CA2113890A1 - Trimer catalyst for aliphatic and aromatic isocyanates - Google Patents
Trimer catalyst for aliphatic and aromatic isocyanatesInfo
- Publication number
- CA2113890A1 CA2113890A1 CA002113890A CA2113890A CA2113890A1 CA 2113890 A1 CA2113890 A1 CA 2113890A1 CA 002113890 A CA002113890 A CA 002113890A CA 2113890 A CA2113890 A CA 2113890A CA 2113890 A1 CA2113890 A1 CA 2113890A1
- Authority
- CA
- Canada
- Prior art keywords
- lithium
- diisocyanate
- compound
- group
- butanediol
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
- C07D251/34—Cyanuric or isocyanuric esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
NEW TRIMER CATALYST FOR ALIPHATIC AND AROMATIC ISOCYANATES
ABSTRACT OF THE DISCLOSURE
This invention relates to a process for trimerizing organic polyisocyanates in the presence of thermally active catalyst systems. The catalyst systems comprise (a) compounds selected from the group consisting of 1) lithium salts of aliphatic or aromatic carboxylic acids, 2) lithium salts of hydroxyl group containing compounds wherein the hydroxyl groups are directed attached to an aromatic ring, and 3) lithium hydroxide; used in conjunction with (b) an organic compound which contains at least one hydroxyl group.
ABSTRACT OF THE DISCLOSURE
This invention relates to a process for trimerizing organic polyisocyanates in the presence of thermally active catalyst systems. The catalyst systems comprise (a) compounds selected from the group consisting of 1) lithium salts of aliphatic or aromatic carboxylic acids, 2) lithium salts of hydroxyl group containing compounds wherein the hydroxyl groups are directed attached to an aromatic ring, and 3) lithium hydroxide; used in conjunction with (b) an organic compound which contains at least one hydroxyl group.
Description
~ 3 ~ ~ ~04 NEW TRIMER CATALYST FOR ALIPHATIC AND AROMATIC ISQÇYA~~
BACKGROUND OF THE INVENTION
This invention relates to a process for the trimerization of isocyanates in the presence of a thermally active catalyst.
The catalyst system comprises A) a lithium compound selected from the group consisting of 1) lithium salts of aliphatic or aromatic mono- or dicarboxylic acids, 2) lithium salts of hydroxyl group containing compounds having from 1 to 3 hydroxyl groups per compound, wherein the hydroxyl groups are directly lo attached to an aromatic ring, and 3) lithium hydroxide; used in -conjunction with B) an organic compound containing at least one hydroxyl group.
The trimerization of isocyanates to form polyisocyanurates is well known in the art. Trimerization catalysts described in - -~
the prior art include alkali carboxylates as described in DE-OS
3~219,608, basic alkali metal salts complexed with acyclic organic compounds as described in U.S. Patent 4,379,905, basic alkali metal salts complexed with crown ethers as described in l~
U.S. Patent 4,487,928, and combinations of tertiary amines with ~ ~ -specific quaternary ammonium salts as described in U.S. Patent 3,954,684.
Catalysts described ;n U.S. Patents 4,632,785 and 4,540,781 comprise alkali metal salts or quaternary ammonium 1~ ~ -salts of carboxylic acids of the formulas R
R300C - C - COO M+
12 .
R
35376DsO124 -` 211 ~'.30 R4NHC - C - COO M~ ~
R -:
.
~' ~
and : -1 o , ' " '' `~
R -~
R5 - C - COO M~ - ;
,:'~
~ `~
. ., - ::
wherein R1 is alkyl having from 2 to 8 carbon atoms, R2 is a ;;~
highly branched alkyl having from 3 to 8 carbon atoms, R3 is ~:
selected from the group consisting of hydrogen, alkyl, and aryl, R4 i!; selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl, R5 is independently selected from aryl, and M+ is a cation selected from the group consisting of alkali metal cations and quaternary ammonium cations of a specific formula.
DESCRIPTTON OF THE INVENTION
This invention relates to a new process for the preparation of a polyisocyanate having isocyanurate structure.
In particular, the process for the preparation of a polyisocyanate having isocyanurate structure comprises heating an organic isocyanate, or mixtures thereof, to a temperature of from about 100 to about 300C, preferably from about 125 to about 250C, in the presence of a catalytic amount of -Mo3904 3 21~3~0 (a) a compound selected from the group consisting of i) lithium salts of aliphatic or aromatic mono- or dicarboxylic acids, ii) lithium salts of hydroxyl group containing compounds having from 1 to 3 hydroxyl groups per compound, wherein said hydroxyl groups are attached directly to an aromatic ring, and iii) lithium hydroxide; used in conjunction with (b) an organic compound having at least one hydroxyl lo group. --According to the invention, from about 0.0001 to about 1 - m part of the lithium salt compound, or lithium hydroxide, should be used in conjunction with from about 0.01 to 10 parts of the ~-organic compound which contains at least one hydroxyl group for -100 parts of isocyanate. The reaction can be run as either a batch or a continuous process. Reaction times vary between 1-240 minutes, and preferably from 2-120 minutes. It is preferred to use from about 0.001 to 0.01 parts of lithium salt or lithium hydroxide, and from about 0.05 to 4.0 parts of organic compound which contains hydroxyl groups per 100 parts - ~
of isocyanate. ~ -Suitable lithium compounds for use in the present ~~
invention include both the monolithium and dilithium salts of aliphatic and aromatic carboxylic acids containing a total of from about 1 to 36 carbon atoms. Both the mono- or dicarboxylic acids are suitable for the process according to the invention.
