CA2128344C - Liquid methylene diphenyl diisocyanate - Google Patents
Liquid methylene diphenyl diisocyanate Download PDFInfo
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- CA2128344C CA2128344C CA002128344A CA2128344A CA2128344C CA 2128344 C CA2128344 C CA 2128344C CA 002128344 A CA002128344 A CA 002128344A CA 2128344 A CA2128344 A CA 2128344A CA 2128344 C CA2128344 C CA 2128344C
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- mdi
- diisocyanate
- allophanate
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- liquid
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
- C07C275/58—Y being a hetero atom
- C07C275/60—Y being an oxygen atom, e.g. allophanic acids
Abstract
The present invention relates to a process for the production of a allophanate-modified MDI which is a storage stable liquid at 25°C comprising (A) reacting (i) one equivalent of a diisocyanate and (ii) one equivalent of an aliphatic alcohol containing from 1 to about 36 carbon atoms or aromatic alcohol containing from 6 to 18 carbon atoms to form a diurethane of the diisocyanate, (B) reacting the product of (A) with 4,4'-diphenylmethane diisocyanate containing from 2 to 60%
by weight 2,4'-MDI and less than 6% by weight of the 2,2'-MDI, in an amount sufficient to provide an allophanate having an isocyanate group content of about 12.0 to 30.0%.
by weight 2,4'-MDI and less than 6% by weight of the 2,2'-MDI, in an amount sufficient to provide an allophanate having an isocyanate group content of about 12.0 to 30.0%.
Description
212~34~
Mo-3969 LIQUID METHYLENE DIPHENYL DIISOCYANATE
BACKGROUND OF THE INDENTION
Field of the Invention:
The present invention relates to liquid methylene s Biphenyl diisocyanates (MDI). More specifically, the present invention relates to liquid allophanate-modified MDI
prepolymers and the methods of making and using the same.
Brief Description of the Prior Art:
Liquid methylene Biphenyl diisocyanates are generally to known in the art. US 3,644,457 discloses room temperature, stable, liquid isocyanates derived from one mole of diphenyl-methane diisocyanate and 0.1 to 0.3 mols of poly-1,2-propylene ether glycol.
US 4,055,548 discloses liquid isocyanate prepolymer 15 compositions obtained by reacting polymethylene polyphenyl-isocyanate containing from about 65 to 85 percent by weight of methylene bis(phenylisocyanate with a polyoxyethylene glycol having molecular weight of from 200 to 600 in an equivalent 2o ratio 0.0185-0.15:1.
US 4,115,429 and 4,118,411 disclose low temperature (as low as -5 degrees Centigrade), storage stable liquid diphenylmethane diisocyanates which are produced by reacting 2s diphenylmethane diisocyanates having a specified 2,4-isomer content with propylene glycol or poly-1,2-propylene ether glycol.
US 4,261,852 discloses liquid polyisocyanate compositions comprising (a) the reaction product of 90 to 50%
3o bY weight of a reaction product of diphenylmethane diisocyanate and a polyoxypropylene diol or triol having hydroxyl equivalent _2-weight of from 750 to 3000, said reaction product having NCO
content of from 8 to 26% by weight, and (B) from about 10 to 50% by weight of a diphenylmethane diisocyanat,e containing from 30 to 65% by weight of diphenylmethane diisocyanate, the s remainder being polymethylene polyphenyl polyisocyanate.
US 4,490,300 discloses room temperature stable liquid isocyanates which are derived by reacting diphenylmethane diisocyanate with an aliphatic diol having a pendant aromatic group, e.g., 2-methyl-2-phenyl-1,3-propanediol or phenyl-1-2 to -ethanediol.
US 4,490,300 discloses room temperature stable liquid isocyanates which are derived by reacting diphenylmethane diisocyanate with monoallylether of trimethylo~lpropane.
US 4,738,991 discloses organic polyisocyanates 15 characterized by allophanate linkages which are prepared by reacting an organic polyisocyanate including 2,4- and 4,4-methylenediphenyl diisocyanate with poly- or monohydric alcohol in the presence of an organo metallic catalyst. The 2o catalyst is then deactivated using a compound such as an inorganic acid, organic acid, organic chloroformate or an organic acid chloride.
US 4,866,103 discloses a polyisocyanate composition for use in producing elastomers in a RIM process, said a5 composition being the product of reacting an alcohol and/or thiol having an average functionality of from about 1.5 to about 4 and an average equivalent weight of at least 500 with at least 2 equivalents per hydroxyl and/or thiol equivalent of an organic polyisocyanate including 4,4- and 2,4-isomers of 3o diphenylmethane diisocyanate under such conditions that at least about 20% of the initially formed urethane and/or thiourethane groups are converted to allophanate and/or thioallophanate groups.
Mo-3969 2~283~~
Mo-3969 LIQUID METHYLENE DIPHENYL DIISOCYANATE
BACKGROUND OF THE INDENTION
Field of the Invention:
The present invention relates to liquid methylene s Biphenyl diisocyanates (MDI). More specifically, the present invention relates to liquid allophanate-modified MDI
prepolymers and the methods of making and using the same.
Brief Description of the Prior Art:
Liquid methylene Biphenyl diisocyanates are generally to known in the art. US 3,644,457 discloses room temperature, stable, liquid isocyanates derived from one mole of diphenyl-methane diisocyanate and 0.1 to 0.3 mols of poly-1,2-propylene ether glycol.
US 4,055,548 discloses liquid isocyanate prepolymer 15 compositions obtained by reacting polymethylene polyphenyl-isocyanate containing from about 65 to 85 percent by weight of methylene bis(phenylisocyanate with a polyoxyethylene glycol having molecular weight of from 200 to 600 in an equivalent 2o ratio 0.0185-0.15:1.
US 4,115,429 and 4,118,411 disclose low temperature (as low as -5 degrees Centigrade), storage stable liquid diphenylmethane diisocyanates which are produced by reacting 2s diphenylmethane diisocyanates having a specified 2,4-isomer content with propylene glycol or poly-1,2-propylene ether glycol.
US 4,261,852 discloses liquid polyisocyanate compositions comprising (a) the reaction product of 90 to 50%
3o bY weight of a reaction product of diphenylmethane diisocyanate and a polyoxypropylene diol or triol having hydroxyl equivalent _2-weight of from 750 to 3000, said reaction product having NCO
content of from 8 to 26% by weight, and (B) from about 10 to 50% by weight of a diphenylmethane diisocyanat,e containing from 30 to 65% by weight of diphenylmethane diisocyanate, the s remainder being polymethylene polyphenyl polyisocyanate.
US 4,490,300 discloses room temperature stable liquid isocyanates which are derived by reacting diphenylmethane diisocyanate with an aliphatic diol having a pendant aromatic group, e.g., 2-methyl-2-phenyl-1,3-propanediol or phenyl-1-2 to -ethanediol.
