methods for removing residual monomers have been described in the Patent literature LeA 28 776-US
, , ~ : - -~ , ~
(e.g. U.S. 3,384,624, DE-OS 2,414,413 and 2,414,391). Such methods of reduction in monomer content, however, require additional and hence expensive process steps which generally produce a pronounced change in the properties of the polyisocyanate. Thus, chemical a~ter-treatment methods are not employed in the industrial production o~ polyisocyanates.
SUMMARY OF ~E INVENTION
It is therefore an object of the present invention to provide urethane group-containing polyisocyanates based on lo tolylene diisocyanate which have a low monomer content and which make longer processing times possible.
It is also an object of the present invention to provide a process for the production of such urethane group-containing polyisocyanates.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting an organic polyhydroxy polyether having a molecular weight of from about 350 to about 500 with an excess of tolylene diisocyanate and distilling the reaction mixture to remove unreacted excess tolylene diisocyanate until the residual diisocyanate content is less than 0.1% by weight. The polyisocyanates thus obtained are characterized by an NCO content of from about 11.8 to about 14.4% by weight, an average NCO functionality of from about 3.1 to about 4.0 and a free tolylene diisocyanate content of less than about 0.1%.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is based on the surprising observation that adducts of tolylene diisocyanate and certain polyether alcohols, in particular polyether triols, have a reduced reactivity with polyhydroxy compounds and at the same time a low melt viscosity so that monomers can easily be removed by distillation down to a residue o~ less than 0.1% by weight.
The present invention relates to polyisocyanates containing ether groups and urethane groups, based on Mo3B16 ' .
SUMMARY OF ~E INVENTION
It is therefore an object of the present invention to provide urethane group-containing polyisocyanates based on lo tolylene diisocyanate which have a low monomer content and which make longer processing times possible.
It is also an object of the present invention to provide a process for the production of such urethane group-containing polyisocyanates.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting an organic polyhydroxy polyether having a molecular weight of from about 350 to about 500 with an excess of tolylene diisocyanate and distilling the reaction mixture to remove unreacted excess tolylene diisocyanate until the residual diisocyanate content is less than 0.1% by weight. The polyisocyanates thus obtained are characterized by an NCO content of from about 11.8 to about 14.4% by weight, an average NCO functionality of from about 3.1 to about 4.0 and a free tolylene diisocyanate content of less than about 0.1%.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is based on the surprising observation that adducts of tolylene diisocyanate and certain polyether alcohols, in particular polyether triols, have a reduced reactivity with polyhydroxy compounds and at the same time a low melt viscosity so that monomers can easily be removed by distillation down to a residue o~ less than 0.1% by weight.
The present invention relates to polyisocyanates containing ether groups and urethane groups, based on Mo3B16 ' .
polyhydroxy polyethers and tolylene diisocyanate, characterized an isocyanate content of from 11.8 to 14.4% by weight, an average isocyanate functionality of from 3.1 to 4.0 and less than about 0.1% by weight of free tolylene diisocyanate.
The present invention also relates to a process for the preparation of such polyisocyanates by the reaction of organic polyhydroxy compounds with excess quantities of tolylene diisocyanate followed by distillation to remove unreacted excess of this starting diisocyanate down to a residue of less ! 10 than 0.1% by weight. The polyhydroxy compounds used are polyhydroxy polyethers having a molecular weight in the range of from 350 to 500.
The invention also relates to the use of the new ` poly;socyanates as polyisocyanate components in polyurethane 15 lacquers, in particular in two-component polyurethane lacquers.
The starting materials for the process according to the invention are tolylene diisocyanate and polyether polyols.
Any of the isomers of tolylene diisocyanate may be used but 2,4-tolylene diisocyanate and commercial mixtures thereof ' 20 in which up to 35% by weight, based on the mixture, of 2,6-tolylene diisocyanate is present are preferred.
The polyether polyols useful in the process of the present ;nvention have a molecular weight, determined from the hydroxyl group content and hydroxyl functionality, of from 350 to 500, 25 preferably from 400 to 470. Polyether triols having a molecular weight within these ranges are preferred. The polyether polyols which may be used in the practice of the present invention may be obtained in known manner by the alkoxylation of suitable starter molecules or suitable mixtures 30 of starter molecules. The preferred compounds used for alkoxylat;on are propylene oxide and/or ethylene oxide. The alkoxylation may be carried out on mixtures of these starting ~- materials or successively on individual startin~ materials in any sequence. It is particularly preferred to use the A, 35 polypropylene oxide polyethers obtained by the propoxylation of Mo3816 ,~
.~. . .
.
~: ' . . ~
The present invention also relates to a process for the preparation of such polyisocyanates by the reaction of organic polyhydroxy compounds with excess quantities of tolylene diisocyanate followed by distillation to remove unreacted excess of this starting diisocyanate down to a residue of less ! 10 than 0.1% by weight. The polyhydroxy compounds used are polyhydroxy polyethers having a molecular weight in the range of from 350 to 500.