Examples of these lithium compounds include lithium formate, -lithium salicylate, lithium acetate, lith;um stearate, lith;um -propanate, lithium butyrate, lithium lactate, lithium laurate, 3o lithium benzoatc, lithium p-hydroxybenzoate, lithium 4-hydroxyphenylacetate, monolithium salt of oxalic acid, dilithium salt of oxalic acid, monolithium salt of glutaric acid, dilithium salt of glutaric acid, monolithium salt of isophthalic acid, dilithium salt of isophthalic acid, monolithium salt of phthalic acid, dilithium salt of phthalic Mo3904 -` Z113~0 acid, monolithium salt of terephthalic acid, and dilithium salt of terephthalic acid. Of these salts, lithium salicylate, lithium acetate, and lith;um stearate are preferred.
The lithium compound may also be the lithium salt of a hydroxy group containing compound wherein the hydroxyl groups are directly attached to an aromatic ring. These compounds may contain from 1 to 3 hydroxyl groups each, and the aromatic ring contains a total of from 6 to 18 carbon atoms. Suitable compounds include lithium phenoxide, 4-methyl lithium lo phenoxide, 2-hydroxy lithium phenoxide, 3-hydroxy lithium phenoxide, 4-hydroxy lithium phenoxide, lithium l-naphthoxide, lithium 2-naphthoxide, etc. Lithium salts of cresols, anthracenes, and phenanthracenes are also suitable ~- -trimerization catalysts. Theoretically, the lithium salts of substituted aromatic compounds are suitable provided the substituents do not deactivate the ring so that it is no longer an effective trimerization catalyst.
Lithium salts of carboxylic acids are readily obtained using standard preparative methods well known to one skilled in the art. Equation (1) represents a general preparative method.
RlCO~H + LiA - > RlC00 Li+ + AH (1) wherein: Rl represents hydrogen or an aliphatic or 2~ aromatic hydrocarbon chain of from 0-35 ~ -carbon atoms, A represents a neutralized anion such as hydroxyl, hydride, alkoxide, etc. ~ -The reactant LiA is used in an amount which is slightly less than molar equivalency, thereby ensuring that no residual reactant will remain in the products.
The lithium salts of hydroxyl group containing compounds wherein the hydroxyl groups are directly attached to an aromatic ring can be prepared by a typical acid base reaction, followed by the distillation of water, methanol, etc. However, Mo3904 ~5- '~11 3890 the base must be stronger than the an~on of the hydroxyl group of the aromatic compound. For example, lithium phenoxide can be prepared by reacting phenol with lithium hydroxide or lithium methoxide.
Suitable carboxylic acids for the preparation of the lithium salts (a)i) include those aliphatic and aromatic carboxylic ac;ds having from about 1 - 36 carbon atoms. These --acids may be either branched or straight chain, and either saturated or unsaturated. Both monocarboxylic acids and lo dicarboxylic acids are suitable. Some examples of these include formic acid, acetic acid, propionic acid, stearic acid, lactic acid, salicylic acid, lauric acid, glutaric acid, p-hydroxy- ~
benzo;c acid, phthal;c acid, isophthalic acid, and terephthalic ~ -acid. Theoretically, any compound having the carboxylic acid group would be suitable provided any additional substituents do not interfere with the formation of the salt.
Hydroxyl group containing compounds having at least one hydroxyl group attached directly to an aromatic ring which are suitable for the preparation of lithium salts (a)ii) include those aromatic alcohols containing from about 6 to 18 carbon atoms, ar,d having from 1 to 3 hydroxyl groups present per aromatic ring. Examples of these aromatic compounds include phenol, m-cresol, resorcinol, hydroquinone, catechol, l-naphthol, 2-naphthol, hydroxyanthracene, hydroxyphenanthrene, etc.
According to the present invention, these lithium compounds (a) are to be used in conjunction with a small amount of (b) an orgar,ic compound which contains hydroxyl groups.
Generally these organic compounds contain from 1 to 4 hydroxyl groups and have about 1 to 18 carbon atoms. Suitable organic compounds include methanol, l-ethanol, 1,2-ethanediol, l-propanol, 2-propanol, l-butanol, 2-butanol, isobutyl alcohol, n-amyl alcohol, sec-amyl alcohol, tert-amyl alcohol, l-methylbutyl alcohol, l-ethyl-l-propanol, n-octyl alcohol, 2-octyl alcohol, n-decyl alcohol, n-dodecyl alcohol, ~ -Mo3904 -6- 2~3~90 neopentylglycol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-2-butanol, 3,3-dimethyl-1-butanol, 2-ethyl-1,3-hexanediol, glycerol, 1,2,4-butanetriol, pentaerythr;tol, etc. It is preferred for these organic compounds to contain from 1 to 2 hydroxyl groups, such as a monoalcohol or a diol, and have from about 1 to 8 carbon atoms. Examples include methanol, 1-ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, n-amyl alcohol, 1-methylbutyl o alcohol, 1-ethyl-1-propanol, n-octyl alcohol, 2-octyl alcohol, neopentylglycol, 1,3-propanediol, 1,4-butanediol, 1,3-butane-diol, 2,3-butaned;ol, 2-ethyl-1,3-hexanediol, etc. It is most preferred to use those compounds which have 2 hydroxyl groups, and contain either 3 or 4 carbon atoms. 1,3-propanediol and 1,3-butanediol are among the most preferred organic compounds.