US 4,490,300 discloses room temperature stable liquid isocyanates which are derived by reacting diphenylmethane diisocyanate with monoallylether of trimethylo~lpropane.
US 4,738,991 discloses organic polyisocyanates 15 characterized by allophanate linkages which are prepared by reacting an organic polyisocyanate including 2,4- and 4,4-methylenediphenyl diisocyanate with poly- or monohydric alcohol in the presence of an organo metallic catalyst. The 2o catalyst is then deactivated using a compound such as an inorganic acid, organic acid, organic chloroformate or an organic acid chloride.
US 4,866,103 discloses a polyisocyanate composition for use in producing elastomers in a RIM process, said a5 composition being the product of reacting an alcohol and/or thiol having an average functionality of from about 1.5 to about 4 and an average equivalent weight of at least 500 with at least 2 equivalents per hydroxyl and/or thiol equivalent of an organic polyisocyanate including 4,4- and 2,4-isomers of 3o diphenylmethane diisocyanate under such conditions that at least about 20% of the initially formed urethane and/or thiourethane groups are converted to allophanate and/or thioallophanate groups.
Mo-3969 2~283~~
Other prior art relating to the preparation of allophanates which contain isocyanates are British Patent 994,890 which relates to the reaction of urethane isocyanates with excess diisocyanate either by heat alone or in the s presence of a catalyst such as a metal carboxylate, a metal chelate or a tertiary amine, until the isocyan ate content is reduced to that which is obtained theoreticallly when the complete reaction of the urethane groups is achieved.
US Patent 4,160,080 discloses a process for producing to allophanate containing aliphatically and/or cycloaliphatically bound isocyanate groups in which compounds containing urethane groups are reacted with polyisocyanates having aliphatic and/or cycloaliphatic isocyanate groups in the presence of a strong acid. The process is generally conducted at a temperature of i5 from 90°C to 140°C for about 4 to 20 hours.
Japanese Patent Application No. 1971.-99176 discloses a method of preparing liquid diphenylmethane diisocyanate by reacting diphenylmethane diisocyanate with aliphatic monovalent alcohol.
2o By the present invention there is provided a novel liquid isocyanate.
SUMMARY OF THE INVENTION
In accordance with the foregoing, the present invention, in the first embodiment encompasses. a process for 2s the production of a prepolymer containing an allophanate -modified MDI which is a storage stable liquid at 25°C
comprising (A) reacting (i) one equivalent of a diiso-cyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (I:PDI), toluene 3o diisocyanate (TDI), diphenylmethylene diisocyanate (MDI), and hydrogenated MDI with (ii) one equivalent of an aliphatic alcohol containing 1 to about 36 carbon atoms or aromatic alcohol containing 6 to 18 carbon atoms to form a diurethane of the diisocyanate, B) reacting the product of (A) with a specified isomer composition of diphenylmethane diisocyanate in Mo-3969 ~12~3~4 an amount sufficient to provide a liquid allophanate modified MDI having an NCO content of about 12.0 to 30.0%. Typically, the diphenylmethane diisocyanate isomer composition contains 4,4'-diphenylmethane diisocyanate, from 2 to 60% by weight 2,4'-MDI and less than 6% by weight of the 2,2'-MDI.
In the second embodiment, the present invention encompasses a process as recited above, further comprising reacting the allophanate-modified MDI with (a) an organic material containing two or more hydroxy, primary amine or to secondary amino groups or any combination thereof having a molecular weight of from 400 to 6000, (b) a diol having a molecular weight of from 60 to 200 or a combination of (a) and (b) wherein the resultant liquid prepolymer has an isocyanate group content of from 5 to 29% by weight.
15 The allophanate-modified MDI prepolymers obtained from the above processes are also encompassed by the invention.
It is a distinct feature of the invention that the resultant allophanate-modified MDI prepolymers are stable and liquid at 25°C. By the term "stable" herein is meant that the 2o isocyanate has no more than one percent absolute change in NCO
content and no more than ten percent change in the viscosity when stored at 25°C for 3 months. By the term "liquid" herein is meant that the modified isocyanate does not precipitate solids when stored at 25°C for 3 months.
2s The prepolymers are particularly useful in that automotive reaction injection molding (RIM), shoe soles and rigid foam applications.
DETAILED DESCRIPTION OF THE INDENTION
In the first embodiment, the prepolymer containing allophanate-modified MDI is characterized in that it is stable 3o and liquid at 25°C and has an isocyanate content of about 12 to 30% and preferably 17 to 28%. In the second embodiment, the allophanate-modified MDI is characterized in that it has an isocyanate group content of about 5 to 29% and preferably 12 to 27% by weight. The allophanate-modified MDI can be prepared by Mo-3969 reacting a diisocyanate with an aliphatic or aromatic alcohol in order produce a diurethane, followed by reacting the diurethane with the specified MDI isomer composition to form a diallophanate. More specifically, the diurethane can be s obtained by reacting one equivalent of a diisocyanate with one equivalent of an aliphatic alcohol containing 1 to about 36 carbon atoms or aromatic alcohol containing 6 to 18 carbon atoms to form a diurethane of the diisocyanate.
The diisocyanate is selected from the group to consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) toluene diisocyanate (TDI), diphenylmethylene diisocyanate (MDI), and hydrogenated MDI.
Aliphatic alcohols useful herein are those that can react with the diphenylmethane diisocyanate to form diurethanes is which can be converted to allophanates in accordance with the invention. The useful aliphatic or aromatic alcohols can contain about 1 to 36 and preferably 4 to 16 carbon atoms.
Illustrative but non-limiting examples of the aliphatic alcohols can be selected from the group consisting of 2o cycloaliphatic alcohols, aliiphatic alcohols containing aromatic groups, and aliphatic alcohols containing groups that do not react with isocyanates e.g., ether groups and halogens such as bromine and chlorine. Specific but non-limiting examples of the aliphatic alcohols can be selected from the 2s group consisting of 1-butanol, cetyl alcohol, 2-methoxy-ethanol and 2-bromoethanol.
Specific examples of the aromatic alcohols can be selected from the group consisting of phenol, m-cresol and 1-naphthol.
In the reaction of the aliphatic or aromatic alcohol 3o with the diisocyanate, the NCO to OH equivalent is about 1:1 with the reaction being monitored till an NCO value of 0 to 0.5 is attained. Solvents which are typically inert to the isocyanate, for example toluene, tetrahydrofuran, o-dichlorobenzene or the like can be employed.
Mo-3969 z~zg~~~
US Patent 4,160,080 discloses a process for producing to allophanate containing aliphatically and/or cycloaliphatically bound isocyanate groups in which compounds containing urethane groups are reacted with polyisocyanates having aliphatic and/or cycloaliphatic isocyanate groups in the presence of a strong acid. The process is generally conducted at a temperature of i5 from 90°C to 140°C for about 4 to 20 hours.