The invention also relates to the use of the new ` poly;socyanates as polyisocyanate components in polyurethane 15 lacquers, in particular in two-component polyurethane lacquers.
The starting materials for the process according to the invention are tolylene diisocyanate and polyether polyols.
Any of the isomers of tolylene diisocyanate may be used but 2,4-tolylene diisocyanate and commercial mixtures thereof ' 20 in which up to 35% by weight, based on the mixture, of 2,6-tolylene diisocyanate is present are preferred.
The polyether polyols useful in the process of the present ;nvention have a molecular weight, determined from the hydroxyl group content and hydroxyl functionality, of from 350 to 500, 25 preferably from 400 to 470. Polyether triols having a molecular weight within these ranges are preferred. The polyether polyols which may be used in the practice of the present invention may be obtained in known manner by the alkoxylation of suitable starter molecules or suitable mixtures 30 of starter molecules. The preferred compounds used for alkoxylat;on are propylene oxide and/or ethylene oxide. The alkoxylation may be carried out on mixtures of these starting ~- materials or successively on individual startin~ materials in any sequence. It is particularly preferred to use the A, 35 polypropylene oxide polyethers obtained by the propoxylation of Mo3816 ,~
.~. . .
.
~: ' . . ~
-4- ~ f~ 3~3 trihydric alcohols which are free from ether groups. Glycerol and/or trimethylolpropane are preferred starter molecules.
To carry out the process of the present invention, the polyether polyols are reacted with tolylene diisocyanate at temperatures of from about 40 to about 140C, preferably at 50 to 110C. The quantities of the reactants generally corresponds to an NCO/OH equivalent ratio of from about 4:1 to about 20:1, preferably from about 5:1 to about 10:1.
After the prepolymerization, the excess of unreacted tolylene diisocyanate is removed, preferably by vacuum thin layer distillation at from 100 to 180C, preferably from 120 to 160CC. The polyisocyanates according to the invention are then obtained in the form of semi-rigid resins.
The polyisocyanates of the present invention have a very low melt viscosity compared with the polyisocyanates known in the art. Their viscosity at 100C is generally less than about 20,000 mPa.s, preferably less than about 10,000 mPa.s. Due to the low melt viscosity, monomeric diisocyanates can be removed particularly effectively by vacuum thin layer distillation so that the residue of free tolylene diisocyanate can easily be reduced to less than 0.1% by weight in the thin layer evaporators conventionally used in the art.
The polyisocyanates of the present invention are polyisocyanate mixtures whose gel chromatographic analysis shows the simultaneous presence of polyisocyanates having a functionality of 3 as the main component and polyisocyanates of higher functionality as subsidiary components. The average functionality which can be calculated from the isocyanate content and from the molecular weight determined by vapor pressure osmometry is therefore generally in the range of from 3.1 to 4.0, preferably from 3.3 to 3.8.
The polyisocyanates of the present invention are generally used in the form of a solution in an organic solvent. Examples of suitable solvents include the known lacquer solvents such as ethyl acetate, butyl acetate, methoxypropyl acetate, toluene, Mo3816 - ; , , . , - :
- ~.
,:
.
To carry out the process of the present invention, the polyether polyols are reacted with tolylene diisocyanate at temperatures of from about 40 to about 140C, preferably at 50 to 110C. The quantities of the reactants generally corresponds to an NCO/OH equivalent ratio of from about 4:1 to about 20:1, preferably from about 5:1 to about 10:1.
After the prepolymerization, the excess of unreacted tolylene diisocyanate is removed, preferably by vacuum thin layer distillation at from 100 to 180C, preferably from 120 to 160CC. The polyisocyanates according to the invention are then obtained in the form of semi-rigid resins.
The polyisocyanates of the present invention have a very low melt viscosity compared with the polyisocyanates known in the art. Their viscosity at 100C is generally less than about 20,000 mPa.s, preferably less than about 10,000 mPa.s. Due to the low melt viscosity, monomeric diisocyanates can be removed particularly effectively by vacuum thin layer distillation so that the residue of free tolylene diisocyanate can easily be reduced to less than 0.1% by weight in the thin layer evaporators conventionally used in the art.
The polyisocyanates of the present invention are polyisocyanate mixtures whose gel chromatographic analysis shows the simultaneous presence of polyisocyanates having a functionality of 3 as the main component and polyisocyanates of higher functionality as subsidiary components. The average functionality which can be calculated from the isocyanate content and from the molecular weight determined by vapor pressure osmometry is therefore generally in the range of from 3.1 to 4.0, preferably from 3.3 to 3.8.
The polyisocyanates of the present invention are generally used in the form of a solution in an organic solvent. Examples of suitable solvents include the known lacquer solvents such as ethyl acetate, butyl acetate, methoxypropyl acetate, toluene, Mo3816 - ; , , . , - :
- ~.
,:
.
