CA2204084A1 - Tdi polyisocyanates containing heteroallophanate groups - Google Patents
Tdi polyisocyanates containing heteroallophanate groupsInfo
- Publication number
- CA2204084A1 CA2204084A1 CA 2204084 CA2204084A CA2204084A1 CA 2204084 A1 CA2204084 A1 CA 2204084A1 CA 2204084 CA2204084 CA 2204084 CA 2204084 A CA2204084 A CA 2204084A CA 2204084 A1 CA2204084 A1 CA 2204084A1
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- Canada
- Prior art keywords
- groups
- component
- isocyanate
- polyisocyanate
- linear aliphatic
- 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
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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
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a process for the production of polyisocyanatescontaining heteroallophanate groups and aromatically bound isocyanate groups by reacting a) a di- and/or polyurethane component which is substantially free from isocyanate groups and is based on the reaction product of a1) a linear aliphatic isocyanate component and a2) a hydroxyl group-containing component having an average OH
functionality of 1 to 1.75 with b) an isocyanate component containing at least 90 wt.% of 2,4- and/or 2,6-diisocyanatotoluene to form allophanate groups at a ratio of NCO groups to urethane groups of 3:1 to100:1 and removing excess distillable isocyanate component b) to a content below0.5%.
The present invention also relates to the use of the polyisocyanate compounds asbinders for coating, adhesive, sealant and polymer molding compositions.
functionality of 1 to 1.75 with b) an isocyanate component containing at least 90 wt.% of 2,4- and/or 2,6-diisocyanatotoluene to form allophanate groups at a ratio of NCO groups to urethane groups of 3:1 to100:1 and removing excess distillable isocyanate component b) to a content below0.5%.
The present invention also relates to the use of the polyisocyanate compounds asbinders for coating, adhesive, sealant and polymer molding compositions.
Description
~ CA 02204084 1997-04-30 Le A 31 750-US / Ecklngb/S-P
TDI POLYISOCYANATES CONTAINING ~ETEROALLOPIIANATE
GROUPS
S BACKGROUND OF THE ~NVENTION
Field of the Invention The present invention relates to a process for the production of polyisocyanatescnnt~ining allophanate groups and having aromatically bound isocyanate groups, and to their use as binders in coating compositions.
Description of the Prior Art Polyisocyanates cont~inin~; allophanate groups and having highly reactive, aromatically bound isocyanate groups and coatings produced therefrom are known (c.~ GB-A 994,980, US-A 3,769,318, 5,283,311, DE-A 2,009,179, 4,040,645 and 2,725,318). These polyisocyanates are produced by reacting excess quantities of 15 aromatic diisocyanates with mono- or polyfunctional alcohols or polymer alcohols.
The properties of the resultant products may be varied within a wide range depending upon the diisocyanate and alcohol used. A disadvantage of prior art allophanate polyisocyanates is their poor thermal stability, such that the alloph~n~te groups decompose and release the incorporated diisocyanates during 20 thin film tli.ctill~tion, which makes it impossible to completely remove excess diisocyanate following the alloph~n~ti7~tion reaction. However, if excess diiso-cyanate is not removed, then the resulting products have an elevated content of volatile isocyanates, which is not acceptable for reasons of occupational hygiene.
The "co-allophanates" produced by reacting hydroxyl components with a mixture 25 of aromatic or aliphatic and aromatic diisocyanates and described in the previously mentioned publications also do not exhibit the required thermal stability. Another disadvantage of these polyisocyanates is their multi-stage drying and cro.~linking mech~ni~m brought about by the presence in the polyisocyanate of isocyanate groups having different reactivities. This is particularly evident in co-allophanates 30 produced from mixtures of aromatic and aliphatic diisocyanates. In coating formulations these co-allophanates exhibit a relatively short pot life due to the highly reactive aromatic isocyanate groups, but complete drying of the resulting ~ CA 02204084 1997-04-30 ~ EeA31 750-US
coatings and the attainment of final properties are greatly retarded by the presence of the sparingly reactive aliphatic isocyanate groups.
An object of the present invention is to provide a process for the production ofhighly reactive polyisocyanates cont~inin~ allophanate groups, which have uniform 5 reactivity and a low monomer content and exhibit sufficient thermal stability.
This object may be achieved in accordance with the process of the present invention, which is described in greater detail below. Thermally stable poly-isocyanates having alloph~n~te groups are produced by using a linear aliphatic isocyanate component for the initial urethanization reaction and tolylene 10 diisocyanate for the subsequent alloph~n~ti7~ion. The resulting polyisocyanates contain different isocyanate groups in chemically incorporated form and are described below as "heteroalloph~n~tçs". Such polyisocyanates contain free (unreacted) aromatic isocyanate groups and thus do not exhibit the difference inreactivity known from HDI/TDI co-allophanates.
SUMMARY OF TIIE INVENTION
The present invention relates to a process for the production of polyisocyanatescont~ining heteroallophanate groups and aromatically bound isocyanate groups by reacting a) a di- and/or polyurethane component which is substantially free from isocyanate groups and is based on the reaction product of al) a linear aliphatic isocyanate component and a2) a hydroxyl group-cont~ining component having an average OH
functionality of 1 to 1.75 with b) an isocyanate component cont~ining at least 90 wt.% of 2,4- and/or 2,6-diisocyanatotoluene ' CA 02204084 1997-04-30 Le A 31 750-US
to form allophanate groups at a ratio of NCO groups to urethane groups of 3 :1 to l00:1 and removing excess distillable isocyanate component b) to a content below0.5%.
The present invention also relates to the use of the polyisocyanate compounds as5 binders for coating, adhesive, sealant and polymer molding compositions.