Japanese Patent Application No. 1971.-99176 discloses a method of preparing liquid diphenylmethane diisocyanate by reacting diphenylmethane diisocyanate with aliphatic monovalent alcohol.
2o By the present invention there is provided a novel liquid isocyanate.
SUMMARY OF THE INVENTION
In accordance with the foregoing, the present invention, in the first embodiment encompasses. a process for 2s the production of a prepolymer containing an allophanate -modified MDI which is a storage stable liquid at 25°C
comprising (A) reacting (i) one equivalent of a diiso-cyanate selected from the group consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (I:PDI), toluene 3o diisocyanate (TDI), diphenylmethylene diisocyanate (MDI), and hydrogenated MDI with (ii) one equivalent of an aliphatic alcohol containing 1 to about 36 carbon atoms or aromatic alcohol containing 6 to 18 carbon atoms to form a diurethane of the diisocyanate, B) reacting the product of (A) with a specified isomer composition of diphenylmethane diisocyanate in Mo-3969 ~12~3~4 an amount sufficient to provide a liquid allophanate modified MDI having an NCO content of about 12.0 to 30.0%. Typically, the diphenylmethane diisocyanate isomer composition contains 4,4'-diphenylmethane diisocyanate, from 2 to 60% by weight 2,4'-MDI and less than 6% by weight of the 2,2'-MDI.
In the second embodiment, the present invention encompasses a process as recited above, further comprising reacting the allophanate-modified MDI with (a) an organic material containing two or more hydroxy, primary amine or to secondary amino groups or any combination thereof having a molecular weight of from 400 to 6000, (b) a diol having a molecular weight of from 60 to 200 or a combination of (a) and (b) wherein the resultant liquid prepolymer has an isocyanate group content of from 5 to 29% by weight.
15 The allophanate-modified MDI prepolymers obtained from the above processes are also encompassed by the invention.
It is a distinct feature of the invention that the resultant allophanate-modified MDI prepolymers are stable and liquid at 25°C. By the term "stable" herein is meant that the 2o isocyanate has no more than one percent absolute change in NCO
content and no more than ten percent change in the viscosity when stored at 25°C for 3 months. By the term "liquid" herein is meant that the modified isocyanate does not precipitate solids when stored at 25°C for 3 months.
2s The prepolymers are particularly useful in that automotive reaction injection molding (RIM), shoe soles and rigid foam applications.
DETAILED DESCRIPTION OF THE INDENTION
In the first embodiment, the prepolymer containing allophanate-modified MDI is characterized in that it is stable 3o and liquid at 25°C and has an isocyanate content of about 12 to 30% and preferably 17 to 28%. In the second embodiment, the allophanate-modified MDI is characterized in that it has an isocyanate group content of about 5 to 29% and preferably 12 to 27% by weight. The allophanate-modified MDI can be prepared by Mo-3969 reacting a diisocyanate with an aliphatic or aromatic alcohol in order produce a diurethane, followed by reacting the diurethane with the specified MDI isomer composition to form a diallophanate. More specifically, the diurethane can be s obtained by reacting one equivalent of a diisocyanate with one equivalent of an aliphatic alcohol containing 1 to about 36 carbon atoms or aromatic alcohol containing 6 to 18 carbon atoms to form a diurethane of the diisocyanate.
The diisocyanate is selected from the group to consisting of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) toluene diisocyanate (TDI), diphenylmethylene diisocyanate (MDI), and hydrogenated MDI.
Aliphatic alcohols useful herein are those that can react with the diphenylmethane diisocyanate to form diurethanes is which can be converted to allophanates in accordance with the invention. The useful aliphatic or aromatic alcohols can contain about 1 to 36 and preferably 4 to 16 carbon atoms.
Illustrative but non-limiting examples of the aliphatic alcohols can be selected from the group consisting of 2o cycloaliphatic alcohols, aliiphatic alcohols containing aromatic groups, and aliphatic alcohols containing groups that do not react with isocyanates e.g., ether groups and halogens such as bromine and chlorine. Specific but non-limiting examples of the aliphatic alcohols can be selected from the 2s group consisting of 1-butanol, cetyl alcohol, 2-methoxy-ethanol and 2-bromoethanol.
Specific examples of the aromatic alcohols can be selected from the group consisting of phenol, m-cresol and 1-naphthol.
In the reaction of the aliphatic or aromatic alcohol 3o with the diisocyanate, the NCO to OH equivalent is about 1:1 with the reaction being monitored till an NCO value of 0 to 0.5 is attained. Solvents which are typically inert to the isocyanate, for example toluene, tetrahydrofuran, o-dichlorobenzene or the like can be employed.
Mo-3969 z~zg~~~
In accordance with the invention, the process comprises reacting the resulting diurethane with the specified isomer composition of diphenylmethane diisocyanate in an amount sufficient to provide an allophanate having an isocyanate group content of about 12.0 to 30.0%. As set forth above, the isomer composition of the diphenylmethane diisocyanate comprises about 2 to 60% and preferably 2 to 30% by weight 2,4'-diphenylmethane diisocyanate and less than 6% and preferably about 0 to 1.0% by weight of the 2,2'-diphenylmethane diisocyanate, and the rest to being 4,4'-diphenylmethane diisocyanate.
The allophanate-forming reaction is usually conducted in the presence of a catalyst. The useful catalysts are those which can be neutralized or otherwise stopped from adversely catalyzing subsequent reactions. Illustratively, a catalyst 15 such as zinc acetylacetonate can be employed, and a catalyst stopper such as acidic materials, e.g., anhydrous hydrochloric acid, sulfuric acid, benzoyl chloride, Lewis acids and the like in the ratio of 2 equivalents of the acid to each mole of the zinc acetylacetonate. Other allophanate catalysts such as zinc 20 2-ethylhexanoate, cobalt 2-ethylhexanoate, cobalt naphthanate, lead linoresinate or the like can be employed.
In a preferred embodiment of the process of the invention, the allophanate can be prepared by reacting the diisocyanate, as described above, with an aliphatic or aromatic 2s alcohol, at about 20°C to about 115°C. The resultant diurethane is dissolved in the specified MDI isomer composition and converted to an allophanate modified MDI at 90-110°C, using zinc acetylacetonate as catalyst, and benzoyl chloride as a stopper for the catalyst in a 2:1 weight ratio of benzoyl chloride to zinc acetylacetonate.
3o In the second embodiment of the invention, the process further to the afore-described process steps comprises reacting the allophanate modified MDI such as described above with a high and/or a low molecular weight organic material containing two or more and preferably 2 to 3 active hydrogen Mo-3969 ~~2834~
_, _ groups such as hydroxyl, primary or secondary amino groups or the like. The high molecular weight organic material can have a molecular weight from 400 to 6000 and preferably 2000 to 5000. The low molecular weight range can be from 60 to 200 and preferably 76 to 90.