-5- ~ 3 the isomeric xylenes and commercial solvents suchasSolvessoof Exxon Chernicals or mixtures of such solvents. It has surprisingly been shown that solutions of the polyisocyanates according to the invention can be much more easily diluted with odorless aliphatic solvents than solutions known in the art.
Examples of such solvents include petroleum ethers, cleaning petrol, light petrol, white spirits and vanous typesoi isop~affi~icsolvents such as Isopar of Exxon Chemicals. This property is particularly advantageous for use in closed work spaces.
lo The polyisocyanates of the present invention are valuable raw materials for one-component and two-component polyurethane lacquers. The particularly preferred field of application of the new polyisocyanates is their use as polyisocyanate components in two-component polyurethane lacquers.
The reactants for the polyisocyanates of the present invention for this preferred application are the polyhydroxy polyesters and polyethers known to those skilled in the technology of polyurethane lacquers, polyhydroxy polyacrylates and optionally low molecular weight polyhydric alcohols.
Polyamines, part;cularly those in blocked form as polyketimines or oxazolidines, could also be used as reactants for the ; production of lacquers from the polyisocyanate of the present invention.
The quantitative ratios in which the polyisocyanates of the present invention and the above-mentioned reactants are used for the preparation of two-component polyurethane lacquers are generally chosen to provide from about 0.8 to about 3 isocyanate reactive groups, preferably from about 0.9 to about 1.1 such groups, for one isocyanate group.
When formulating two-component polyurethane coating compounds from the polyisocyanates of the present invention and polyhydroxy compounds, it was surprisingly found that these systems have a substantially longer pot life than state of the art formulations.
:
Mo3816 , .
Examples of such solvents include petroleum ethers, cleaning petrol, light petrol, white spirits and vanous typesoi isop~affi~icsolvents such as Isopar of Exxon Chemicals. This property is particularly advantageous for use in closed work spaces.
lo The polyisocyanates of the present invention are valuable raw materials for one-component and two-component polyurethane lacquers. The particularly preferred field of application of the new polyisocyanates is their use as polyisocyanate components in two-component polyurethane lacquers.
The reactants for the polyisocyanates of the present invention for this preferred application are the polyhydroxy polyesters and polyethers known to those skilled in the technology of polyurethane lacquers, polyhydroxy polyacrylates and optionally low molecular weight polyhydric alcohols.
Polyamines, part;cularly those in blocked form as polyketimines or oxazolidines, could also be used as reactants for the ; production of lacquers from the polyisocyanate of the present invention.
The quantitative ratios in which the polyisocyanates of the present invention and the above-mentioned reactants are used for the preparation of two-component polyurethane lacquers are generally chosen to provide from about 0.8 to about 3 isocyanate reactive groups, preferably from about 0.9 to about 1.1 such groups, for one isocyanate group.
When formulating two-component polyurethane coating compounds from the polyisocyanates of the present invention and polyhydroxy compounds, it was surprisingly found that these systems have a substantially longer pot life than state of the art formulations.
:
Mo3816 , .
When exceptionally rapid complete hardening is required, the catalysts commonly used in isocyanate chemistry may be added. Specific examples of suitable catalysts include: amines such as triethylamine, pyridine, methyl pyridine, benzyl dimethylamine, N,N'-dimethylpiperazine and metal salts such as iron(III) chloride, zinc chloride, zinc-2-ethylcaproate, t;n(II)-2-ethylcaproate, dibutyl tin(IV) dilaurate or molybdenum glycolate.
One-component polyurethane lacquers containing the polyisocyanates of the present invention as binders and two-component polyurethane lacquers containing the polyisocyanates of the present invention as cross-linking agents produce lacquer films which have outstanding abrasion resistance combined with excellent adherence to a wide variety of substrates. In addition, the lacquer films are distinguished ` by great hardness and elasticity.
The polyurethane lacquers which contain polyisocyanates produced in accordance with the present invention as binders or hardeners may, of course, contain the usual auxiliary agents and additives used in lacquer technology, such as pigments, levelling agents, fillers, and the like.
Having thus described our invention, the following Examples are given as being illustratiYe thereof. The percentages in these Examples are all percentages by weight.
` 25 EXAMPLES
Example 1 Preparation of a polyisocyanate 440 9 of a polyether having an average molecular weight of 440 prepared by the propoxylation of trimethylolpropane ~ere slowly added dropwise to 3654 g of a mi~ture of 80% of 2,4-tolylene diisocyanate and 20% of 2,6-tolylene diisocyanate at 60C. Stirring was continued for 2 hours at 60C after all the polyether had been added. The product was then freed from monomeric diisocyanate by vacuum thin layer distillation at 140C/O.l mm. The almost colorless resin obtained had a Mo3816 - - ~
~. , ; : ,. :. ~ - .. .
:
r ~ 3 ~ ~
One-component polyurethane lacquers containing the polyisocyanates of the present invention as binders and two-component polyurethane lacquers containing the polyisocyanates of the present invention as cross-linking agents produce lacquer films which have outstanding abrasion resistance combined with excellent adherence to a wide variety of substrates. In addition, the lacquer films are distinguished ` by great hardness and elasticity.