DETAILED DESCRIPTION OF TI~E INVENTION
Compounds a) c~-nt~inin~; urethane groups are substantially free from isocyanategroups. This means that the NCO content of compounds a) is at most 2%, preferably at most 0.5 and more preferably at most 0.2%. These levels are 10 achieved by reacting starting components al) and a2) to form compounds a) at an NCO/OH equivalent ratio of 1:1.201 to 1:2, preferably 1:1.4 to 1:1.9. Urethane formation reaction is generally performed at a temperature of 20 to 140~C, preferably 50 to 120~C and more preferably 70 to 90~C, preferably as a bulk reaction.
15 Isocyanate component al) is selected from linear aliphatic isocyanates having an average molecular weight of 110 to 1000, preferably of 140 to 340; an NCO
content of 8 to 75, preferably 22 to 60 and more preferably 40 to 60 wt.%; and an average NCO functionality of 1.8 to 4.0, preferably 2.0 to 3.0 and more preferably 2Ø Preferably, isocyanate component al) exclusively contains diisocyanates.
20 Examples of linear aliphatic diisocyanates include 1,2-diisocyanatoethane, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocy~n~tohex~ne (HDI), 1,11-diisocyanatoundecane, dodecamethylene diisocyanate, trimethyl- 1 ,6-diisocyanato-hexane and mixtures thereof.
Diisocyanates cc nt~ining ester or ether groups may also be used, although this is 25 less preferred.
It is also possible, but not preferred, to use monoisocyanates, such as hexyl isocyanate, 2-ethylhexyl isocyanate and other monoisocyanates having 4 to 18 carbon atoms.
' CA 02204084 1997-04-30 LeA31 750-US
Also suitable as starting isocyanates al) are modification products of the preceding di- and monoisocyanates, which contain biuret, uretidione, isocyanurate, allopha-nate and/or carbodiimide groups.
1,6-diisocyanatohexane and/or 1,4-butane diisocyanate are preferably used as the5 isocyanate component al); 1,6-diisocyanato-hexane is most preferably used.
Alcohol component a2) have an average functionality of 1 to 1.75, preferably 1 to 1.5 and more preferably 1 and is selected from alcohols having a number average molecular weight of 32 to 4000, preferably of 60 to 2000 and more preferably of 70 to 300. Examples of suitable compounds include saturated monoalcohols such 10 as methanol, ethanol, n-propanol, isopropanol, metho~yplopanol, isomeric buta-nols, pentanols, hexanols, n-heptanols, n-octanols, n-nonanols, n-decanols, n-dodecanols, n-octadecanol, Lorol alcohols (Henkel KGaA) and saturated fatty alcohols (for example Stenol and Guerbitol alcohols, Henkel KGaA); highly -functional polyalcohols such as ethylene glycol, 1,2- and 1,3-propanediol, 1,4 and 1 ,3-butanediol, 1,6-hexanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1,1 0-decanediol, 1,12-dodecanediol, 1,12-octadecanediol, neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl- 1,3 -propanediol, 2,2,4-trimethyl- 1,3 -pentanediol, 2-ethyl-1,3-hexanediol, dimer fatty alcohols, trimer fatty alcohols, glycerol, trimethylol-propane, trimethylol-ethane, isomeric hexanetriols, pentaerythritol and sorbitol; and 20 mixtures thereof.
It is also possible to use unsaturated alcohols such as allyl alcohol, trimethylol-propane diallyl ether, butenediol, and monofunctional alcohols derived from corresponding acids or acid mixtures cont~ining unsaturated synthetic and natural fatty acids (for example HD-Ocenol alcohols, Henkel KGaA). Naturally occurring 25 fatty acid mixtures include the acids derived from castor oil, peanut oil, cottonseed oil, safflower oil, tung oil, soya oil, sunflower oil, linseed oil, rapeseed oil, tall oil, sperm oil and herring oil.
In addition to these unsaturated monofunctional alcohols, reaction products prepared from the previously described unsaturated fatty acids and epoxy 30 compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide and 2-ethylhexyl oxide may also be used as the alcohol component a2).
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Prior art polymer polyols having ether, ester and/or carbonate groups may also be used. Of these polymer polyols, hydroxy-functional polyethers based on propyleneoxide and/or ethylene oxide are preferably used.
If the alcohol component a2) is selected from alcohol having a number average molecular weight of 901 to 4000 the NCO/OH equivalent ratio of starting component al) to a2) should be 1,2:1 to 1:2 preferably 1,1:1 to 1:1,9 and more preferably 1:1.
Most preferably, only monofunctional alcohols are used, especially alcohols having an average chain length of 12 to 22 carbon atoms.
As previously set forth, component a) is produced by reacting individual components al) and a2) to form urethane groups. It is also possible, although not preferred, to use compounds a), which were produced by a different method, for example, by using a known "phosgene-free urethane synthesis", as described, for example, in EP-A 27,940, EP-A 27,952, EP-A 27,953, EP-~ 323,514 and EP-A
355,443.
2,4- or 2,6-diisocyanatotoluene or mixtures thereof are used as the aromatic diisocyanate component b). Preferably, mixtures c~-nt~ining a minimllm of 65% of2,4-diisocyanatotoluene are used.
In order to achieve certain properties, up to 10 wt.% of other known aromatic oraliphatic mono-, di- or polyisocyanates may be added to diisocyanate component b). However, this is not preferred.
Urethane component a) is reacted with the diisocyanate component b) at an NCO/urethane equivalent ratio of 3:1 to 100:1, preferably 4:1 to 60:1 and more preferably 6:1 to 30:1 at a temperature of 20~C to 149~C, preferably 50~C to 120~C and more preferably 60~C to 90~C. Known catalysts for accelerating the alloph~n~ti7~tion reaction are also preferably used. Examples of usable catalysts include tetraalkyl-ammonium hydroxides and arylalkylammonium hydroxides.