The subject urethane, urea, or biuret reaction is carried out in a manner which is well known by, say, heating the reactants to a temperature from about 40 to 150°C and preferably from 50 to 100°C to form urethane or urea and to heating to a temperature of 100 to 150°C and preferably 110 to 120°C to form the biuret.
The useful organic materials containing two or more hydroxyl groups having a molecular weight of 400 to 6000 can be a polyol selected from the group consisting of polyester 1s polyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides and polyhydroxy polythioethers. The polyester polyols, polyether polyols and polyhydroxy polycarbonates are preferred.
2o Suitable polyester polyols include reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added and polybasic, preferably dibasic carboxylic acids. Instead of these polycarboxylic acids, the corresponding carboxylic acid anhydrides or polycarboxylic acid 2s esters of lower alcohols or mixtures thereof may be used for preparing the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and they may be substituted, e.g. by halogen atoms, and/or unsaturated. The following are mentioned as examples: succinic acid; adipic acid; suberic acid; azelaic acid; sebacic acid;
phthalic acid; isophthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acid anhydride; hexahydro-phthalic acid anhydride; tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride; glutaric acid anhydride; malefic acid; malefic acid anhydride; fumaric acid;
Mo-3969 2,12834 _$_ dimeric and trimeric fatty acids such as oleic: acid, which may be mixed with monomeric fatty acids; dimethyl terephthalates and bis-glycol terephthalate. Suitable polyhydric alcohols include, e.g. ethylene glycol; propylene glycol-(1,2) and s -(1,3); butylene glycol-(1,4) and -{1,3); hexa,nediol-(1,6);
octanediol-(1,8); neopentyl glycol; cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane); 2-methyl-1,3-propanediol;
2,2,4-trimethyl-1,3-pentanediol; triethylene glycol; tetra-ethylene glycol; polyethylene glycol; dipropylene glycol;
io polypropylene glycol; dibutylene glycol and polybutylene glycol, glycerine and trimethlyolpropane. The polyesters may also contain a portion of carboxyl end groups. Polyesters of lactones, e.g. e-caprolactone or hydroxyl carboxylic acids, e.g. w-hydroxycaproic acid, may also be used.
15 Polycarbonates containing hydroxyl groups include those known per se such as the products obtained from the reaction of diols such as propanediol-{1,3), butanediol-(1,4) and/or hexanediol-(1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with phosgene, diarylcarbonates such as 2o diphenylcarbonate or with cyclic carbonates such as ethylene or propylene carbonate. Also suitable are polyester carbonates obtained from the above-mentioned polyesters or polylactones with phosgene, diaryl carbonates or cyclic carbonates.
Suitable polyether polyols are obtained in known 2s manner by the reaction of starting compounds which contain reactive hydrogen atoms with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin or mixtures of these alkylene oxides. It is preferred that the polyethers do not contain more than about 10% by weight of ethylene oxide units. Most 3o Preferably, polyethers obtained without the addition of ethylene oxide are used. Suitable starting compounds containing reactive hydrogen atoms include the polyhydric alcohols set forth for preparing the polyester' polyols and, in addition, water, methanol, ethanol, 1,2,6-hexane triol, Mo-3969 1,2,4-butane triol, trimethylol ethane, pentaerythritol, mannitol, sorbitol, methyl glycoside, sucrose, phenol, isononyl phenol, resorcinol, hydroquinone, 1,1,1- or 1,1,2-tris(hydroxylphenyl)-ethane.
Polyethers modified by vinyl polymers are also suitable for the process according to the invention. Products of this kind may be obtained by polymerizing, e.g. styrene and acrylonitrile in the presence of polyethers (U.S. Patent Nos. 3,383,351; 3,304,273; 3,523,095; 3,110,695 and German Patent No. 1,152,536).
Among the polythioethers which should be particularly mentioned are the condensation products obtained from thiodiglycol on its own and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. The products obtained are either polythio-mixed ethers, polythioether esters or polythioether ester amides, depending on the co-components.
Amine-terminated polyether useful herein can be prepared by reacting a primary amine with a polyether containing terminal leaving groups such as halides, or mesylates as disclosed in U.S. Patents 3,666,726, 3,691,112 and 5,066,824.
Suitable polyacetals include the compounds which can be prepared from aldehydes, e.g. formaldehyde, and glycols such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-dihydroxy-diphenyldimethylmethane, and hexanediol-(1,6). Polyacetals suitable for the purpose of the invention may also be prepared by the polymerization of cyclic acetals.
Suitable polyhydroxy polyester amides and polyamines include the predominantly linear condensates obtained from polybasic saturated and unsaturated carboxylic acids or their anhydrides and palyvalent saturated or unsaturated aminoalcohols, diamines, polyamines and mixtures thereof.
Mo3969 2128~4~
-lo-Suitable monomers for producing hydroxy-functional polyacrylates include acrylic acid, methacrylic acid, crotonic acid, malefic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
The low molecular weight material preferably containing two hydroxyl groups having an average molecular to weight of 60 to 200 may be used in combination with or instead of the high molecular weight material containing two or more hydroxyl groups. The useful low molecular weight materials include the polyhydric alcohols which have previously been described for the preparation of the polyester polyols and polyether polyols. Dihydric alcohols are preferred. The weight ratio of the low molecular weight to the high molecular weight material containing two or more hydroxyl groups can be from 0.001 to 2 and preferably 0.01 to 0.40.
In addition to the above-mentioned components which 2o are preferably difunctional, monofunctional and even small portions of trifunctional and higher functional components generally known in polyurethane chemistry, such as trimethylolpropane, may be used in special cases in which slight branching of the resultant product is desired.
In the process of the invention, the hydroxyl functional materials) can be reacted with the allophanate over the temperature range of 40 to 150 and preferably 50 to 100°C, over a period of time sufficient to complete the reaction.
Catalysts and solvents can be employed to aid the reaction.
Examples of the useful catalysts to promote the urethane 3o reactions can be selected from the group consisting of di-n-butyltin dichloride, di-n-butyltin diacetate, di-n-butyltin dilaurate, triethylenediamine, bismuth nitrate and the like.
Mo-3969 2~28~44 Examples of the useful solvents can be selected from the group consisting of toluene, tetrahydrofuran, and chlorobenzene.
The resultant product of the first embodiment is a liquid isocyanate prepolymer having an isocyanate group content of 12 to 30 percent and preferably 17 to 28 percent. The resultant product of the second embodiment is a liquid isocyanate prepolymer having an isocyanate group content of 5 to 29% and preferably 12 to 27%. These liquid isocyanate to prepolymerd have been found to be particularly useful in the preparation of isocyanate reaction products such as polyurethanes.
The invention is further illustrated but is not intended to be limited by the following examples in which all 15 parts and percentages are by weight unless otherwise specified.
EXAMPLES
MDI-X: Diphenylmethane diisocyanate which contains less than 6% by weight 2,2'-MDI and in which X represents the percent by weight 2,4'-MDI with the remainder being the 4,4'- and 20 2,2'-MDI.