The polyurethane lacquers which contain polyisocyanates produced in accordance with the present invention as binders or hardeners may, of course, contain the usual auxiliary agents and additives used in lacquer technology, such as pigments, levelling agents, fillers, and the like.
Having thus described our invention, the following Examples are given as being illustratiYe thereof. The percentages in these Examples are all percentages by weight.
` 25 EXAMPLES
Example 1 Preparation of a polyisocyanate 440 9 of a polyether having an average molecular weight of 440 prepared by the propoxylation of trimethylolpropane ~ere slowly added dropwise to 3654 g of a mi~ture of 80% of 2,4-tolylene diisocyanate and 20% of 2,6-tolylene diisocyanate at 60C. Stirring was continued for 2 hours at 60C after all the polyether had been added. The product was then freed from monomeric diisocyanate by vacuum thin layer distillation at 140C/O.l mm. The almost colorless resin obtained had a Mo3816 - - ~
~. , ; : ,. :. ~ - .. .
:
r ~ 3 ~ ~
viscosity of 4700 mPa.s/100C. The product was dissolved to form an 80% solution in methoxy-propyl acetate. The solution had the following characteristics:
Solids content: 80 %
Viscosity: 10,500 mPa.s/22C
NC0 content: 10.5 %
Molecular weight: 1150 g/mol (determined by vapor pressure osmometry) 10 Calculated NC0 functionality: 3.59 Monomer content: 0.03 % by weight.
The solution was diluted with white spirits down to a proportion by weight of 45%.
ExamDle 2 Preparation of a polyisocyanate Example 1 was repeated with th~ exception that 440 g of a mixture of 65% of 2,4-tolylene diisocyanate and 35% of 2,6-tolylene di;socyanate were used as the isocyanate. The resulting solvent-free, pale yellow resin had a melt viscosity of 5500 mPa.s/100C and was dissolved in ethyl acetate to a concentration of 80%. The solution had the following characteristics:
Solids content: 80 %
Viscosity: 1500 mPa.s/22C
NC0 content: 10.3 %
Molecular weight: 1160 g/mol (determined by vapor pressure ssmometry) Calc. NC0 functionality:3.57 Monomer content: 0.03 % by weight The solution was diluted with white spirits down to a proportion by weight of 50%.
Mo3816 . ~ , . . . ... . . .
- - . . ,: ~
;~ :
~' ..
' ~
Solids content: 80 %
Viscosity: 10,500 mPa.s/22C
NC0 content: 10.5 %
Molecular weight: 1150 g/mol (determined by vapor pressure osmometry) 10 Calculated NC0 functionality: 3.59 Monomer content: 0.03 % by weight.
The solution was diluted with white spirits down to a proportion by weight of 45%.
ExamDle 2 Preparation of a polyisocyanate Example 1 was repeated with th~ exception that 440 g of a mixture of 65% of 2,4-tolylene diisocyanate and 35% of 2,6-tolylene di;socyanate were used as the isocyanate. The resulting solvent-free, pale yellow resin had a melt viscosity of 5500 mPa.s/100C and was dissolved in ethyl acetate to a concentration of 80%. The solution had the following characteristics:
Solids content: 80 %
Viscosity: 1500 mPa.s/22C
NC0 content: 10.3 %
Molecular weight: 1160 g/mol (determined by vapor pressure ssmometry) Calc. NC0 functionality:3.57 Monomer content: 0.03 % by weight The solution was diluted with white spirits down to a proportion by weight of 50%.
Mo3816 . ~ , . . . ... . . .
- - . . ,: ~
;~ :
~' ..
' ~
8 Zq~ 3 Example 3 Preparation of a polyisocyanate 360 g of a polyether having a molecular weight of 360 prepared by the propoxylation of trimethylolpropane were slowly added dropwise to 4698 9 of 2,4-tolylene diisocyanate at 60C.
The product was worked up as in Example 1 after 2 hours of stirring at 60C. The almost colorless resin obtained had a melt viscosity of 18,400 mPa.s/100C. The product was dissolved to a concentration of 80% in ethyl acetate. The solution had lo the following characteristics:
Solids content: 80 %
Viscosity: 3700 mPa.s/22C
NCO content: 11.2 %
Molecular weight: 978 g/mol (determined by vapor pressure osmometry) Calc. NC0 functionality: 3.26 Monomer content: 0.04 % by weight.
Example 4 20 Preparation of a polyisocyanate ~Comparison Example) A mixture of 252 g of trimethylolpropane and 120 g of diethylene glycol was slowly added dropwise to 3864 g of a ; mixture of 65% of 2,4-tolylene diisocyanate and 35% of 2,6-tolylene diisocyanate at 80C. The product was worked up as in Example 1 after 2 hours of stirring at 80~C.
.~
.~
Mo3816 , .