Also suitable are metal salts such as iron(III) chloride; potassium octoate; zinc compounds such as zinc stearate, zinc octoate, zinc naphthenate and zinc acetyl-acetonate; tin compounds such as tin(II) octoate, tin(II) ethylhexanoate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin ' CA 022040X4 1997-04-30 Le A 31 750-US
dilaurate, dibutyltin maleate and dioctyltin diacetate; aluminum tri-(ethylacetoacetate); and m~ng~nese, cobalt and nickel compounds, together with mineral acids such as trifluoroacetic acid, sulphuric acid7 hydrogen chloride, hydrogen bromide, phosphoric acid and perchloric acid; and mixtures of these 5 catalysts. When reacting urethane groups with isocyanate compounds, strong acids, such as those described in EP 000 194, are less preferred. Preferably, zinc compounds are used to catalyze allophanate formation.
The catalysts may be added before the alloph~n~ti~tion reaction or before the ureth~ni7~tion reaction. They are used in concentrations of 0.001% to 5%, preferably of 0.004% to 1%, based on the weight of the reaction components. The catalyst may, if possible, be removed from the reaction mixture by (li.~till~tion.
The catalytic action may also be t~rmin~ted by the addition of catalyst poisons,such as acid chlorides or alkylating agents.
After the reaction excess, distillable starting diisocyanate b) is preferably removed 15 by thin film distillation to a residual content in the product of the at most0.5 wt.%, preferably at most 0.2 wt.%.
Depending upon the viscosity of the products obtained according to the invention, it may be appropriate to dilute them with inert solvents to a solids content of approximately 50%, preferably 80%. Suitable solvents include toluene, xylene, 20 cyclohexane, chlorobenzene, butyl acetate, ethyl acetate, ethylene glycol mono-ethyl ether acetate, pentyl acetate, hexyl acetate, methoxypropyl acetate, tetra-hydrofuran, dioxane, acetone, methyl ethyl ketone, mineral spirits, higher substituted aromatics (such as Solvent Naphtha, Solvesso, Shellsol, Isopar, Nappar and Diasol solvents), crude benzene, Tetralin solvent, Decalin solvent, alkanes 25 c~-nt~ining more than 6 carbon atoms and mixtures of these solvents. The products produced according to the invention are preferably used in solvent-free form.
The isocyanate compounds according to the invention are valuable binders for coating compositions, which may be cured under the action of atmospheric moisture and optionally atmospheric oxygen.
30 The polyisocyanates according to the invention may also be used as a cro.c.~linking component in two component coatings in combination with known compounds cont~ining two or more isocyanate-reactive groups, preferably hydroxyl groups.
LeA31 750-US
Examples include polyols such as hydroxy-functional polyethers, polyesters, polycarbonates, polyacrylates, polyamides or mixtures thereof.
The compounds produced according to the invention may also be used in blocked form in heat curing coating compositions.
The coating compositions may also contain other additives such as wetting agents, levelli~g agents, anti-~kinnin~ agents, anti-~oaming agents, Iqatting agents (such as silica, alllmimlm silicates and high-boiling waxes), viscosity-controlling sub-stances, pigments, dyes, W absorbers and stabilizers against thermal or oxidative degradation.
The coating compositions may be used for coating any desired substrates such as wood, plastics, leather, paper, textiles, glass, ceramics, rendering, masonry, metals or concrete. They may be applied using conventional application methods such as spraying, brushing, flow coating, pouring, dipping or roller application. The coating compositions may be either clear or pigmented.
The products produced using the process according to the invention are distinguished by low viscosities and good thermal stability. The thermally stable polyisocyanates have aromatic isocyanate groups and uniform reactivity. The polyisocyanates may be used as crosslinkers in one- and two-component coating compositions, which may be cured without a multi-stage curing mech~ni.~m In the following examples all parts and percentages are by weight, unless otherwise indicated.
EXAMPLES
ExamPle 1 815.4 g (3.0 moles) of an unsaturated alcohol (HD-Ocenol 110/130, product of Henkel KGaA, OH number: 200-220, iodine value: 110-130, approx. 95%
hydrocarbon chains having 18 carbon atoms) were introduced into a stirred apparatus purged with nitrogen and combined at 70~C with 168 g (1.0 mole) of 1,6-hexamethylene diisocyanate. After reacting for approximately 3 hours at a temperature of 90~C, the NCO content of the resulting urethane component had ' CA 02204084 1997-04-30 Le A 31 750-US
fallen to below 0.1%. The alloph~n~ti7~tion reaction was then initiated at 88~C by the addition of 1740 g (10.0 moles) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) and subsequent catalysis with 140 mg of zinc stearate. After 9 hours, the reaction was termin~ted at an NCO content of 24.2% by adding 140 mg 5 of isophthaloyl dichloride. The excess tolylene diisocyanate was then removed by thin film distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 1 SO~C.