Example 1 7.1 parts of MDI-20 and 5.0 parts of 2-pentanol were charged to a stirred reactor and heated at 80°C for about 2 hours. 92.9 parts of MDI-20 is then added to the reactor.
0.1 part of zinc acetylacetonate is then added to the reaction 2s mixture which is then heated to 110°C and held for 2 hours.
0.3 part of benzoyl chloride is then added and the reaction mixture is cooled to about 25°C to afford a clear liquid having an NCO content of 27.1% and a viscosity at 25°C of 100 mPa.s.
Examples 2-8 The same procedure and conditions as described in Example 1. In the first step, equal equivalents of MDI and the 3o alcohol are first reacted followed by addition of the remainder MDI. Any changes from Example 1 are set forth in the following table along with the % NCO and viscosity of the resulting clear liquid modified isocyanate.
Mo-3969 Alcohol/ Time % Uisc.
Example MDI-XJpbw pbw min. NCO 25C mPa.s 2 55/100 methanol/2.3 157 27.0 330 3 20/100 1-propanol/3.778 27.4 182 4 30/100 1-propanol/3.785 27.4 110 40/100 1-propanol/3.765 27.4 101 6 30/100 1-pentanol/5.090 27.4 130 7 20/100 1-pentanol/5.073 27.4 105 8 40/100 1-pentanol/5.040 27.4 84 to Example 9: 10 parts 2,4-toluene-diisocyanate (TDI) and 14.9 parts 2-octanol were charged to a stirred flask, 0.005 parts dibutyltin dilaurate catalyst was added and heated to 80°C for about 1 hour 30 min. To the diurethane is added 112.7 parts MDI-2 and 0.01 parts zinc acetylacetonate, which is then heated to 90°C and held for about 60 min. 0.03 part benzoyl chloride is then added at 90°C and the reaction mixture is cooled to about 25°C to afford a clear liquid, having an NCO content of 24.0% and a viscosity at 25°C of 1700 mPa.s.
2o Examples 10 through 21: Used the same procedure and conditions as described in Example 9. In the first step equal equivalents of the alcohol and the diisocyanate, for example hexamethylene diisocyanate (HDI), MDI-2 or TDI, are first reacted followed by addition of MDI-2. Any changes from Example 9 are set forth in 2s the following table along with the % NCO and viscosity.
Mo-3969 Diisocyanate Alcohol MDI-2 % Uisc @
Example (pbw) {pbw) {pbw) NCO 25°C mPa.s TDI/10 1-butanol/8.5 111.5 25.3 1300 s 11 TDI/10 2-butanol/8.5 115.0 25.3 1700 12 TDI/10 1-decylalcohol/18.2120.8 23.9 1100 13 TDI/10 1-pentanol/10.1 100.6 24.1 2200 14 TDI/10 2-pentanol/10.1 100.6 24.1 2500 HDI/10 2-octanol/16.1 119.2 23.9 1200 l0 16 HDI/10 2-pentanol/10.9 106.2 23.9 2150 17 HDI/10 2-butanol/9.2 101.9 23.9 3300 18 MDI/10 1-decylalcohol/12.791.7 24.1 1700 19 MDI/10 2-octanol/10.4 86.0 24.1 2200 MDI/10 2-pentanol/7.0 77.6 23.1 3900 15 21 MDI/10 2-butanol/5.9 74.8 23.9 4010 Althoughthe invention ribed detail has been desc in in the foregoing r the purpose on, s to fo of illustrati it be i understood that h detail is solely purposeand suc for that. that 2o variations constituting other embodiments be madetherein can by those s killed the art without from spirit in departing the and scope of the vention except may limitedby the in as it be claims.
Mo-3969
The allophanate-forming reaction is usually conducted in the presence of a catalyst. The useful catalysts are those which can be neutralized or otherwise stopped from adversely catalyzing subsequent reactions. Illustratively, a catalyst 15 such as zinc acetylacetonate can be employed, and a catalyst stopper such as acidic materials, e.g., anhydrous hydrochloric acid, sulfuric acid, benzoyl chloride, Lewis acids and the like in the ratio of 2 equivalents of the acid to each mole of the zinc acetylacetonate. Other allophanate catalysts such as zinc 20 2-ethylhexanoate, cobalt 2-ethylhexanoate, cobalt naphthanate, lead linoresinate or the like can be employed.
In a preferred embodiment of the process of the invention, the allophanate can be prepared by reacting the diisocyanate, as described above, with an aliphatic or aromatic 2s alcohol, at about 20°C to about 115°C. The resultant diurethane is dissolved in the specified MDI isomer composition and converted to an allophanate modified MDI at 90-110°C, using zinc acetylacetonate as catalyst, and benzoyl chloride as a stopper for the catalyst in a 2:1 weight ratio of benzoyl chloride to zinc acetylacetonate.
3o In the second embodiment of the invention, the process further to the afore-described process steps comprises reacting the allophanate modified MDI such as described above with a high and/or a low molecular weight organic material containing two or more and preferably 2 to 3 active hydrogen Mo-3969 ~~2834~
_, _ groups such as hydroxyl, primary or secondary amino groups or the like. The high molecular weight organic material can have a molecular weight from 400 to 6000 and preferably 2000 to 5000. The low molecular weight range can be from 60 to 200 and preferably 76 to 90.
The subject urethane, urea, or biuret reaction is carried out in a manner which is well known by, say, heating the reactants to a temperature from about 40 to 150°C and preferably from 50 to 100°C to form urethane or urea and to heating to a temperature of 100 to 150°C and preferably 110 to 120°C to form the biuret.
The useful organic materials containing two or more hydroxyl groups having a molecular weight of 400 to 6000 can be a polyol selected from the group consisting of polyester 1s polyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides and polyhydroxy polythioethers. The polyester polyols, polyether polyols and polyhydroxy polycarbonates are preferred.
2o Suitable polyester polyols include reaction products of polyhydric, preferably dihydric alcohols to which trihydric alcohols may be added and polybasic, preferably dibasic carboxylic acids. Instead of these polycarboxylic acids, the corresponding carboxylic acid anhydrides or polycarboxylic acid 2s esters of lower alcohols or mixtures thereof may be used for preparing the polyesters. The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/or heterocyclic and they may be substituted, e.g. by halogen atoms, and/or unsaturated. The following are mentioned as examples: succinic acid; adipic acid; suberic acid; azelaic acid; sebacic acid;
phthalic acid; isophthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrophthalic acid anhydride; hexahydro-phthalic acid anhydride; tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride; glutaric acid anhydride; malefic acid; malefic acid anhydride; fumaric acid;
Mo-3969 2,12834 _$_ dimeric and trimeric fatty acids such as oleic: acid, which may be mixed with monomeric fatty acids; dimethyl terephthalates and bis-glycol terephthalate. Suitable polyhydric alcohols include, e.g. ethylene glycol; propylene glycol-(1,2) and s -(1,3); butylene glycol-(1,4) and -{1,3); hexa,nediol-(1,6);
octanediol-(1,8); neopentyl glycol; cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane); 2-methyl-1,3-propanediol;
2,2,4-trimethyl-1,3-pentanediol; triethylene glycol; tetra-ethylene glycol; polyethylene glycol; dipropylene glycol;
io polypropylene glycol; dibutylene glycol and polybutylene glycol, glycerine and trimethlyolpropane. The polyesters may also contain a portion of carboxyl end groups. Polyesters of lactones, e.g. e-caprolactone or hydroxyl carboxylic acids, e.g. w-hydroxycaproic acid, may also be used.