, B
g The pale yellow resin obtained had a viscosity above 400,000 mPa.s/100C. A 75% solution in ethyl acetate had the following characteristics:
Solids content: 75 %
Viscosity: 1400 mPa.s/22DC
NCO content: 13 %
Molecular weight: 787 g/mol (determined by vapor pressure osmometry) o Calc. NCO functionality: 3.25 Monomer content: 0.23 % by weight.
The solution was diluted with white spirits down to a proportion by weight of 15%.
Example 5 (Use) The polyisocyanates from Example 2 and Example 4 were each mixed with a commercial polyester polyol (Desmophen (R) 1300, Trade Product of Bayer AG, OH content 4%) to a total concentration of 50% in ethyl acetate at an NCO/OH ratio of l:l. The properties of each lacquer are summarized in the Table below, ;
i 3o ; Mo3816 ..
:
Polyisocyanate Polyisocyanate Example 2 Example 4 Pot life 5 days 51 hours (until gelling occurs) Drying 13 hours 5.5 hours (180 ~m) Outflow time (DIN 4) immediately 14 seconds 15 seconds 4 h 14 seconds 16 seconds 8 h 15 seconds 17 seconds 24 h 19 seconds 29 seconds 32 h 20 seconds 48 seconds Pendulum hardness 159 seconds 174 seconds (after 7 days Room Temp.) Solvent attack 0/0/0/4 0/0/0/3 (after 7 days Room Temp.) (toluene, metho~ypropyl-acetate, ethyl acetate, acetone) Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3816 ;^ . . ~ .
: ' , . . .
- ~ :
.
The product was worked up as in Example 1 after 2 hours of stirring at 60C. The almost colorless resin obtained had a melt viscosity of 18,400 mPa.s/100C. The product was dissolved to a concentration of 80% in ethyl acetate. The solution had lo the following characteristics:
Solids content: 80 %
Viscosity: 3700 mPa.s/22C
NCO content: 11.2 %
Molecular weight: 978 g/mol (determined by vapor pressure osmometry) Calc. NC0 functionality: 3.26 Monomer content: 0.04 % by weight.
Example 4 20 Preparation of a polyisocyanate ~Comparison Example) A mixture of 252 g of trimethylolpropane and 120 g of diethylene glycol was slowly added dropwise to 3864 g of a ; mixture of 65% of 2,4-tolylene diisocyanate and 35% of 2,6-tolylene diisocyanate at 80C. The product was worked up as in Example 1 after 2 hours of stirring at 80~C.
.~
.~
Mo3816 , .
, B
g The pale yellow resin obtained had a viscosity above 400,000 mPa.s/100C. A 75% solution in ethyl acetate had the following characteristics:
Solids content: 75 %
Viscosity: 1400 mPa.s/22DC
NCO content: 13 %
Molecular weight: 787 g/mol (determined by vapor pressure osmometry) o Calc. NCO functionality: 3.25 Monomer content: 0.23 % by weight.
The solution was diluted with white spirits down to a proportion by weight of 15%.
Example 5 (Use) The polyisocyanates from Example 2 and Example 4 were each mixed with a commercial polyester polyol (Desmophen (R) 1300, Trade Product of Bayer AG, OH content 4%) to a total concentration of 50% in ethyl acetate at an NCO/OH ratio of l:l. The properties of each lacquer are summarized in the Table below, ;
i 3o ; Mo3816 ..
:
Polyisocyanate Polyisocyanate Example 2 Example 4 Pot life 5 days 51 hours (until gelling occurs) Drying 13 hours 5.5 hours (180 ~m) Outflow time (DIN 4) immediately 14 seconds 15 seconds 4 h 14 seconds 16 seconds 8 h 15 seconds 17 seconds 24 h 19 seconds 29 seconds 32 h 20 seconds 48 seconds Pendulum hardness 159 seconds 174 seconds (after 7 days Room Temp.) Solvent attack 0/0/0/4 0/0/0/3 (after 7 days Room Temp.) (toluene, metho~ypropyl-acetate, ethyl acetate, acetone) Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3816 ;^ . . ~ .
: ' , . . .
- ~ :
.
Claims (9)
1. Polyisocyanates based on a polyhydroxy polyether and tolylene diisocyanate containing ether and urethane groups having a) an MCO content of from about 11.8 to about 14.4% by weight, b) an average NCO functionality of from about 3.1 to about 4.0 and c) a free tolylene diisocyanate content of less than about 0.1% by weight.
2. A process for the preparation of polyisocyanates containing ether groups and urethane groups of Claim 1 comprising a) reacting an organic polyhydroxy polyether having a molecular weight of from about 350 to about 500 compound with an excess of tolylene diisocyanate and b) distilling the reaction mixture of a) to remove unreacted excess diisocyanate down to a residual diisocyanate content of less than 0.1% by weight.
3. The process of Claim 2 in which the polyhydroxy polyether used is a polyether triol having a molecular weight in the range of from 350 to 500.
4. The process of Claim 3 in which the polyhydroxy polyether used is a polyether triol having a molecular weight in the range of from 400 to 470 which has been prepared by propoxylating a trihydric alcohol which is free of ether groups.