Suitable polyisocyanates to be trimerized according to the present invention, to yield polyisocyanates having an isocyanurate structure, include the known aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic 20: polyisocyanates, and mixtures thereof. Examples of these polyisocyanates include those described by W. Siefen in ~ustus Liebigs Annalen der Chemie, 562, pages 75 to 136. More specifically, suitable polyisocyanates include, but are not limited to, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, diphenyl methane-4,4-diisocyanate, naphthylene 1,5-diiso-cyanate, hexamethylene-1,6 diisocyanate, 1-isocyanato-3,5,5-trimethyl-5-isocyanato-methyl-cyclohexane, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato~
3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (i.e. isophorone ~ -diisocyanate), 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'diphenylmethane diisocyanate, 1,3- and/or 1,4-phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, naphthalene-1,5-Mo3904 ::
` 7 21~3 diisocyanate, trlphenylmethane-4,4',4"-trlisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensation products. Also suitable are polyisocyanate adducts containing urea, biuret, urethane, allophanate, uretdione, or carbodiimide groups or isocyanurate rings. Preferred polyisocyanates include aromatic and aliphatic isocyanates, with hexamethylene-1,6-diisocyanate, 2,4-diisocyanatotoluene, 2,6-d;isocyanatotoluene, and diphenyl methane-4,4'-diisocyanate, and mixtures thereof, being lo particularly preferred.
EXAMPLES
The followin~ examples further illustrate details for the process of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all parts are parts by weight.
Example 1:
To a 250 ml 3-neck flask equipped with a condenser, thermometer, mechanical stirrer, and purged with dry nitrogen was added 100 grams of hexamethylene diisocyanate (HDI), 0.1 9.
of 1,3-butanediol, and 0.002 9. of lithium salicylate. The reaction mlxture was heated over a 4 minute period to 250~C and - -~
held there for about 4 minutes. At the end of the time, it was cooled over a 3 minute period to about 40C and 0.01 9 of benzoyl chloride was added. The resulting reaction mixture has --~ -a NC0 content of 39.3%. The hexamethylene diisocyanate (HDI) monomer was removed by thin film evaporation to give a clear liquid having a viscosity of 7820 mPa.s at 25C, and a NC0 content of 20.4%.
: ~-' ~ ' Mo3904 Example 2:
The same reaction was ran as in Example 1, except that 0.006 9 of lithium salicylate was used and no 1,3-butanediol was used. No trimerization was observed.
Example 3:
The same reaction was ran as in Example 1, except that the lithium salicylate was dissolved in the 1,3-butanediol and this clear solution was added to the hexamethylene-1,6-diisocyanate (HDI). The reaction mixture has a NC0 content of 39.1% after lo heating.
The following formulations were also tested. All amounts are in parts by weight (pbw) unless otherwise indicated.
BACKGROUND OF THE INVENTION
This invention relates to a process for the trimerization of isocyanates in the presence of a thermally active catalyst.
The catalyst system comprises A) a lithium compound selected from the group consisting of 1) lithium salts of aliphatic or aromatic mono- or dicarboxylic acids, 2) lithium salts of hydroxyl group containing compounds having from 1 to 3 hydroxyl groups per compound, wherein the hydroxyl groups are directly lo attached to an aromatic ring, and 3) lithium hydroxide; used in -conjunction with B) an organic compound containing at least one hydroxyl group.
The trimerization of isocyanates to form polyisocyanurates is well known in the art. Trimerization catalysts described in - -~
the prior art include alkali carboxylates as described in DE-OS
3~219,608, basic alkali metal salts complexed with acyclic organic compounds as described in U.S. Patent 4,379,905, basic alkali metal salts complexed with crown ethers as described in l~
U.S. Patent 4,487,928, and combinations of tertiary amines with ~ ~ -specific quaternary ammonium salts as described in U.S. Patent 3,954,684.
Catalysts described ;n U.S. Patents 4,632,785 and 4,540,781 comprise alkali metal salts or quaternary ammonium 1~ ~ -salts of carboxylic acids of the formulas R
R300C - C - COO M+
12 .
R
35376DsO124 -` 211 ~'.30 R4NHC - C - COO M~ ~
R -:
.
~' ~
and : -1 o , ' " '' `~
R -~
R5 - C - COO M~ - ;
,:'~
~ `~
. ., - ::
wherein R1 is alkyl having from 2 to 8 carbon atoms, R2 is a ;;~
highly branched alkyl having from 3 to 8 carbon atoms, R3 is ~:
selected from the group consisting of hydrogen, alkyl, and aryl, R4 i!; selected from the group consisting of alkyl, aryl, aralkyl, and cycloalkyl, R5 is independently selected from aryl, and M+ is a cation selected from the group consisting of alkali metal cations and quaternary ammonium cations of a specific formula.
DESCRIPTTON OF THE INVENTION
This invention relates to a new process for the preparation of a polyisocyanate having isocyanurate structure.
In particular, the process for the preparation of a polyisocyanate having isocyanurate structure comprises heating an organic isocyanate, or mixtures thereof, to a temperature of from about 100 to about 300C, preferably from about 125 to about 250C, in the presence of a catalytic amount of -Mo3904 3 21~3~0 (a) a compound selected from the group consisting of i) lithium salts of aliphatic or aromatic mono- or dicarboxylic acids, ii) lithium salts of hydroxyl group containing compounds having from 1 to 3 hydroxyl groups per compound, wherein said hydroxyl groups are attached directly to an aromatic ring, and iii) lithium hydroxide; used in conjunction with (b) an organic compound having at least one hydroxyl lo group. --According to the invention, from about 0.0001 to about 1 - m part of the lithium salt compound, or lithium hydroxide, should be used in conjunction with from about 0.01 to 10 parts of the ~-organic compound which contains at least one hydroxyl group for -100 parts of isocyanate. The reaction can be run as either a batch or a continuous process. Reaction times vary between 1-240 minutes, and preferably from 2-120 minutes. It is preferred to use from about 0.001 to 0.01 parts of lithium salt or lithium hydroxide, and from about 0.05 to 4.0 parts of organic compound which contains hydroxyl groups per 100 parts - ~
of isocyanate. ~ -Suitable lithium compounds for use in the present ~~
invention include both the monolithium and dilithium salts of aliphatic and aromatic carboxylic acids containing a total of from about 1 to 36 carbon atoms. Both the mono- or dicarboxylic acids are suitable for the process according to the invention.