15 Polycarbonates containing hydroxyl groups include those known per se such as the products obtained from the reaction of diols such as propanediol-{1,3), butanediol-(1,4) and/or hexanediol-(1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with phosgene, diarylcarbonates such as 2o diphenylcarbonate or with cyclic carbonates such as ethylene or propylene carbonate. Also suitable are polyester carbonates obtained from the above-mentioned polyesters or polylactones with phosgene, diaryl carbonates or cyclic carbonates.
Suitable polyether polyols are obtained in known 2s manner by the reaction of starting compounds which contain reactive hydrogen atoms with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin or mixtures of these alkylene oxides. It is preferred that the polyethers do not contain more than about 10% by weight of ethylene oxide units. Most 3o Preferably, polyethers obtained without the addition of ethylene oxide are used. Suitable starting compounds containing reactive hydrogen atoms include the polyhydric alcohols set forth for preparing the polyester' polyols and, in addition, water, methanol, ethanol, 1,2,6-hexane triol, Mo-3969 1,2,4-butane triol, trimethylol ethane, pentaerythritol, mannitol, sorbitol, methyl glycoside, sucrose, phenol, isononyl phenol, resorcinol, hydroquinone, 1,1,1- or 1,1,2-tris(hydroxylphenyl)-ethane.
Polyethers modified by vinyl polymers are also suitable for the process according to the invention. Products of this kind may be obtained by polymerizing, e.g. styrene and acrylonitrile in the presence of polyethers (U.S. Patent Nos. 3,383,351; 3,304,273; 3,523,095; 3,110,695 and German Patent No. 1,152,536).
Among the polythioethers which should be particularly mentioned are the condensation products obtained from thiodiglycol on its own and/or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. The products obtained are either polythio-mixed ethers, polythioether esters or polythioether ester amides, depending on the co-components.
Amine-terminated polyether useful herein can be prepared by reacting a primary amine with a polyether containing terminal leaving groups such as halides, or mesylates as disclosed in U.S. Patents 3,666,726, 3,691,112 and 5,066,824.
Suitable polyacetals include the compounds which can be prepared from aldehydes, e.g. formaldehyde, and glycols such as diethylene glycol, triethylene glycol, ethoxylated 4,4'-dihydroxy-diphenyldimethylmethane, and hexanediol-(1,6). Polyacetals suitable for the purpose of the invention may also be prepared by the polymerization of cyclic acetals.
Suitable polyhydroxy polyester amides and polyamines include the predominantly linear condensates obtained from polybasic saturated and unsaturated carboxylic acids or their anhydrides and palyvalent saturated or unsaturated aminoalcohols, diamines, polyamines and mixtures thereof.
Mo3969 2128~4~
-lo-Suitable monomers for producing hydroxy-functional polyacrylates include acrylic acid, methacrylic acid, crotonic acid, malefic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.
The low molecular weight material preferably containing two hydroxyl groups having an average molecular to weight of 60 to 200 may be used in combination with or instead of the high molecular weight material containing two or more hydroxyl groups. The useful low molecular weight materials include the polyhydric alcohols which have previously been described for the preparation of the polyester polyols and polyether polyols. Dihydric alcohols are preferred. The weight ratio of the low molecular weight to the high molecular weight material containing two or more hydroxyl groups can be from 0.001 to 2 and preferably 0.01 to 0.40.
In addition to the above-mentioned components which 2o are preferably difunctional, monofunctional and even small portions of trifunctional and higher functional components generally known in polyurethane chemistry, such as trimethylolpropane, may be used in special cases in which slight branching of the resultant product is desired.
In the process of the invention, the hydroxyl functional materials) can be reacted with the allophanate over the temperature range of 40 to 150 and preferably 50 to 100°C, over a period of time sufficient to complete the reaction.
Catalysts and solvents can be employed to aid the reaction.
Examples of the useful catalysts to promote the urethane 3o reactions can be selected from the group consisting of di-n-butyltin dichloride, di-n-butyltin diacetate, di-n-butyltin dilaurate, triethylenediamine, bismuth nitrate and the like.
Mo-3969 2~28~44 Examples of the useful solvents can be selected from the group consisting of toluene, tetrahydrofuran, and chlorobenzene.
The resultant product of the first embodiment is a liquid isocyanate prepolymer having an isocyanate group content of 12 to 30 percent and preferably 17 to 28 percent. The resultant product of the second embodiment is a liquid isocyanate prepolymer having an isocyanate group content of 5 to 29% and preferably 12 to 27%. These liquid isocyanate to prepolymerd have been found to be particularly useful in the preparation of isocyanate reaction products such as polyurethanes.
The invention is further illustrated but is not intended to be limited by the following examples in which all 15 parts and percentages are by weight unless otherwise specified.
EXAMPLES
MDI-X: Diphenylmethane diisocyanate which contains less than 6% by weight 2,2'-MDI and in which X represents the percent by weight 2,4'-MDI with the remainder being the 4,4'- and 20 2,2'-MDI.
Example 1 7.1 parts of MDI-20 and 5.0 parts of 2-pentanol were charged to a stirred reactor and heated at 80°C for about 2 hours. 92.9 parts of MDI-20 is then added to the reactor.
0.1 part of zinc acetylacetonate is then added to the reaction 2s mixture which is then heated to 110°C and held for 2 hours.
0.3 part of benzoyl chloride is then added and the reaction mixture is cooled to about 25°C to afford a clear liquid having an NCO content of 27.1% and a viscosity at 25°C of 100 mPa.s.
Examples 2-8 The same procedure and conditions as described in Example 1. In the first step, equal equivalents of MDI and the 3o alcohol are first reacted followed by addition of the remainder MDI. Any changes from Example 1 are set forth in the following table along with the % NCO and viscosity of the resulting clear liquid modified isocyanate.
Mo-3969 Alcohol/ Time % Uisc.