5. The process of Claim 4 in which the tolylene diisocyanate used is 2,4-tolylene diisocyanate or a commercial mixture thereof in which up to 35% by weight, based on the mixture, is 2,6-diisocyanatotoluene.
6. The process of Claim 3 in which the tolylene diisocyanate used is 2,4-tolylene diisocyanate or a mixture thereof in which up to 35% by weight, based on the mixture, is 2,6-diisocyanatotoluene.
Mo3816
Mo3816
7. The process of Claim 2 in which the polyhydroxy polyether is a polyether triol having a molecular weight in the range of from about 400 to about 470 which has been prepared by propoxylating a trihydric alcohol free of ether groups.
8. A process for the production of a polyurethane lacquer comprising mixing the polyisocyanate containing urethane groups of Claim 1 with a polyhydroxy compound.
9. The process of Claim 8 in which the polyisocyanate containing urethane and the polyhydroxy compound are used in quantities such that from about 0.8 to about 3 isocyanate reactive groups are present for each isocyanate group.
Mo3816
Mo3816
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4140660A DE4140660A1 (en) | 1991-12-10 | 1991-12-10 | POLYISOCYANATES HAVING ETHER AND URETHANE GROUPS, A METHOD FOR THE PRODUCTION AND THEIR USE |
| DEP4140660.5 | 1991-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2084698A1 true CA2084698A1 (en) | 1993-06-11 |
Family
ID=6446691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002084698A Abandoned CA2084698A1 (en) | 1991-12-10 | 1992-12-07 | Polyisocyanates containing ether and urethane groups, a process for their preparation and their use in the production of polyurethane lacquers |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5747628A (en) |
| EP (1) | EP0546399B1 (en) |
| JP (1) | JP3169461B2 (en) |
| AT (1) | ATE128121T1 (en) |
| CA (1) | CA2084698A1 (en) |
| DE (2) | DE4140660A1 (en) |
| ES (1) | ES2079131T3 (en) |
| GR (1) | GR3017883T3 (en) |
| MX (1) | MX9206884A (en) |
Families Citing this family (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ202995A3 (en) * | 1993-02-10 | 1996-01-17 | Rathor Ag | Composition of pre-polymers for insulation foams |
| US6552097B1 (en) * | 1993-02-10 | 2003-04-22 | Rathor Ag | Prepolymer compositions for insulating foams |
| US7101955B1 (en) | 1998-11-12 | 2006-09-05 | Alliant Techsystems Inc. | Synthesis of energetic thermoplastic elastomers containing both polyoxirane and polyoxetane blocks |
| US6997997B1 (en) | 1998-11-12 | 2006-02-14 | Alliant Techsystems Inc. | Method for the synthesis of energetic thermoplastic elastomers in non-halogenated solvents |
| DE69911647T2 (en) * | 1998-11-12 | 2004-04-29 | Alliant Techsystems Inc., Edina | MANUFACTURE OF ENERGETIC THERMOPLASTIC ELASTOMERS WHICH CONTAIN POLYOXIRANE AS POLYOXETANE BLOCKS |
| US6815522B1 (en) * | 1998-11-12 | 2004-11-09 | Alliant Techsystems Inc. | Synthesis of energetic thermoplastic elastomers containing oligomeric urethane linkages |
| US6362302B1 (en) | 1999-11-29 | 2002-03-26 | Carl E. Boddie | Method and compositions for spray molding polyurethane three dimensional objects |
| DE19957351A1 (en) * | 1999-11-29 | 2001-10-31 | Henkel Kgaa | Monomer-free reactive polyurethane adhesive or sealant composition, e.g. for use as a hot melt, obtained by reacting polyol with high-mol. wt. di-isocyanate with a low monomer content |
| DE10157488A1 (en) | 2000-12-15 | 2002-06-20 | Henkel Kgaa | Polyurethane prepolymer with low polyisocyanate monomer content, useful in e.g. food packaging and adhesive bonding, comprises mixing urethane group-containing component with low monomer content urethane-group containing polyisocyanate |
| MXPA02002226A (en) * | 2001-03-14 | 2002-09-30 | Rohm & Haas | Method for preparing isocyanate-functional prepolymers with low residual isocyanate monomer content. |
| GB0108060D0 (en) * | 2001-03-30 | 2001-05-23 | Baxenden Chem | Low monomer prepolymer |
| US20030092848A1 (en) * | 2001-09-11 | 2003-05-15 | Ashok Sengupta | Sprayable liner for supporting the rock surface of a mine |
| DE10225982B4 (en) * | 2002-06-11 | 2012-04-19 | Jowat Ag | Polyurethane compositions with a low proportion of diisocyanate monomers |