Examples of these lithium compounds include lithium formate, -lithium salicylate, lithium acetate, lith;um stearate, lith;um -propanate, lithium butyrate, lithium lactate, lithium laurate, 3o lithium benzoatc, lithium p-hydroxybenzoate, lithium 4-hydroxyphenylacetate, monolithium salt of oxalic acid, dilithium salt of oxalic acid, monolithium salt of glutaric acid, dilithium salt of glutaric acid, monolithium salt of isophthalic acid, dilithium salt of isophthalic acid, monolithium salt of phthalic acid, dilithium salt of phthalic Mo3904 -` Z113~0 acid, monolithium salt of terephthalic acid, and dilithium salt of terephthalic acid. Of these salts, lithium salicylate, lithium acetate, and lith;um stearate are preferred.
The lithium compound may also be the lithium salt of a hydroxy group containing compound wherein the hydroxyl groups are directly attached to an aromatic ring. These compounds may contain from 1 to 3 hydroxyl groups each, and the aromatic ring contains a total of from 6 to 18 carbon atoms. Suitable compounds include lithium phenoxide, 4-methyl lithium lo phenoxide, 2-hydroxy lithium phenoxide, 3-hydroxy lithium phenoxide, 4-hydroxy lithium phenoxide, lithium l-naphthoxide, lithium 2-naphthoxide, etc. Lithium salts of cresols, anthracenes, and phenanthracenes are also suitable ~- -trimerization catalysts. Theoretically, the lithium salts of substituted aromatic compounds are suitable provided the substituents do not deactivate the ring so that it is no longer an effective trimerization catalyst.
Lithium salts of carboxylic acids are readily obtained using standard preparative methods well known to one skilled in the art. Equation (1) represents a general preparative method.
RlCO~H + LiA - > RlC00 Li+ + AH (1) wherein: Rl represents hydrogen or an aliphatic or 2~ aromatic hydrocarbon chain of from 0-35 ~ -carbon atoms, A represents a neutralized anion such as hydroxyl, hydride, alkoxide, etc. ~ -The reactant LiA is used in an amount which is slightly less than molar equivalency, thereby ensuring that no residual reactant will remain in the products.
The lithium salts of hydroxyl group containing compounds wherein the hydroxyl groups are directly attached to an aromatic ring can be prepared by a typical acid base reaction, followed by the distillation of water, methanol, etc. However, Mo3904 ~5- '~11 3890 the base must be stronger than the an~on of the hydroxyl group of the aromatic compound. For example, lithium phenoxide can be prepared by reacting phenol with lithium hydroxide or lithium methoxide.
Suitable carboxylic acids for the preparation of the lithium salts (a)i) include those aliphatic and aromatic carboxylic ac;ds having from about 1 - 36 carbon atoms. These --acids may be either branched or straight chain, and either saturated or unsaturated. Both monocarboxylic acids and lo dicarboxylic acids are suitable. Some examples of these include formic acid, acetic acid, propionic acid, stearic acid, lactic acid, salicylic acid, lauric acid, glutaric acid, p-hydroxy- ~
benzo;c acid, phthal;c acid, isophthalic acid, and terephthalic ~ -acid. Theoretically, any compound having the carboxylic acid group would be suitable provided any additional substituents do not interfere with the formation of the salt.
Hydroxyl group containing compounds having at least one hydroxyl group attached directly to an aromatic ring which are suitable for the preparation of lithium salts (a)ii) include those aromatic alcohols containing from about 6 to 18 carbon atoms, ar,d having from 1 to 3 hydroxyl groups present per aromatic ring. Examples of these aromatic compounds include phenol, m-cresol, resorcinol, hydroquinone, catechol, l-naphthol, 2-naphthol, hydroxyanthracene, hydroxyphenanthrene, etc.
According to the present invention, these lithium compounds (a) are to be used in conjunction with a small amount of (b) an orgar,ic compound which contains hydroxyl groups.
Generally these organic compounds contain from 1 to 4 hydroxyl groups and have about 1 to 18 carbon atoms. Suitable organic compounds include methanol, l-ethanol, 1,2-ethanediol, l-propanol, 2-propanol, l-butanol, 2-butanol, isobutyl alcohol, n-amyl alcohol, sec-amyl alcohol, tert-amyl alcohol, l-methylbutyl alcohol, l-ethyl-l-propanol, n-octyl alcohol, 2-octyl alcohol, n-decyl alcohol, n-dodecyl alcohol, ~ -Mo3904 -6- 2~3~90 neopentylglycol, n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-2-butanol, 3,3-dimethyl-1-butanol, 2-ethyl-1,3-hexanediol, glycerol, 1,2,4-butanetriol, pentaerythr;tol, etc. It is preferred for these organic compounds to contain from 1 to 2 hydroxyl groups, such as a monoalcohol or a diol, and have from about 1 to 8 carbon atoms. Examples include methanol, 1-ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, n-amyl alcohol, 1-methylbutyl o alcohol, 1-ethyl-1-propanol, n-octyl alcohol, 2-octyl alcohol, neopentylglycol, 1,3-propanediol, 1,4-butanediol, 1,3-butane-diol, 2,3-butaned;ol, 2-ethyl-1,3-hexanediol, etc. It is most preferred to use those compounds which have 2 hydroxyl groups, and contain either 3 or 4 carbon atoms. 1,3-propanediol and 1,3-butanediol are among the most preferred organic compounds.