Example MDI-XJpbw pbw min. NCO 25C mPa.s 2 55/100 methanol/2.3 157 27.0 330 3 20/100 1-propanol/3.778 27.4 182 4 30/100 1-propanol/3.785 27.4 110 40/100 1-propanol/3.765 27.4 101 6 30/100 1-pentanol/5.090 27.4 130 7 20/100 1-pentanol/5.073 27.4 105 8 40/100 1-pentanol/5.040 27.4 84 to Example 9: 10 parts 2,4-toluene-diisocyanate (TDI) and 14.9 parts 2-octanol were charged to a stirred flask, 0.005 parts dibutyltin dilaurate catalyst was added and heated to 80°C for about 1 hour 30 min. To the diurethane is added 112.7 parts MDI-2 and 0.01 parts zinc acetylacetonate, which is then heated to 90°C and held for about 60 min. 0.03 part benzoyl chloride is then added at 90°C and the reaction mixture is cooled to about 25°C to afford a clear liquid, having an NCO content of 24.0% and a viscosity at 25°C of 1700 mPa.s.
2o Examples 10 through 21: Used the same procedure and conditions as described in Example 9. In the first step equal equivalents of the alcohol and the diisocyanate, for example hexamethylene diisocyanate (HDI), MDI-2 or TDI, are first reacted followed by addition of MDI-2. Any changes from Example 9 are set forth in 2s the following table along with the % NCO and viscosity.
Mo-3969 Diisocyanate Alcohol MDI-2 % Uisc @
Example (pbw) {pbw) {pbw) NCO 25°C mPa.s TDI/10 1-butanol/8.5 111.5 25.3 1300 s 11 TDI/10 2-butanol/8.5 115.0 25.3 1700 12 TDI/10 1-decylalcohol/18.2120.8 23.9 1100 13 TDI/10 1-pentanol/10.1 100.6 24.1 2200 14 TDI/10 2-pentanol/10.1 100.6 24.1 2500 HDI/10 2-octanol/16.1 119.2 23.9 1200 l0 16 HDI/10 2-pentanol/10.9 106.2 23.9 2150 17 HDI/10 2-butanol/9.2 101.9 23.9 3300 18 MDI/10 1-decylalcohol/12.791.7 24.1 1700 19 MDI/10 2-octanol/10.4 86.0 24.1 2200 MDI/10 2-pentanol/7.0 77.6 23.1 3900 15 21 MDI/10 2-butanol/5.9 74.8 23.9 4010 Althoughthe invention ribed detail has been desc in in the foregoing r the purpose on, s to fo of illustrati it be i understood that h detail is solely purposeand suc for that. that 2o variations constituting other embodiments be madetherein can by those s killed the art without from spirit in departing the and scope of the vention except may limitedby the in as it be claims.
Mo-3969
Claims (6)
1. A process for the production of a allophanate-modified MDI
which is a storage stable liquid at 25°C comprising (A) reacting (i) one equivalent of a diisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and hydrogenated MDI and ii) one equivalent of an aliphatic alcohol containing 1 to 36 carbon atoms or aromatic alcohol containing 6 to 18 carbon atoms to form a diurethane of the diisocyanate, B) reacting the product of (A) with 4,4'-diphenylmethane diisocyanate containing from 2 to 60% by weight 2,4'-MDI and less than 6% by weight of the 2,2'-MDI, in an amount sufficient to provide an allophanate having an isocyanate group content of 12.0 to 30.0%.
which is a storage stable liquid at 25°C comprising (A) reacting (i) one equivalent of a diisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and hydrogenated MDI and ii) one equivalent of an aliphatic alcohol containing 1 to 36 carbon atoms or aromatic alcohol containing 6 to 18 carbon atoms to form a diurethane of the diisocyanate, B) reacting the product of (A) with 4,4'-diphenylmethane diisocyanate containing from 2 to 60% by weight 2,4'-MDI and less than 6% by weight of the 2,2'-MDI, in an amount sufficient to provide an allophanate having an isocyanate group content of 12.0 to 30.0%.
2. The process of Claim 1 wherein the allophanate is prepared at 90-110°C in the presence of a zinc acetylacetonate catalyst.
3. The process of Claim 2 wherein benzoyl chloride is used as the stopper for the catalyst.
4. The process of Claim 1 further comprising reacting the allophanate-modified MDI with (a) an organic material containing two or more hydroxy, primary amine or secondary amino groups or any combination having a molecular weight of from 400 to 6000 (b) a diol having a molecular weight of from 60 to 200 or a combination of (a) and (b) to produce a liquid prepolymer having an isocyanate group content of from 5 to 29% by weight.
5. An allophanate-modified MDI which is stable and liquid at 25°C and has an isocyanate content of about 12 to 30.0% which is prepared by the process of Claim 1.
6. An allophanate-modified MDI which is stable and liquid at 25°C and has an isocyanate content of about 5 to 29% which is prepared by the process of Claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/116,096 US5319054A (en) | 1993-09-02 | 1993-09-02 | Liquid methylene diphenyl diisocyanate |
| US08/116,096 | 1993-09-02 |
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| Publication Number | Publication Date |
|---|---|
| CA2128344A1 CA2128344A1 (en) | 1995-03-03 |
| CA2128344C true CA2128344C (en) | 2005-11-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002128344A Expired - Fee Related CA2128344C (en) | 1993-09-02 | 1994-07-19 | Liquid methylene diphenyl diisocyanate |
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| Country | Link |
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| US (1) | US5319054A (en) |
| CA (1) | CA2128344C (en) |
Families Citing this family (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5440003A (en) * | 1993-09-02 | 1995-08-08 | Miles Inc. | Liquid methylene diphenyl diisocyanate |
| CA2117741A1 (en) * | 1993-10-28 | 1995-04-29 | Michael F. Hurley | Rim process utilizing isocyanates based upon 2,4'-and 4,4'- diphenylmethane diisocyanate |
| DE4403233A1 (en) * | 1994-02-03 | 1995-08-10 | Bayer Ag | Liquid polyisocyanate mixtures above 5 ° C |
| DE4441176A1 (en) * | 1994-11-18 | 1996-05-23 | Bayer Ag | Polyisocyanates containing allophanate groups |
| DE19502198A1 (en) * | 1995-01-25 | 1996-08-01 | Bayer Ag | Process for the production of molded articles |
| US5567793A (en) * | 1995-06-06 | 1996-10-22 | Bayer Corporation | Urethane-free, diphenylmethane diisocyanate prepolymers and process for their production |
| US5686042A (en) * | 1995-06-07 | 1997-11-11 | Bayer Corporation | Rim process using liquid methylene diphenyl diisocyanate |
| US5606001A (en) * | 1995-09-14 | 1997-02-25 | Bayer Corporation | Polyisocyanates containing allophanate groups and optionally isocyanurate groups |
| DE19534162A1 (en) * | 1995-09-15 | 1997-03-20 | Bayer Ag | Binder combination for the production of solvent-free coating compositions |
| US5648445A (en) * | 1995-12-22 | 1997-07-15 | Bayer Corporation | Liquid 1,3-phenylene diisocyanate, 1,1'-biphenyl diisocyanate and 1,1'-oxy-bis-(isocyanato-benzene) |
| US5663272A (en) * | 1995-12-22 | 1997-09-02 | Bayer Corporation | Allophanate-modified diphenylmethane diisocyanates and processes for their production and use |
| DE19618230A1 (en) * | 1996-05-07 | 1997-11-13 | Bayer Ag | TDI polyisocyanates containing heteroallophanate groups |
| US5874485A (en) * | 1997-11-10 | 1999-02-23 | Bayer Corporation | Flexible foams and flexible molded foams based on allophanate-modified diphenylmethane diisocyanates and processes for the production of these foams |
| US5821275A (en) * | 1997-11-10 | 1998-10-13 | Bayer Corporation | Flexible foams and flexible molded foams based on liquid isocyanate-terminated allophanate-modified MDI prepolymer blends and processes for the production of these foams |
| US6228472B1 (en) * | 1998-12-21 | 2001-05-08 | Basf Corporation | Process for synthesis of allophanate compounds and compositions including the product thereof |
| US6214470B1 (en) | 1998-12-21 | 2001-04-10 | Basf Corporation | Cathodic electrocoat composition |
| US6482913B1 (en) | 2000-02-07 | 2002-11-19 | Bayer Aktiengesellschaft | Liquid MDI adducts wtih improved freeze stability |
| US6271279B1 (en) | 2000-07-10 | 2001-08-07 | Bayer Corporation | High resilient flexible urethane foam and flexible molded foams based on allophanate modified isocyanates |
| US6765080B2 (en) * | 2002-06-06 | 2004-07-20 | Bayer Corporation | High performance RIM elastomers and a process for their production |
| US6887399B2 (en) * | 2002-09-09 | 2005-05-03 | Bayer Materialscience Llp | Polymeric allophanates of diphenylmethane diisocyanate, prepolymers of these polymeric allophanates, and processes for the preparation of the polymeric allophanates and the prepolymers thereof |
| US6797799B1 (en) | 2003-04-02 | 2004-09-28 | Bayer Materialscience Llc | High 2,4′-diphenylmethane diisocyanate content prepolymers |
| US6838542B1 (en) | 2003-07-24 | 2005-01-04 | Bayer Materialscience Llc | Stable liquid biuret modified and biuret allophanate modified diphenylmethane diisocyanates, prepolymers thereof, and processes for their preparation |
| DK1778755T3 (en) | 2004-07-21 | 2011-03-07 | Stichting Tech Wetenschapp | Polyacylurethanes based on diisocyanates and polyester polyols |
| DE102004051026A1 (en) * | 2004-10-20 | 2006-04-27 | Bayer Materialscience Ag | Crystallization-stable MDI allophanates according to a two-stage process |
| US7790907B2 (en) * | 2006-07-21 | 2010-09-07 | Basf Corporation | Method of producing a uretonimine-modified isocyanate composition |
| US20080085987A1 (en) * | 2006-10-05 | 2008-04-10 | Thomas Savino | Method of producing a uretonimine-modified isocyanate composition |
| US7776969B2 (en) * | 2006-12-04 | 2010-08-17 | Bayer Materialscience Llc | Allophanate-modified stabilizers and the polymer polyols prepared from these stabilizers |
| US20080132724A1 (en) * | 2006-12-04 | 2008-06-05 | Bayer Materialscience Llc | Allophanate modified isocyanates which contain reactive unsaturation |
| 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 |
| US20090030161A1 (en) * | 2007-07-27 | 2009-01-29 | Bayer Materialscience Llc | Allophanate modified diphenylmethane diisocyanates, prepolymers thereof, and their use in the preparation of polyureas and polyurethanes |
| CA2638522A1 (en) * | 2007-08-06 | 2009-02-06 | Crowley Chemical Company | Reactive aromatic oils with improved adhesive properties |
| US20090156777A1 (en) | 2007-12-17 | 2009-06-18 | Nodelman Neil H | Freeze-stable aromatic diisocyanates and processes for the preparation of these freeze-stable products |
| US8410213B2 (en) * | 2009-01-26 | 2013-04-02 | Michael James Barker | Primerless two-part polyurethane adhesive |
| US8808495B2 (en) | 2011-04-15 | 2014-08-19 | H.B. Fuller Company | Modified diphenylmethane diisocyanate-based adhesives |
| WO2018071920A1 (en) * | 2016-10-14 | 2018-04-19 | Dm Healthcare Products, Inc | Curable urethane dimethacrylates and dental restorative compositions thereof |
| JP7326700B2 (en) * | 2017-09-19 | 2023-08-16 | 東ソー株式会社 | POLYURETHANE RESIN FORMABLE COMPOSITION AND SEALING MATERIAL AND MEMBRANE MODULE USING THE FORMABLE COMPOSITION |
| DE102018114690A1 (en) | 2018-06-19 | 2019-12-19 | Voco Gmbh | Thermally effective dental composite composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1618380C3 (en) * | 1967-03-08 | 1975-09-11 | Bayer Ag, 5090 Leverkusen | Process for the production of a diphenylmethane diisocyanate preparation which is liquid at room temperature |
| US4055548A (en) * | 1976-09-17 | 1977-10-25 | The Upjohn Company | Storage-stable liquid polyisocyanate composition |
| US4118411A (en) * | 1977-02-09 | 1978-10-03 | Mobay Chemical Corporation | Low-temperature storage stable liquid diphenylmethane diisocyanates |
| US4115429A (en) * | 1977-03-18 | 1978-09-19 | Mobay Chemical Corporation | Low-temperature storage stable liquid diphenylmethane diisocyanates |
| DE2729990A1 (en) * | 1977-07-02 | 1979-01-18 | Bayer Ag | PROCESS FOR THE PREPARATION OF ALLOPHANATES HAVING ISOCYANATE GROUPS |
| EP0010850B2 (en) * | 1978-10-03 | 1990-01-31 | Imperial Chemical Industries Plc | Liquid polyisocyanate compositions |
| US4490300A (en) * | 1983-09-30 | 1984-12-25 | Mobay Chemical Corporation | Liquid diphenylmethane diisocyanate compositions |
| US4738991A (en) * | 1987-01-23 | 1988-04-19 | Basf Corporation | Storage stable polyisocyanates characterized by allophanate linkages |
| US4910333A (en) * | 1987-06-03 | 1990-03-20 | Mobay Corporation | Liquid diphenylmethane diisocyanate compositions |
| US4906674A (en) * | 1987-10-16 | 1990-03-06 | Ici Americas Inc/Imperial Chemical Industries Plc | Polysocyanate compositions |
-
1993
- 1993-09-02 US US08/116,096 patent/US5319054A/en not_active Expired - Lifetime
-
1994
- 1994-07-19 CA CA002128344A patent/CA2128344C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2128344A1 (en) | 1995-03-03 |
| US5319054A (en) | 1994-06-07 |
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Effective date: 20140721 |