Product data:
Yield: 1536 g Viscosity: 3300 mPa-s at 23~C
Free TDI content: 0.04%
NCO content: 9.1%
Example 2 325 g (2.5 moles) of 2-ethylhexanol were introduced into a stirred apparatus purged with nitrogen and combined at 70~C with 168 g (1.0 mole) of 1,6-hexamethylene diisocyanate. After reacting for approximately 3 hours at a temperature of 90~C, the NCO content of the resulting urethane component had fallen to below 0.1%. The alloph~n~ti~tion reaction was then initiated at 88~C by the addition of 1914 g (11.0 moles) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) and subsequent catalysis with 100 mg of zinc acetylacetonate. After 9 hours, the reaction was t~rmin~ted at an NCO content of 29% by adding 100 mg of isophthaloyl dichloride. The excess tolylene diisocyanate was then removed bythin film distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 150~C. When dissolved in butyl acetate, the highly viscous product had the following properties:
Solids content: 85%
Viscosity: 400 mPa s at 23 ~C
Free TDI content: 0.04%
NCO content: 10.68%
Le A 31 750-US
Example 3 203.3 g (1.0 mole) of a monofunctional alcohol (Lorol, product of Henkel KGaA, OH number: 265-275, iodine value: < 0.5, hydrocarbon chains having 12 to 18 carbon atoms) were introduced with 500 g (0.125 moles) of a polyether produced 5 by the propoxylation of propylene glycol and subsequent ethoxylation of the propoxylation product (PO/EO ratio 79/21, OH number: 28.5) into a stirred apparatus purged with nitrogen and combined at 70~C with 105 g (0.625 moles) of 1,6-hexamethylene diisocyanate. After reacting for approximately 13 hours at a temperature of 100~C, the NCO content of the resulting diurethane had fallen to below 0.2%. The alloph~n~ti7~tion reaction was then initiated at 85~C by the addition of 652.5 g (3.75 moles) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) and subsequent catalysis with 73 mg of zinc stearate. After 9 hours, an NCO content of 17.3% was obtained and the reaction was t~rrnin~ted with 70 mg of isophthaloyl dichloride. The excess TDI was then removed by thin film distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 140~C.
Product data:
Yield: 995 g Viscosity: 7500 mPa s at 23~C
Free TDI content: < 0.03%
NCO content (i): 5.4%
Example 4 (Comparison) 1392 g (16 equiv) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) were introduced into a stirred apparatus purged with nitrogen and combined at 60~C with 158 g (1 equiv) of dodecanol. After reacting for approximately 2 hours25 under a nitrogen atmosphere, the reaction temperature was raised to 120~C and the reaction was catalyzed with 150 ppm of tin(II) octoate. After an alloph~n~ti7~ion period of approximately 16 hours, an NCO content of 37.5% was achieved. The excess diisocyanate was then removed by thin i~llm distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 150~C.
~ CA 02204084 1997-04-30 Le A 31 750-US
Product data:
Yield: 364 g NCO content: 9.4%
Viscosity: 400,000 mPa-s 5 Free l'L)I content: 1.7%
The resulting homoallophanate groups exhibited inadequate thermal stability during removal of the excess monomer by distillation and partially dissociated into urethane groups and free monomer. This was detected by l3C-NMR spectroscopy.
Despite a relatively high monomer content, which diluted the polyisocyanate, the10 final product was a highly viscous resin.
Even if a renewed attempt was made to remove monomeric diisocyanate by thin film distillation, the TDI content could not be reduced below 0.5%.
Example 5 - Use of the products produced according to the invention as one-component clear composition 15 The polyisocyanate from Example 2 was applied in combination with 0.22% of dibutyltin dilaurate as catalyst as a 120 llm wet film onto a cleaned glass sheet and dried at room temperature. The resulting high gloss film exhibited the following properties:
Sand dry 40 min Touch dry 180 min Pendulum hardness after 1 day (s) 154 Pendulum hardness after 7 days (s) 172 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 25 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.
TDI POLYISOCYANATES CONTAINING ~ETEROALLOPIIANATE
GROUPS
S BACKGROUND OF THE ~NVENTION
Field of the Invention The present invention relates to a process for the production of polyisocyanatescnnt~ining allophanate groups and having aromatically bound isocyanate groups, and to their use as binders in coating compositions.
Description of the Prior Art Polyisocyanates cont~inin~; allophanate groups and having highly reactive, aromatically bound isocyanate groups and coatings produced therefrom are known (c.~ GB-A 994,980, US-A 3,769,318, 5,283,311, DE-A 2,009,179, 4,040,645 and 2,725,318). These polyisocyanates are produced by reacting excess quantities of 15 aromatic diisocyanates with mono- or polyfunctional alcohols or polymer alcohols.
The properties of the resultant products may be varied within a wide range depending upon the diisocyanate and alcohol used. A disadvantage of prior art allophanate polyisocyanates is their poor thermal stability, such that the alloph~n~te groups decompose and release the incorporated diisocyanates during 20 thin film tli.ctill~tion, which makes it impossible to completely remove excess diisocyanate following the alloph~n~ti7~tion reaction. However, if excess diiso-cyanate is not removed, then the resulting products have an elevated content of volatile isocyanates, which is not acceptable for reasons of occupational hygiene.
The "co-allophanates" produced by reacting hydroxyl components with a mixture 25 of aromatic or aliphatic and aromatic diisocyanates and described in the previously mentioned publications also do not exhibit the required thermal stability. Another disadvantage of these polyisocyanates is their multi-stage drying and cro.~linking mech~ni~m brought about by the presence in the polyisocyanate of isocyanate groups having different reactivities. This is particularly evident in co-allophanates 30 produced from mixtures of aromatic and aliphatic diisocyanates. In coating formulations these co-allophanates exhibit a relatively short pot life due to the highly reactive aromatic isocyanate groups, but complete drying of the resulting ~ CA 02204084 1997-04-30 ~ EeA31 750-US
coatings and the attainment of final properties are greatly retarded by the presence of the sparingly reactive aliphatic isocyanate groups.
An object of the present invention is to provide a process for the production ofhighly reactive polyisocyanates cont~inin~ allophanate groups, which have uniform 5 reactivity and a low monomer content and exhibit sufficient thermal stability.