Suitable polyisocyanates to be trimerized according to the present invention, to yield polyisocyanates having an isocyanurate structure, include the known aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic 20: polyisocyanates, and mixtures thereof. Examples of these polyisocyanates include those described by W. Siefen in ~ustus Liebigs Annalen der Chemie, 562, pages 75 to 136. More specifically, suitable polyisocyanates include, but are not limited to, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, diphenyl methane-4,4-diisocyanate, naphthylene 1,5-diiso-cyanate, hexamethylene-1,6 diisocyanate, 1-isocyanato-3,5,5-trimethyl-5-isocyanato-methyl-cyclohexane, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato~
3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (i.e. isophorone ~ -diisocyanate), 2,4- and/or 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4'- and/or -4,4'diphenylmethane diisocyanate, 1,3- and/or 1,4-phenylene diisocyanate, diphenylmethane-2,4'-diisocyanate, naphthalene-1,5-Mo3904 ::
` 7 21~3 diisocyanate, trlphenylmethane-4,4',4"-trlisocyanate and polyphenyl polymethylene polyisocyanates obtained by phosgenating aniline/formaldehyde condensation products. Also suitable are polyisocyanate adducts containing urea, biuret, urethane, allophanate, uretdione, or carbodiimide groups or isocyanurate rings. Preferred polyisocyanates include aromatic and aliphatic isocyanates, with hexamethylene-1,6-diisocyanate, 2,4-diisocyanatotoluene, 2,6-d;isocyanatotoluene, and diphenyl methane-4,4'-diisocyanate, and mixtures thereof, being lo particularly preferred.
EXAMPLES
The followin~ examples further illustrate details for the process of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions of the following procedures can be used. Unless otherwise noted, all temperatures are degrees Celsius and all parts are parts by weight.
Example 1:
To a 250 ml 3-neck flask equipped with a condenser, thermometer, mechanical stirrer, and purged with dry nitrogen was added 100 grams of hexamethylene diisocyanate (HDI), 0.1 9.
of 1,3-butanediol, and 0.002 9. of lithium salicylate. The reaction mlxture was heated over a 4 minute period to 250~C and - -~
held there for about 4 minutes. At the end of the time, it was cooled over a 3 minute period to about 40C and 0.01 9 of benzoyl chloride was added. The resulting reaction mixture has --~ -a NC0 content of 39.3%. The hexamethylene diisocyanate (HDI) monomer was removed by thin film evaporation to give a clear liquid having a viscosity of 7820 mPa.s at 25C, and a NC0 content of 20.4%.
: ~-' ~ ' Mo3904 Example 2:
The same reaction was ran as in Example 1, except that 0.006 9 of lithium salicylate was used and no 1,3-butanediol was used. No trimerization was observed.
Example 3:
The same reaction was ran as in Example 1, except that the lithium salicylate was dissolved in the 1,3-butanediol and this clear solution was added to the hexamethylene-1,6-diisocyanate (HDI). The reaction mixture has a NC0 content of 39.1% after lo heating.
The following formulations were also tested. All amounts are in parts by weight (pbw) unless otherwise indicated.
4. 100 hexamethylene-1,6-diisocyanate 0.105 1,3-propanediol 0.002 lithium salicylate 5. 100 hexamethylene-1,6-diisocyanate 0.102 2-ethyl-1,3-hexanediol 0.002 lithium salicylate 6. 100 hexamethylene-1,6-diisocyanate 0.201 1,4-butanediol 0.004 lithium salicylate 7. 100 hexamethylene-1,6-diisocyanate 0.300 1,3-butanediol 0.001 lithium salicylate 8. 100 hexamethylene-1,6-diisocyanate 0.201 1,3-butanediol 0.002 lithium salicylate 9. 100 hexamethylene-1,6-diisocyanate ~ ~ ~
2.70 1,3-butanediol ~ ~ -3o 0.001 lithium salicylate 10. 100 hexamethylene-1,6-diisocyanate - -1.11 1-butanol 0.004 lithium salicylate Mo3904 - : , ~-,-- - :
.,.; ~,''',~ ~' ,, ', ' ' :
9 2113P,9~
2.70 1,3-butanediol ~ ~ -3o 0.001 lithium salicylate 10. 100 hexamethylene-1,6-diisocyanate - -1.11 1-butanol 0.004 lithium salicylate Mo3904 - : , ~-,-- - :
.,.; ~,''',~ ~' ,, ', ' ' :
9 2113P,9~
11. 50 2,4-diisocyanatotoluene 50 hexamethylene-1,6-diisocyanate 0.200 1,3-butanediol 0.002 lithium salicylate 12. 10 2,4-diisocyanatotoluene 90 hexamethylene-1,6-diisocyanate 0.200 1,3-butanediol 0.004 lithium salicylate 13. 100 2,4-diisocyanatotoluene 0.200 1,3-butanediol 0.002 lithium salicylate 14. 60 diphenylmethane-4,4'-diisocyanate 40 hexamethylene-1,6-diisocyanate 0.200 1,3-butanediol 0.002 lithium salicylate ~
lS. 60 diphenylmethane-4,4'-diisocyanate ~ -:
40 hexamethylene-1,6-diisocyanate ~
0.200 1,3-butanediol -0.002 lithium salicylate 16. 100 diphenylmethane-4,4'-diisocyanate 0.200 1,3-butanediol 0.002 lithium salicylate ~ -17. 100 hexamethylene-1,6-diisocyanate ~- 0.204 1,3-butanediol 0.004 lithium acetate 18. 100 hexamethylene-1~6-diisocyanate --0.201 1,3-butanediol 0.005 lithium hydroxide 19. 100 hexamethylene-1,6-diisocyanate 0.107 1,3-butanediol 0.004 lithium stearate 20. 100 hexamethylene-1,6-diisocyanate 0.103 1,3-butanediol 0.002 lithium propanate 21. 100 hexamethylene-1,6-diisocyanate Mo3904 ~o 2113g90 0.101 1,3-butanediol 0.006 lithium lactate 22. 100 hexamethylene-1,6-diisocyanate 0.202 1,3-butanediol 0.006 lithium p-hydroxybenzoate 23. 100 hexamethylene-1,6-diisocyanate 0.200 1,3-butanediol 0.006 monolithium salt of isophthalic acid 24. 100 hexamethylene-1,6-diisocyanate 10. 0.103 1,3-~utanediol 0.006 monolithium salt of phthalic acid 25. 100 hexamethylene-1,6-diisocyanate 0.201 1,3-butanediol : ;
0.006 dilithium salt of phthalic acid Table 1 presents the results for formulations 4-25. These experiments followed the same procedure as described in - -Example 1. Reaction temperatures and reaction times are listed in Table 1.
'~''",'' ''.'' ::.: : '-. ~ .
. ~ --- -- :.
, ~..~- ,...
- .
Mo3904 :. ~
' ~ ~
11 2113~90 TABLE ~
Formulation Reaction Reaction Final Temp. C Time. min. % NC0 4 250 4 37.7 250 4 46.0 6 160 20 28.7 7 220 5 40.0 8 1~5 155 39.5 9 125 154 41.7 125 51 37.5 11 125 4 40.3 12 125 37 40.5 13 125 65 40.6 14 125 2.25 30.5 - -175 41 29.9 16 200 60 21.8 ~-17 250 2 38.6 -~
18 250 4 34.2 19 250 4 39.1 250 4 40.3 21 250 4 31.1 22 250 4 41.9 23 250 4 32.1 24 250 4 41.0 250 4 41.3 ExamDle 26: To a 250 ml. 3-neck flask equipped with a condenser, thermometer, mechanical stirrer, and purged with dry nitrogen, was added 100 parts hexamethylene-1,6-diisocyanate, 0.106 parts oF 1,3-butanediol and 0.002 parts lithium salicylate. The reaction mixture was heated over a 5 minute period to 250-C and held there for 8 minutes. At the end of this time, the mixture was cooled over a 3 minute period to about 50C and 0.01 parts of benzoyl chloride was added. The resulting mixture had an NC0 content of 40.5%.
Mo3904 -12- s~ i ~ 3 8 9 0 Comparison Examples:
Example 27: The identical procedure as described in Example 26 was followed, except 0.002 parts of sodium salicylate was substituted for the lithium salicylate. The resulting mixture ~
had an NC0 content of 48.6%. --Example 28: The identical procedure as described in Example 26 was followed, except 0.002 parts of potassium salicylate was substituted for the lithium salicylate. The resulting mixture had an NC0 content of 47.9%. - ; -lo 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. ~ --~
:''',', ~,'~ ~: ' ' ' '':', :'~' ' , . - ~
Mo3904
lS. 60 diphenylmethane-4,4'-diisocyanate ~ -:
40 hexamethylene-1,6-diisocyanate ~
0.200 1,3-butanediol -0.002 lithium salicylate 16. 100 diphenylmethane-4,4'-diisocyanate 0.200 1,3-butanediol 0.002 lithium salicylate ~ -17. 100 hexamethylene-1,6-diisocyanate ~- 0.204 1,3-butanediol 0.004 lithium acetate 18. 100 hexamethylene-1~6-diisocyanate --0.201 1,3-butanediol 0.005 lithium hydroxide 19. 100 hexamethylene-1,6-diisocyanate 0.107 1,3-butanediol 0.004 lithium stearate 20. 100 hexamethylene-1,6-diisocyanate 0.103 1,3-butanediol 0.002 lithium propanate 21. 100 hexamethylene-1,6-diisocyanate Mo3904 ~o 2113g90 0.101 1,3-butanediol 0.006 lithium lactate 22. 100 hexamethylene-1,6-diisocyanate 0.202 1,3-butanediol 0.006 lithium p-hydroxybenzoate 23. 100 hexamethylene-1,6-diisocyanate 0.200 1,3-butanediol 0.006 monolithium salt of isophthalic acid 24. 100 hexamethylene-1,6-diisocyanate 10. 0.103 1,3-~utanediol 0.006 monolithium salt of phthalic acid 25. 100 hexamethylene-1,6-diisocyanate 0.201 1,3-butanediol : ;
0.006 dilithium salt of phthalic acid Table 1 presents the results for formulations 4-25. These experiments followed the same procedure as described in - -Example 1. Reaction temperatures and reaction times are listed in Table 1.
'~''",'' ''.'' ::.: : '-. ~ .
. ~ --- -- :.
, ~..~- ,...
- .
Mo3904 :. ~
' ~ ~
11 2113~90 TABLE ~
Formulation Reaction Reaction Final Temp. C Time. min. % NC0 4 250 4 37.7 250 4 46.0 6 160 20 28.7 7 220 5 40.0 8 1~5 155 39.5 9 125 154 41.7 125 51 37.5 11 125 4 40.3 12 125 37 40.5 13 125 65 40.6 14 125 2.25 30.5 - -175 41 29.9 16 200 60 21.8 ~-17 250 2 38.6 -~
18 250 4 34.2 19 250 4 39.1 250 4 40.3 21 250 4 31.1 22 250 4 41.9 23 250 4 32.1 24 250 4 41.0 250 4 41.3 ExamDle 26: To a 250 ml. 3-neck flask equipped with a condenser, thermometer, mechanical stirrer, and purged with dry nitrogen, was added 100 parts hexamethylene-1,6-diisocyanate, 0.106 parts oF 1,3-butanediol and 0.002 parts lithium salicylate. The reaction mixture was heated over a 5 minute period to 250-C and held there for 8 minutes. At the end of this time, the mixture was cooled over a 3 minute period to about 50C and 0.01 parts of benzoyl chloride was added. The resulting mixture had an NC0 content of 40.5%.
Mo3904 -12- s~ i ~ 3 8 9 0 Comparison Examples:
Example 27: The identical procedure as described in Example 26 was followed, except 0.002 parts of sodium salicylate was substituted for the lithium salicylate. The resulting mixture ~
had an NC0 content of 48.6%. --Example 28: The identical procedure as described in Example 26 was followed, except 0.002 parts of potassium salicylate was substituted for the lithium salicylate. The resulting mixture had an NC0 content of 47.9%. - ; -lo 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. ~ --~
:''',', ~,'~ ~: ' ' ' '':', :'~' ' , . - ~
Mo3904
Claims (6)
1. A process for the preparation of a polyisocyanate having isocyanurate structure which comprises heating an organic polyisocyanate, or mixtures thereof, to a temperature of from about 100 to 300°C in the presence of a catalytic amount of (a) a compound selected from the group consisting of i) lithium salts of aliphatic or aromatic monocarboxylic or dicarboxylic acids, ii) lithium salts of hydroxyl group containing compounds having from 1 to 3 hydroxyl groups per compound, wherein said hydroxyl groups are directed attached to an aromatic ring, and iii) lithium hydroxide; and (b) an organic compound containing at least one hydroxyl group for a period of from about 1 minute to about 240 minutes.
2. The process of Claim 1 wherein (a) said compound is selected from the group consisting of lithium salicylate, lithium acetate, and lithium stearate.
3. The process of Claim 1 wherein said temperature range is from 125 to 250°C.
4. The process of Claim 1 wherein (b) said organic compound containing at least one hydroxyl group is selected from the group consisting of 1,3-propanediol, and 1,3-butanediol.
5. The process of Claim 1 wherein (a) said compound is lithium hydroxide.
6. The process of Claim 1 wherein said organic polyisocyanate compound is selected from the group consisting of hexamethylene-1,6-diisocyanate, diphenylmethane-4,4-diisocyanate, toluylene diisocyanate, and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/018,830 | 1993-02-18 | ||
| US08/018,830 US5905151A (en) | 1993-02-18 | 1993-02-18 | Trimer catalyst for aliphatic and aromatic isocyanates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2113890A1 true CA2113890A1 (en) | 1994-08-19 |
Family
ID=21789982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002113890A Abandoned CA2113890A1 (en) | 1993-02-18 | 1994-01-20 | Trimer catalyst for aliphatic and aromatic isocyanates |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5905151A (en) |
| CA (1) | CA2113890A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955609A (en) * | 1997-12-31 | 1999-09-21 | Bayer Corporation | Trimer catalyst system for aliphatic and aromatic isocyanates |
| US6028158A (en) * | 1997-12-31 | 2000-02-22 | Bayer Corporation | Freeze-stable allophanate-modified toluene diisocyanate trimers |
| US6452003B1 (en) | 2000-07-07 | 2002-09-17 | Degussa Ag | Process for preparing low-odor and storage-stable monomer-containing polyisocyanurates from isophorone diisocyanate |
| US6515125B1 (en) | 2001-03-09 | 2003-02-04 | Bayer Corporation | Liquid partially trimerized polyisocyanates based on toluene diisocyanate and diphenylmethane diisocyanate |
| US6703471B2 (en) | 2001-07-02 | 2004-03-09 | Degussa Ag | Preparation of low-odor-storage-stable monomer-containing polyisocyanurates based on isophorone diisocyante |
| US7553963B2 (en) | 2003-10-29 | 2009-06-30 | Bayer Materialscience Llc | Liquid partially trimerized and allophanized polyisocyanates based on toluene diisocyanate and diphenylmethane diisocyanate |
| CN105032490A (en) * | 2015-07-17 | 2015-11-11 | 华南理工大学 | Complex catalyst and application thereof to preparation of mixed diisocyanate trimer |
| EP3401344A1 (en) | 2017-05-09 | 2018-11-14 | Evonik Degussa GmbH | Method for the preparation of trimers and/or oligomers of diisocyanates |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7205374B2 (en) * | 2002-10-11 | 2007-04-17 | Bfs Diversified Products, Llc | Two-part polyurethane adhesive for bonding insulation boards to a roof deck |
| US20050101754A1 (en) * | 2003-11-12 | 2005-05-12 | Slack William E. | Stable liquid, allophanate-modified diphenylmethane diisocyanate trimers, prepolymers thereof, and processes for their preparation |
| DE102004012903A1 (en) * | 2004-03-17 | 2005-10-06 | Bayer Materialscience Ag | Low-viscosity allophanates with actinically curable groups |
| US20080227878A1 (en) * | 2007-03-14 | 2008-09-18 | James Garrett | Trimer and allophanate modified isocyanates, a process for their production, foams comprising these modified isocyanates, and a process for the production of these foams |
| US8864423B2 (en) * | 2008-01-07 | 2014-10-21 | Firestone Building Products Company, Llc | Geomembrane protective cover |
| WO2020016119A1 (en) | 2018-07-16 | 2020-01-23 | Covestro Deutschland Ag | Method for oligomerizing isocyanates by means of polyhedral silsesquioxane catalysts |
| US11827808B2 (en) | 2019-02-01 | 2023-11-28 | Praxair S.T. Technology, Inc. | Erosion and corrosion resistant overlay coating systems for protection of metal components |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3697485A (en) * | 1969-07-10 | 1972-10-10 | Minnesota Mining & Mfg | Process for preparing polyisocyanurates and polyurethanes using organic orthoborate catalysts |
| US4080345A (en) * | 1973-08-21 | 1978-03-21 | Metzeler Schaum Gmbh | Catalyst mixture for use in trimerizing and/or polymerizing isocyanates and/or for the polyaddition of active hydrogen atom containing polyethers and polyisocyanates |
| US3860565A (en) * | 1973-10-01 | 1975-01-14 | Minnesota Mining & Mfg | Encapsulated isocyanurate catalyst |
| US3954684A (en) * | 1974-07-09 | 1976-05-04 | The Upjohn Company | Foam process using tertiary amine/quaternary ammonium salt catalyst |
| US4126741A (en) * | 1978-05-15 | 1978-11-21 | The Upjohn Company | High-modulus polyisocyanurate elastomers |
| US4126742A (en) * | 1978-05-15 | 1978-11-21 | The Upjohn Company | High-modulus polyisocyanurate elastomers |
| DE2832253A1 (en) * | 1978-07-22 | 1980-01-31 | Bayer Ag | METHOD FOR PRODUCING MOLDED FOAMS |
| DE3100263A1 (en) * | 1981-01-08 | 1982-08-12 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS AND THE USE THEREOF IN THE PRODUCTION OF POLYURETHANES |
| DE3100262A1 (en) * | 1981-01-08 | 1982-08-05 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF POLYISOCYANATES CONTAINING ISOCYANURATE GROUPS, SOLUTIONS SUITABLE AS CATALYST COMPONENTS FOR THIS METHOD, AND THE USE OF THE PROCESS PRODUCTS AS THE ISOCYANATE COMPONENT PRODUCT |
| PL141806B1 (en) * | 1981-02-03 | 1987-08-31 | Rhone Poulenc Spec Chim | Method of obtaining compounds with isocyanure groups |
| JPS58162581A (en) * | 1982-03-19 | 1983-09-27 | Nippon Polyurethan Kogyo Kk | Composition for polyurethane paints |
| US4632785A (en) * | 1983-08-11 | 1986-12-30 | The Dow Chemical Company | Thermally activable trimerization catalyst |
| US4540781A (en) * | 1983-08-11 | 1985-09-10 | The Upjohn Company | Product and process trimerization of organic isocyanates |
| US5248703A (en) * | 1992-03-13 | 1993-09-28 | Basf Corporation | Rigid polyurethane foams containing lithium salts for energy absorbing applications |
| US5453455A (en) * | 1993-01-25 | 1995-09-26 | Basf Corporation | Rigid polyurethane foams containing lithium salts for energy absorbing applications |
-
1993
- 1993-02-18 US US08/018,830 patent/US5905151A/en not_active Expired - Lifetime
-
1994
- 1994-01-20 CA CA002113890A patent/CA2113890A1/en not_active Abandoned
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955609A (en) * | 1997-12-31 | 1999-09-21 | Bayer Corporation | Trimer catalyst system for aliphatic and aromatic isocyanates |
| US6028158A (en) * | 1997-12-31 | 2000-02-22 | Bayer Corporation | Freeze-stable allophanate-modified toluene diisocyanate trimers |
| US6063891A (en) * | 1997-12-31 | 2000-05-16 | Bayer Corporation | Freeze stable allophanate-modified toluene diisocyanate trimers |
| US6127308A (en) * | 1997-12-31 | 2000-10-03 | Bayer Corporation | Trimer catalyst system for aliphatic and aromatic isocyanates |
| US6452003B1 (en) | 2000-07-07 | 2002-09-17 | Degussa Ag | Process for preparing low-odor and storage-stable monomer-containing polyisocyanurates from isophorone diisocyanate |
| US6515125B1 (en) | 2001-03-09 | 2003-02-04 | Bayer Corporation | Liquid partially trimerized polyisocyanates based on toluene diisocyanate and diphenylmethane diisocyanate |
| US6703471B2 (en) | 2001-07-02 | 2004-03-09 | Degussa Ag | Preparation of low-odor-storage-stable monomer-containing polyisocyanurates based on isophorone diisocyante |
| US7553963B2 (en) | 2003-10-29 | 2009-06-30 | Bayer Materialscience Llc | Liquid partially trimerized and allophanized polyisocyanates based on toluene diisocyanate and diphenylmethane diisocyanate |
| CN105032490A (en) * | 2015-07-17 | 2015-11-11 | 华南理工大学 | Complex catalyst and application thereof to preparation of mixed diisocyanate trimer |
| EP3401344A1 (en) | 2017-05-09 | 2018-11-14 | Evonik Degussa GmbH | Method for the preparation of trimers and/or oligomers of diisocyanates |
| US10793664B2 (en) | 2017-05-09 | 2020-10-06 | Evonik Operations Gmbh | Process for preparing trimers and/or oligomers of diisocyanates |
Also Published As
| Publication number | Publication date |
|---|---|
| US5905151A (en) | 1999-05-18 |
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