| DE50309990D1 (en) * | 2002-02-22 | 2008-07-31 | Jowat Ag | Polyurethane compositions with low content of diisocyanate monomer (s) |
| DE102005035000A1 (en) * | 2005-07-22 | 2007-01-25 | Basf Ag | Isocyanate group-containing prepolymers |
| KR20080103082A (en) * | 2006-02-21 | 2008-11-26 | 미쓰이 가가쿠 가부시키가이샤 | Polymerizable composition for polythiourethane optical material |
| DE102007025659A1 (en) | 2007-06-01 | 2008-12-11 | Bayer Materialscience Ag | NCO prepolymers with a low content of free monomeric diisocyanate and their preparation |
| CN105026364B (en) * | 2013-03-12 | 2021-04-02 | 科思创德国股份有限公司 | Process for preparing light-colored TDI-polyisocyanates |
| FR3014441B1 (en) * | 2013-12-05 | 2016-01-08 | Merylithe | PROCESS FOR THE PREPARATION OF ISOCYANATE-TERMINATING PREPOLYMERS FOR THE PREPARATION OF POLYURETHANES |
| JP6296798B2 (en) * | 2014-01-14 | 2018-03-20 | 保土谷化学工業株式会社 | Main agent for polyurethane coating waterproof material and production method thereof, polyurethane coating waterproofing material, polyurethane waterproof coating, and method for reducing free tolylene diisocyanate content |
| CN113651944B (en) | 2018-07-20 | 2022-07-15 | 科思创知识产权两合公司 | Ionically hydrophilicized polyisocyanates having improved drying properties |
| EP3599255A1 (en) | 2018-07-23 | 2020-01-29 | Covestro Deutschland AG | Ionically hydrophilized polyisocyanates with improved drying |
| EP3611204A1 (en) | 2018-08-13 | 2020-02-19 | Covestro Deutschland AG | Process for preparing polyisocyanates containing urethane groups |
| EP3827043A1 (en) | 2018-07-26 | 2021-06-02 | Covestro Intellectual Property GmbH & Co. KG | Process for preparing polyisocyanates containing urethane groups |
| EP3750934A1 (en) | 2019-06-12 | 2020-12-16 | Covestro Deutschland AG | Method for the production of isocyanate-group terminated polyoxazolidinones |
| EP3750933A1 (en) | 2019-06-12 | 2020-12-16 | Covestro Deutschland AG | Method for the production of epoxy-group terminated polyoxazolidinones |
| EP3760658A1 (en) | 2019-07-03 | 2021-01-06 | Covestro Deutschland AG | Resistant 2k-pur coatings |
| EP4010311A1 (en) * | 2019-08-09 | 2022-06-15 | Covestro Intellectual Property GmbH & Co. KG | Polyisocyanate and process for preparing the same |
| US20230080775A1 (en) | 2020-02-17 | 2023-03-16 | Covestro Deutschland Ag | Polyisocyanate preparations |
| EP3885387A1 (en) | 2020-03-25 | 2021-09-29 | Covestro Deutschland AG | Polyisocyanate-based polyaddition compounds having five-membered cyclic iminoether structural elements |
| WO2022122606A1 (en) | 2020-12-10 | 2022-06-16 | Covestro Deutschland Ag | Composition comprising epoxy-functional oxazolidinone |
| EP4011927A1 (en) | 2020-12-10 | 2022-06-15 | Covestro Deutschland AG | Composition comprising epoxy-functional oxazolidinone |
| WO2022228955A1 (en) | 2021-04-26 | 2022-11-03 | Covestro Deutschland Ag | Method for the production of an isocyanate-group terminated polyoxazolidinone composition |
| EP4083100A1 (en) | 2021-04-26 | 2022-11-02 | Covestro Deutschland AG | Method for the production of an isocyanate-group terminated polyoxazolidinone composition |
| WO2022263306A1 (en) | 2021-06-18 | 2022-12-22 | Covestro Deutschland Ag | Aldehyde-blocked organic polyisocyanates |
| EP4105251A1 (en) | 2021-06-18 | 2022-12-21 | Covestro Deutschland AG | Crosslinkable compositions containing imine and / or aminal-forming components |
| EP4108695A1 (en) | 2021-06-21 | 2022-12-28 | Covestro Deutschland AG | Coating agent and coatings produced therefrom having improved soiling resistances and (self) cleaning properties |
| EP4108694A1 (en) | 2021-06-21 | 2022-12-28 | Covestro Deutschland AG | Coating agent and coatings produced therefrom having improved soiling resistances and (self) cleaning properties |
| EP4198094A1 (en) | 2021-12-20 | 2023-06-21 | Covestro Deutschland AG | Multilayer structure on metal substrates based on polyaspartate coatings |
| EP4265663A1 (en) | 2022-04-21 | 2023-10-25 | Covestro Deutschland AG | Polyaspartate-based two-component coating compositions for the production of coatings having improved self-heating properties and low adhesion |