This object may be achieved in accordance with the process of the present invention, which is described in greater detail below. Thermally stable poly-isocyanates having alloph~n~te groups are produced by using a linear aliphatic isocyanate component for the initial urethanization reaction and tolylene 10 diisocyanate for the subsequent alloph~n~ti7~ion. The resulting polyisocyanates contain different isocyanate groups in chemically incorporated form and are described below as "heteroalloph~n~tçs". Such polyisocyanates contain free (unreacted) aromatic isocyanate groups and thus do not exhibit the difference inreactivity known from HDI/TDI co-allophanates.
SUMMARY OF TIIE INVENTION
The present invention relates to a process for the production of polyisocyanatescont~ining heteroallophanate groups and aromatically bound isocyanate groups by reacting a) a di- and/or polyurethane component which is substantially free from isocyanate groups and is based on the reaction product of al) a linear aliphatic isocyanate component and a2) a hydroxyl group-cont~ining component having an average OH
functionality of 1 to 1.75 with b) an isocyanate component cont~ining at least 90 wt.% of 2,4- and/or 2,6-diisocyanatotoluene ' CA 02204084 1997-04-30 Le A 31 750-US
to form allophanate groups at a ratio of NCO groups to urethane groups of 3 :1 to l00:1 and removing excess distillable isocyanate component b) to a content below0.5%.
The present invention also relates to the use of the polyisocyanate compounds as5 binders for coating, adhesive, sealant and polymer molding compositions.
DETAILED DESCRIPTION OF TI~E INVENTION
Compounds a) c~-nt~inin~; urethane groups are substantially free from isocyanategroups. This means that the NCO content of compounds a) is at most 2%, preferably at most 0.5 and more preferably at most 0.2%. These levels are 10 achieved by reacting starting components al) and a2) to form compounds a) at an NCO/OH equivalent ratio of 1:1.201 to 1:2, preferably 1:1.4 to 1:1.9. Urethane formation reaction is generally performed at a temperature of 20 to 140~C, preferably 50 to 120~C and more preferably 70 to 90~C, preferably as a bulk reaction.
15 Isocyanate component al) is selected from linear aliphatic isocyanates having an average molecular weight of 110 to 1000, preferably of 140 to 340; an NCO
content of 8 to 75, preferably 22 to 60 and more preferably 40 to 60 wt.%; and an average NCO functionality of 1.8 to 4.0, preferably 2.0 to 3.0 and more preferably 2Ø Preferably, isocyanate component al) exclusively contains diisocyanates.
20 Examples of linear aliphatic diisocyanates include 1,2-diisocyanatoethane, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocy~n~tohex~ne (HDI), 1,11-diisocyanatoundecane, dodecamethylene diisocyanate, trimethyl- 1 ,6-diisocyanato-hexane and mixtures thereof.
Diisocyanates cc nt~ining ester or ether groups may also be used, although this is 25 less preferred.
It is also possible, but not preferred, to use monoisocyanates, such as hexyl isocyanate, 2-ethylhexyl isocyanate and other monoisocyanates having 4 to 18 carbon atoms.
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Also suitable as starting isocyanates al) are modification products of the preceding di- and monoisocyanates, which contain biuret, uretidione, isocyanurate, allopha-nate and/or carbodiimide groups.
1,6-diisocyanatohexane and/or 1,4-butane diisocyanate are preferably used as the5 isocyanate component al); 1,6-diisocyanato-hexane is most preferably used.
Alcohol component a2) have an average functionality of 1 to 1.75, preferably 1 to 1.5 and more preferably 1 and is selected from alcohols having a number average molecular weight of 32 to 4000, preferably of 60 to 2000 and more preferably of 70 to 300. Examples of suitable compounds include saturated monoalcohols such 10 as methanol, ethanol, n-propanol, isopropanol, metho~yplopanol, isomeric buta-nols, pentanols, hexanols, n-heptanols, n-octanols, n-nonanols, n-decanols, n-dodecanols, n-octadecanol, Lorol alcohols (Henkel KGaA) and saturated fatty alcohols (for example Stenol and Guerbitol alcohols, Henkel KGaA); highly -functional polyalcohols such as ethylene glycol, 1,2- and 1,3-propanediol, 1,4 and 1 ,3-butanediol, 1,6-hexanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1,1 0-decanediol, 1,12-dodecanediol, 1,12-octadecanediol, neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl- 1,3 -propanediol, 2,2,4-trimethyl- 1,3 -pentanediol, 2-ethyl-1,3-hexanediol, dimer fatty alcohols, trimer fatty alcohols, glycerol, trimethylol-propane, trimethylol-ethane, isomeric hexanetriols, pentaerythritol and sorbitol; and 20 mixtures thereof.
It is also possible to use unsaturated alcohols such as allyl alcohol, trimethylol-propane diallyl ether, butenediol, and monofunctional alcohols derived from corresponding acids or acid mixtures cont~ining unsaturated synthetic and natural fatty acids (for example HD-Ocenol alcohols, Henkel KGaA). Naturally occurring 25 fatty acid mixtures include the acids derived from castor oil, peanut oil, cottonseed oil, safflower oil, tung oil, soya oil, sunflower oil, linseed oil, rapeseed oil, tall oil, sperm oil and herring oil.
In addition to these unsaturated monofunctional alcohols, reaction products prepared from the previously described unsaturated fatty acids and epoxy 30 compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide and 2-ethylhexyl oxide may also be used as the alcohol component a2).
' CA 02204084 1997-04-30 ~ LeA31 750-US
Prior art polymer polyols having ether, ester and/or carbonate groups may also be used. Of these polymer polyols, hydroxy-functional polyethers based on propyleneoxide and/or ethylene oxide are preferably used.
If the alcohol component a2) is selected from alcohol having a number average molecular weight of 901 to 4000 the NCO/OH equivalent ratio of starting component al) to a2) should be 1,2:1 to 1:2 preferably 1,1:1 to 1:1,9 and more preferably 1:1.
Most preferably, only monofunctional alcohols are used, especially alcohols having an average chain length of 12 to 22 carbon atoms.
As previously set forth, component a) is produced by reacting individual components al) and a2) to form urethane groups. It is also possible, although not preferred, to use compounds a), which were produced by a different method, for example, by using a known "phosgene-free urethane synthesis", as described, for example, in EP-A 27,940, EP-A 27,952, EP-A 27,953, EP-~ 323,514 and EP-A
355,443.
2,4- or 2,6-diisocyanatotoluene or mixtures thereof are used as the aromatic diisocyanate component b). Preferably, mixtures c~-nt~ining a minimllm of 65% of2,4-diisocyanatotoluene are used.
In order to achieve certain properties, up to 10 wt.% of other known aromatic oraliphatic mono-, di- or polyisocyanates may be added to diisocyanate component b). However, this is not preferred.
Urethane component a) is reacted with the diisocyanate component b) at an NCO/urethane equivalent ratio of 3:1 to 100:1, preferably 4:1 to 60:1 and more preferably 6:1 to 30:1 at a temperature of 20~C to 149~C, preferably 50~C to 120~C and more preferably 60~C to 90~C. Known catalysts for accelerating the alloph~n~ti7~tion reaction are also preferably used. Examples of usable catalysts include tetraalkyl-ammonium hydroxides and arylalkylammonium hydroxides.
Also suitable are metal salts such as iron(III) chloride; potassium octoate; zinc compounds such as zinc stearate, zinc octoate, zinc naphthenate and zinc acetyl-acetonate; tin compounds such as tin(II) octoate, tin(II) ethylhexanoate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin ' CA 022040X4 1997-04-30 Le A 31 750-US
dilaurate, dibutyltin maleate and dioctyltin diacetate; aluminum tri-(ethylacetoacetate); and m~ng~nese, cobalt and nickel compounds, together with mineral acids such as trifluoroacetic acid, sulphuric acid7 hydrogen chloride, hydrogen bromide, phosphoric acid and perchloric acid; and mixtures of these 5 catalysts. When reacting urethane groups with isocyanate compounds, strong acids, such as those described in EP 000 194, are less preferred. Preferably, zinc compounds are used to catalyze allophanate formation.
The catalysts may be added before the alloph~n~ti~tion reaction or before the ureth~ni7~tion reaction. They are used in concentrations of 0.001% to 5%, preferably of 0.004% to 1%, based on the weight of the reaction components. The catalyst may, if possible, be removed from the reaction mixture by (li.~till~tion.
The catalytic action may also be t~rmin~ted by the addition of catalyst poisons,such as acid chlorides or alkylating agents.
After the reaction excess, distillable starting diisocyanate b) is preferably removed 15 by thin film distillation to a residual content in the product of the at most0.5 wt.%, preferably at most 0.2 wt.%.
Depending upon the viscosity of the products obtained according to the invention, it may be appropriate to dilute them with inert solvents to a solids content of approximately 50%, preferably 80%. Suitable solvents include toluene, xylene, 20 cyclohexane, chlorobenzene, butyl acetate, ethyl acetate, ethylene glycol mono-ethyl ether acetate, pentyl acetate, hexyl acetate, methoxypropyl acetate, tetra-hydrofuran, dioxane, acetone, methyl ethyl ketone, mineral spirits, higher substituted aromatics (such as Solvent Naphtha, Solvesso, Shellsol, Isopar, Nappar and Diasol solvents), crude benzene, Tetralin solvent, Decalin solvent, alkanes 25 c~-nt~ining more than 6 carbon atoms and mixtures of these solvents. The products produced according to the invention are preferably used in solvent-free form.
The isocyanate compounds according to the invention are valuable binders for coating compositions, which may be cured under the action of atmospheric moisture and optionally atmospheric oxygen.
30 The polyisocyanates according to the invention may also be used as a cro.c.~linking component in two component coatings in combination with known compounds cont~ining two or more isocyanate-reactive groups, preferably hydroxyl groups.
LeA31 750-US
Examples include polyols such as hydroxy-functional polyethers, polyesters, polycarbonates, polyacrylates, polyamides or mixtures thereof.
The compounds produced according to the invention may also be used in blocked form in heat curing coating compositions.
The coating compositions may also contain other additives such as wetting agents, levelli~g agents, anti-~kinnin~ agents, anti-~oaming agents, Iqatting agents (such as silica, alllmimlm silicates and high-boiling waxes), viscosity-controlling sub-stances, pigments, dyes, W absorbers and stabilizers against thermal or oxidative degradation.
The coating compositions may be used for coating any desired substrates such as wood, plastics, leather, paper, textiles, glass, ceramics, rendering, masonry, metals or concrete. They may be applied using conventional application methods such as spraying, brushing, flow coating, pouring, dipping or roller application. The coating compositions may be either clear or pigmented.
The products produced using the process according to the invention are distinguished by low viscosities and good thermal stability. The thermally stable polyisocyanates have aromatic isocyanate groups and uniform reactivity. The polyisocyanates may be used as crosslinkers in one- and two-component coating compositions, which may be cured without a multi-stage curing mech~ni.~m In the following examples all parts and percentages are by weight, unless otherwise indicated.
EXAMPLES
ExamPle 1 815.4 g (3.0 moles) of an unsaturated alcohol (HD-Ocenol 110/130, product of Henkel KGaA, OH number: 200-220, iodine value: 110-130, approx. 95%
hydrocarbon chains having 18 carbon atoms) were introduced into a stirred apparatus purged with nitrogen and combined at 70~C with 168 g (1.0 mole) of 1,6-hexamethylene diisocyanate. After reacting for approximately 3 hours at a temperature of 90~C, the NCO content of the resulting urethane component had ' CA 02204084 1997-04-30 Le A 31 750-US
fallen to below 0.1%. The alloph~n~ti7~tion reaction was then initiated at 88~C by the addition of 1740 g (10.0 moles) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) and subsequent catalysis with 140 mg of zinc stearate. After 9 hours, the reaction was termin~ted at an NCO content of 24.2% by adding 140 mg 5 of isophthaloyl dichloride. The excess tolylene diisocyanate was then removed by thin film distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 1 SO~C.
Product data:
Yield: 1536 g Viscosity: 3300 mPa-s at 23~C
Free TDI content: 0.04%
NCO content: 9.1%
Example 2 325 g (2.5 moles) of 2-ethylhexanol were introduced into a stirred apparatus purged with nitrogen and combined at 70~C with 168 g (1.0 mole) of 1,6-hexamethylene diisocyanate. After reacting for approximately 3 hours at a temperature of 90~C, the NCO content of the resulting urethane component had fallen to below 0.1%. The alloph~n~ti~tion reaction was then initiated at 88~C by the addition of 1914 g (11.0 moles) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) and subsequent catalysis with 100 mg of zinc acetylacetonate. After 9 hours, the reaction was t~rmin~ted at an NCO content of 29% by adding 100 mg of isophthaloyl dichloride. The excess tolylene diisocyanate was then removed bythin film distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 150~C. When dissolved in butyl acetate, the highly viscous product had the following properties:
Solids content: 85%
Viscosity: 400 mPa s at 23 ~C
Free TDI content: 0.04%
NCO content: 10.68%
Le A 31 750-US
Example 3 203.3 g (1.0 mole) of a monofunctional alcohol (Lorol, product of Henkel KGaA, OH number: 265-275, iodine value: < 0.5, hydrocarbon chains having 12 to 18 carbon atoms) were introduced with 500 g (0.125 moles) of a polyether produced 5 by the propoxylation of propylene glycol and subsequent ethoxylation of the propoxylation product (PO/EO ratio 79/21, OH number: 28.5) into a stirred apparatus purged with nitrogen and combined at 70~C with 105 g (0.625 moles) of 1,6-hexamethylene diisocyanate. After reacting for approximately 13 hours at a temperature of 100~C, the NCO content of the resulting diurethane had fallen to below 0.2%. The alloph~n~ti7~tion reaction was then initiated at 85~C by the addition of 652.5 g (3.75 moles) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) and subsequent catalysis with 73 mg of zinc stearate. After 9 hours, an NCO content of 17.3% was obtained and the reaction was t~rrnin~ted with 70 mg of isophthaloyl dichloride. The excess TDI was then removed by thin film distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 140~C.
Product data:
Yield: 995 g Viscosity: 7500 mPa s at 23~C
Free TDI content: < 0.03%
NCO content (i): 5.4%
Example 4 (Comparison) 1392 g (16 equiv) of tolylene diisocyanate (TDI, 2,4-:2,6-isomer ratio = 80:20) were introduced into a stirred apparatus purged with nitrogen and combined at 60~C with 158 g (1 equiv) of dodecanol. After reacting for approximately 2 hours25 under a nitrogen atmosphere, the reaction temperature was raised to 120~C and the reaction was catalyzed with 150 ppm of tin(II) octoate. After an alloph~n~ti7~ion period of approximately 16 hours, an NCO content of 37.5% was achieved. The excess diisocyanate was then removed by thin i~llm distillation under a high vacuum (0.1-0.3 mbar) at a temperature of 150~C.
~ CA 02204084 1997-04-30 Le A 31 750-US
Product data:
Yield: 364 g NCO content: 9.4%
Viscosity: 400,000 mPa-s 5 Free l'L)I content: 1.7%
The resulting homoallophanate groups exhibited inadequate thermal stability during removal of the excess monomer by distillation and partially dissociated into urethane groups and free monomer. This was detected by l3C-NMR spectroscopy.
Despite a relatively high monomer content, which diluted the polyisocyanate, the10 final product was a highly viscous resin.
Even if a renewed attempt was made to remove monomeric diisocyanate by thin film distillation, the TDI content could not be reduced below 0.5%.
Example 5 - Use of the products produced according to the invention as one-component clear composition 15 The polyisocyanate from Example 2 was applied in combination with 0.22% of dibutyltin dilaurate as catalyst as a 120 llm wet film onto a cleaned glass sheet and dried at room temperature. The resulting high gloss film exhibited the following properties:
Sand dry 40 min Touch dry 180 min Pendulum hardness after 1 day (s) 154 Pendulum hardness after 7 days (s) 172 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 25 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.
Claims (11)
1. A process for the production of a polyisocyanate containing heteroallophanate groups and aromatically bound isocyanate groups which comprises reacting a) a di- and/or polyurethane component which is substantially free from isocyanate groups and is based on the reaction product of a1) a linear aliphatic isocyanate component and a2) a hydroxyl group-containing component having an average OH functionality of 1 to 1.75 with b) an isocyanate component containing at least 90 wt.% of 2,4- and/or
2,6-diisocyanatotoluene to form allophanate groups at a ratio of NCO groups to urethane groups of 3:1 to 100:1 and removing excess distillable isocyanate component b) to a content below 0.5%.
2. The process of Claim 1 wherein linear aliphatic isocyanate component a1) comprises hexamethylene diisocyanate.
2. The process of Claim 1 wherein linear aliphatic isocyanate component a1) comprises hexamethylene diisocyanate.
3. The process of Claim 1 wherein component a2) consists essentially of monofunctional alcohols having an average chain length of 12 to 22 carbon atoms.
4. The process of Claim 2 wherein component a2) consists essentially of monofunctional alcohols having an average chain length of 12 to 22 carbon atoms.
5. The process of Claim 1 which comprises carrying out allophanate formation in the presence a catalyst containing zinc.
6. A polyisocyanate containing heteroallophanate groups and aromatically bound isocyanate groups which is prepared by a process which comprises reacting a) a di- and/or polyurethane component which is substantially free from isocyanate groups and is based on the reaction product of a1) a linear aliphatic isocyanate component and a2) a hydroxyl group-containing component having an average OH functionality of 1 to 1.75 with b) an isocyanate component containing at least 90 wt.% of 2,4- and/or 2,6-diisocyanatotoluene to form allophanate groups at a ratio of NCO groups to urethane groups of 3:1 to 100:1 and removing excess distillable isocyanate component b) to a content below 0.5%.
7. The polyisocyanate of Claim 6 wherein linear aliphatic isocyanate component a1) comprises hexamethylene diisocyanate.
8. The polyisocyanate of Claim 6 wherein component a2) consists essentially of monofunctional alcohols having an average chain length of 12 to 22 carbon atoms.
9. The polyisocyanate of Claim 7 wherein component a2) consists essentially of monofunctional alcohols having an average chain length of 12 to 22 carbon atoms.
10. A one-component coating composition containing the polyisocyanate of Claim 6.
11. A two-component coating composition containing the polyisocyanate of Claim 6 and a compound containing two or more isocyanate-reactive groups.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19618230.1 | 1996-05-07 | ||
DE1996118230 DE19618230A1 (en) | 1996-05-07 | 1996-05-07 | TDI polyisocyanates containing heteroallophanate groups |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2204084A1 true CA2204084A1 (en) | 1997-11-07 |
Family
ID=7793541
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2204084 Abandoned CA2204084A1 (en) | 1996-05-07 | 1997-04-30 | Tdi polyisocyanates containing heteroallophanate groups |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0807623A3 (en) |
JP (1) | JPH1067845A (en) |
CA (1) | CA2204084A1 (en) |
DE (1) | DE19618230A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6936678B2 (en) | 2002-07-03 | 2005-08-30 | Bayer Aktiengesellschaft | Process for preparing low-monomer-content TDI trimers |
CN103119077A (en) * | 2010-07-20 | 2013-05-22 | 拜耳知识产权有限责任公司 | Polyurethane having high light refraction |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19804432A1 (en) * | 1998-02-05 | 1999-08-12 | Bayer Ag | Polyurethane-polyacrylate hybrid dispersions containing allophanate groups |
IT1391369B1 (en) | 2008-10-06 | 2011-12-13 | Azionaria Per L Ind Chimica Italiana S A P I C I Spa Soc | POLYISOCYANATES SUITABLE FOR THE FORMULATION OF LOW-SOLVENT PAINTS AND PROCESS FOR THEIR PREPARATION |
WO2019157625A1 (en) | 2018-02-13 | 2019-08-22 | Covestro Deutschland Ag | Aromatic polyisocyanates with a high solids content |
EP3599255A1 (en) | 2018-07-23 | 2020-01-29 | Covestro Deutschland AG | Ionically hydrophilized polyisocyanates with improved drying |
EP3824009B1 (en) | 2018-07-20 | 2022-03-09 | Covestro Intellectual Property GmbH & Co. KG | Ionically hydrophilized polyisocyanates with improved drying |
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 |
CN115066445A (en) | 2020-02-17 | 2022-09-16 | 科思创德国股份有限公司 | Polyisocyanate formulations |
CN112625570A (en) * | 2020-12-08 | 2021-04-09 | 默利卡高分子材料(上海)有限公司 | Coating polyurethane mortar |
EP4011927A1 (en) | 2020-12-10 | 2022-06-15 | Covestro Deutschland AG | Composition comprising epoxy-functional oxazolidinone |
US20240076439A1 (en) | 2020-12-10 | 2024-03-07 | Covestro Deutschland Ag | Composition Comprising Epoxy-Functional Oxazolidinone |
US20240199787A1 (en) | 2021-04-26 | 2024-06-20 | 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 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5319054A (en) * | 1993-09-02 | 1994-06-07 | Miles Inc. | Liquid methylene diphenyl diisocyanate |
DE4441176A1 (en) * | 1994-11-18 | 1996-05-23 | Bayer Ag | Polyisocyanates containing allophanate groups |
DE19534162A1 (en) * | 1995-09-15 | 1997-03-20 | Bayer Ag | Binder combination for the production of solvent-free coating compositions |
-
1996
- 1996-05-07 DE DE1996118230 patent/DE19618230A1/en not_active Withdrawn
-
1997
- 1997-04-24 EP EP97106777A patent/EP0807623A3/en not_active Withdrawn
- 1997-04-30 CA CA 2204084 patent/CA2204084A1/en not_active Abandoned
- 1997-05-06 JP JP9130556A patent/JPH1067845A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6936678B2 (en) | 2002-07-03 | 2005-08-30 | Bayer Aktiengesellschaft | Process for preparing low-monomer-content TDI trimers |
CN103119077A (en) * | 2010-07-20 | 2013-05-22 | 拜耳知识产权有限责任公司 | Polyurethane having high light refraction |
CN103119077B (en) * | 2010-07-20 | 2015-10-21 | 拜耳知识产权有限责任公司 | There is the urethane of high light refraction |
Also Published As
Publication number | Publication date |
---|---|
JPH1067845A (en) | 1998-03-10 |
EP0807623A2 (en) | 1997-11-19 |
DE19618230A1 (en) | 1997-11-13 |
EP0807623A3 (en) | 1998-01-07 |
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