| EP4279522A1 (en) | 2022-05-17 | 2023-11-22 | Covestro Deutschland AG | Water-dispersible polyisocyanates with aldehyde blocking and aqueous compositions obtainable therefrom |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE870400C (en) * | 1942-07-08 | 1953-03-12 | Bayer Ag | Process for the production of polyisocyanates |
| DE953012C (en) * | 1952-07-04 | 1956-11-22 | Bayer Ag | Process for the production of soluble, preferably higher molecular weight, polyisocyanates capable of further conversion |
| US3183112A (en) * | 1955-12-06 | 1965-05-11 | Bayer Ag | Isocyanates and method of preparing same |
| US3049513A (en) * | 1959-03-26 | 1962-08-14 | Wyandotte Chemicals Corp | Ordered isocyanate-terminated polyether-based urethane compositions |
| DE1090186B (en) * | 1959-06-23 | 1960-10-06 | Demag Elektrometallurgie Gmbh | Pressure-resistant ozone device |
| DE1090196B (en) * | 1959-07-15 | 1960-10-06 | Bayer Ag | Process for the production of physiologically harmless mono- or polyisocyanates with low vapor pressure |
| US3384624A (en) * | 1965-03-01 | 1968-05-21 | Mobay Chemical Corp | Prepolymer composition |
| US3268488A (en) * | 1965-06-01 | 1966-08-23 | Mobay Chemical Corp | Urethane prepolymer from a mixture of a polyether glycol and a polyhydric alcohol |
| FR1565597A (en) * | 1968-03-18 | 1969-05-02 | Naphtachimie Sa | |
| FR2052174A6 (en) * | 1969-07-25 | 1971-04-09 | Naphtachimie Sa | |
| US3839491A (en) * | 1972-12-14 | 1974-10-01 | Peritech Int Corp | Low volatility polyurethane prepolymer |
| US3992316A (en) * | 1973-06-27 | 1976-11-16 | Bayer Aktiengesellschaft | Organic polyisocyanate solutions adapted for use in laquer |
| GB1458564A (en) * | 1973-06-27 | 1976-12-15 | Bayer Ag | Process for the preparation of solutions of polyisocyanates |
| US4169175A (en) * | 1976-06-14 | 1979-09-25 | W. R. Grace & Co. | Removal of unreacted tolylene diisocyanate from urethane prepolymers |
| US4385171A (en) * | 1982-04-30 | 1983-05-24 | Olin Corporation Research Center | Removal of unreacted diisocyanate from polyurethane prepolymers |
| US4579929A (en) * | 1985-04-18 | 1986-04-01 | The Firestone Tire & Rubber Company | Urethane compositions prepared via preformed adducts |
| US4683279A (en) * | 1986-07-08 | 1987-07-28 | Air Products And Chemicals, Inc. | Low melting urethane linked toluenediisocyanates |
| GB8725217D0 (en) * | 1987-10-28 | 1987-12-02 | Ici Plc | Polyisocyanate prepolymer |
| DE3739261A1 (en) * | 1987-11-18 | 1989-06-01 | Bayer Ag | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING URETHANE GROUPS AND THE USE THEREOF |
| US5051152A (en) * | 1989-09-26 | 1991-09-24 | Air Products And Chemicals, Inc. | Preparation of urethane prepolymers having low levels of residual toluene diisocyanate |
| US5654390A (en) * | 1995-11-17 | 1997-08-05 | Uniroyal Chemical Company, Inc. | Trimodal molecular weight polyether polyol prepolymers |
-
1991
- 1991-12-10 DE DE4140660A patent/DE4140660A1/en not_active Withdrawn
-
1992
- 1992-11-27 AT AT92120305T patent/ATE128121T1/en not_active IP Right Cessation
- 1992-11-27 DE DE59203756T patent/DE59203756D1/en not_active Expired - Fee Related
- 1992-11-27 ES ES92120305T patent/ES2079131T3/en not_active Expired - Lifetime
- 1992-11-27 EP EP92120305A patent/EP0546399B1/en not_active Expired - Lifetime
- 1992-11-30 MX MX9206884A patent/MX9206884A/en not_active IP Right Cessation
- 1992-12-02 US US07/984,596 patent/US5747628A/en not_active Expired - Fee Related
- 1992-12-07 CA CA002084698A patent/CA2084698A1/en not_active Abandoned
- 1992-12-08 JP JP35141292A patent/JP3169461B2/en not_active Expired - Fee Related
-
1995
- 1995-10-25 GR GR950402991T patent/GR3017883T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR3017883T3 (en) | 1996-01-31 |
| DE59203756D1 (en) | 1995-10-26 |
| US5747628A (en) | 1998-05-05 |
| JP3169461B2 (en) | 2001-05-28 |
| ATE128121T1 (en) | 1995-10-15 |
| MX9206884A (en) | 1993-06-01 |
| DE4140660A1 (en) | 1993-06-17 |
| JPH05247174A (en) | 1993-09-24 |
| EP0546399B1 (en) | 1995-09-20 |
| ES2079131T3 (en) | 1996-01-01 |
| EP0546399A3 (en) | 1993-09-29 |
| EP0546399A2 (en) | 1993-06-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |