CA1178603A - 2,2,4,4-tetraalkyl-1,3-cyclobutanediol modified diphenylmethane diisocyanate - Google Patents
2,2,4,4-tetraalkyl-1,3-cyclobutanediol modified diphenylmethane diisocyanateInfo
- Publication number
- CA1178603A CA1178603A CA000399666A CA399666A CA1178603A CA 1178603 A CA1178603 A CA 1178603A CA 000399666 A CA000399666 A CA 000399666A CA 399666 A CA399666 A CA 399666A CA 1178603 A CA1178603 A CA 1178603A
- Authority
- CA
- Canada
- Prior art keywords
- diphenylmethane diisocyanate
- diisocyanate
- liquid
- temperature
- tetraalkylcyclobutanediol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The instant invention is directed to a process for the production of diisocyanate compounds which are both stable and liquid at room temperature, comprising reacting a diisocyanate selected from the group consisting of 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane di-isocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof with 2,2,4,4-tetraalkylcyclobutanediol at a temperature of from about 40°C to about 120°C in such a ratio as to afford a product having a percent NCO value in the range of 20 to 30%. The instant invention is also direct-ed to the product prepared by this process.
The instant invention is directed to a process for the production of diisocyanate compounds which are both stable and liquid at room temperature, comprising reacting a diisocyanate selected from the group consisting of 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane di-isocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof with 2,2,4,4-tetraalkylcyclobutanediol at a temperature of from about 40°C to about 120°C in such a ratio as to afford a product having a percent NCO value in the range of 20 to 30%. The instant invention is also direct-ed to the product prepared by this process.
Description
Mo-2119 ~1- PU-109
2,2,q,4-TETR~ALKYL-1,3-CYCLOBUTANEDIOL
~ODIFIED DIPHENYLMETHANE DIISOCYANATE
BAC~GROUND OF THE INVENTIOM
This invention relates to organic diisocyanates and mixtures of organic diisocyanates based on 2,2'-, 2,4'-and/or 4,4'-diphenylmethane diisocyanates which are liquid at room temperature. The invention also relates to a process for preparing these diisocyanates.
Diisocyanates which are liquid at room temperature 10 have numerous advantages over solid diisocyanates because they are easier to mix and work with. Diisocyanates, however, which are liquid at room temperature, are as a rule physiologically harmful because of their high vapor pressure and Call only be handled if certain precautions are taken. For this reason, 15 various attempts have been made to start with diisocyanates that are solid at room temperature and convert these into the liquid form by certain measures. However, one usually obtains isocyanates with lligh functionality, i.e., tri-or polyisocyanates or higher molecular weight diisocyanates 20 or a combination of these~
The most important diisocyanates which are solid at room temperature and which are readily available on a large commercial scale are 4,4'-diphenylmethane diisocyanate and the 2,4'-isomer thereof which melt at 39C and 34.5C, 25 respectively. Attempts have been made also to liquefy the 4,4'-diphenylmethane diisocyanate isomer. Thus, for example, according to U.S. Patent 3,152,162, 4,4'-diphenyl-methane diisocyanate is heated at temperatures above 150C
to affect a partial carbodiimization of the isocyanate.
30 The isocyanate groups still present partly react with the resulting carbodiimide groups to form uretone imine. The resultant liquid products are not diisocyanates but are polyisocyanates. This manifests itself in the reaction of the products with bifunctional low molecular weight or 35 higher molecular weight hydroxyl compounds, the reaction Mo-2119 ~.
~: i ' ~ . . , ' : ~, . ' ' ' ~l~7~
leading not to soluble linear ~roducts but to insoluble cross-linked products.
It is known from U.S. Patent 3,644,457 to react 4,4'- and/or 2,4'-diphenylmethane diisocyanate with a branched aliphatic dihydroxy compound which yields a product which is liquid at room temperature.
It is therefore an object of this invention to provide improved liquid organic diisocyanates which are liquid at room temperature. ~nother object of this invention is to provide a mixture or diphenylmethane diisocyanates which i's liquid at room temperature. A further object of this invention is to provide organic diisocyanates which remain liquid even on prolonged storage at low temperatures.
Still another object of this invention is to provide an improved process for preparing liquid organic diisocyanates.
DESCRIPTION OF THE INV~NTION
The instant invention is directed to a process for preparing a liquid modified diphenylmethane diisocyanate comprising reacting a 2,2,4,4-tetraalkylcyclobutanediol and preferably, 2,2,4,4-tetramethylcyclobutanediol, with diphenylmethane diisocyanate at a temperature between about 40 to 120C, preferably between 40 to 100C, more preferably be~ween 45 to 80C, and most preferably between 50 to 60C
in such a ratio as to produce a product having a weight percent NCO value in the range of 20 to 30%, and preferably in the range of 21 to 27%. In general, the weight ratio of diphenylmethane diisocyanate to diol will be from 15:1 to 5:1 and is preferably from 10:1 to 6:1. The liquid modified diphenylmethane diisocyanate may also be prepared as a concen-trate (that is, with a lower percent NCO) and diluted with additional diphenylmethane diisocyanate to adjust the , percent NCO to the desired value.
The instant invention is a'lso directed to d'iisocyanatecompounds which are both stable and liquid at room temperature, prepared by reacting a diphenylmethane diisocyanate with a 2,2,4,4-tetraalkylcyclobutanediol at a temperature of from about 40C to about 120C in such a ratio as to afford A''~o-A!il 9 ~L~7~
- ` I
~ODIFIED DIPHENYLMETHANE DIISOCYANATE
BAC~GROUND OF THE INVENTIOM
This invention relates to organic diisocyanates and mixtures of organic diisocyanates based on 2,2'-, 2,4'-and/or 4,4'-diphenylmethane diisocyanates which are liquid at room temperature. The invention also relates to a process for preparing these diisocyanates.
Diisocyanates which are liquid at room temperature 10 have numerous advantages over solid diisocyanates because they are easier to mix and work with. Diisocyanates, however, which are liquid at room temperature, are as a rule physiologically harmful because of their high vapor pressure and Call only be handled if certain precautions are taken. For this reason, 15 various attempts have been made to start with diisocyanates that are solid at room temperature and convert these into the liquid form by certain measures. However, one usually obtains isocyanates with lligh functionality, i.e., tri-or polyisocyanates or higher molecular weight diisocyanates 20 or a combination of these~
The most important diisocyanates which are solid at room temperature and which are readily available on a large commercial scale are 4,4'-diphenylmethane diisocyanate and the 2,4'-isomer thereof which melt at 39C and 34.5C, 25 respectively. Attempts have been made also to liquefy the 4,4'-diphenylmethane diisocyanate isomer. Thus, for example, according to U.S. Patent 3,152,162, 4,4'-diphenyl-methane diisocyanate is heated at temperatures above 150C
to affect a partial carbodiimization of the isocyanate.
30 The isocyanate groups still present partly react with the resulting carbodiimide groups to form uretone imine. The resultant liquid products are not diisocyanates but are polyisocyanates. This manifests itself in the reaction of the products with bifunctional low molecular weight or 35 higher molecular weight hydroxyl compounds, the reaction Mo-2119 ~.
~: i ' ~ . . , ' : ~, . ' ' ' ~l~7~
leading not to soluble linear ~roducts but to insoluble cross-linked products.
It is known from U.S. Patent 3,644,457 to react 4,4'- and/or 2,4'-diphenylmethane diisocyanate with a branched aliphatic dihydroxy compound which yields a product which is liquid at room temperature.
It is therefore an object of this invention to provide improved liquid organic diisocyanates which are liquid at room temperature. ~nother object of this invention is to provide a mixture or diphenylmethane diisocyanates which i's liquid at room temperature. A further object of this invention is to provide organic diisocyanates which remain liquid even on prolonged storage at low temperatures.
Still another object of this invention is to provide an improved process for preparing liquid organic diisocyanates.
DESCRIPTION OF THE INV~NTION
The instant invention is directed to a process for preparing a liquid modified diphenylmethane diisocyanate comprising reacting a 2,2,4,4-tetraalkylcyclobutanediol and preferably, 2,2,4,4-tetramethylcyclobutanediol, with diphenylmethane diisocyanate at a temperature between about 40 to 120C, preferably between 40 to 100C, more preferably be~ween 45 to 80C, and most preferably between 50 to 60C
in such a ratio as to produce a product having a weight percent NCO value in the range of 20 to 30%, and preferably in the range of 21 to 27%. In general, the weight ratio of diphenylmethane diisocyanate to diol will be from 15:1 to 5:1 and is preferably from 10:1 to 6:1. The liquid modified diphenylmethane diisocyanate may also be prepared as a concen-trate (that is, with a lower percent NCO) and diluted with additional diphenylmethane diisocyanate to adjust the , percent NCO to the desired value.
The instant invention is a'lso directed to d'iisocyanatecompounds which are both stable and liquid at room temperature, prepared by reacting a diphenylmethane diisocyanate with a 2,2,4,4-tetraalkylcyclobutanediol at a temperature of from about 40C to about 120C in such a ratio as to afford A''~o-A!il 9 ~L~7~
- ` I
-3-a product having a weight percent NCO value in the range of 20 to 30%. As used herein, the term "diphenylmethane diisocyanate" is defined as 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and mixtures thereof.
Most short chain diols, such as 1,4- and 1,3-butane-diol, ethylene glycol, and the like when reacted with diphenylmethane diisocyanate result in solids at room temperature. In contrast, the instant li~uid modified 10 diphenylmethane diisocyanate remains a liquid at 25C.
The process of the instant invention may also be used to increase the hard block concentration via the prepolymer of the RIM formulation instead of increasing the butanediol concentration in the polyol side which leads to mixing 15 problems. Heat sag values are specially improved when the instant prepolymers are used. ;
The liquid diisocyanates which can be prepared according to the invention, preferably from 4,4'- and/cr 2,4'-diphenylmethane diisocyanate, have a very low viscosity 20 and can therefore be processed very easily. For example, they can be cast or metered through pumps. Additionally, they have a very low vapor pressure and are therefore less physiologically harmful.
The process may be carried out by introducing the 25 2,2,4,4-tetraalkylcyclobutanediol into the diisocyanate at temperatures of about 40 to about 120C with stirring. The isocyanate content of the products of the process amounts to about 20% by weight NCO to about 30~ by weight NCO, and preferably 21 to 27%.
2,2,4,4-tetraalkylcyclobutanediols wherein each alkyl group, which may be the same or different, contains from 1 to 7 carbon atoms are preferably used. The presently preferred compound is 2,2-,4,4-tetramethylcyclobutanediol.
It is also possible to blend the tetraalkylcyclo-35 butanediol of the present invention with other hydroxy functional materials. If the hydroxyl functional material Mo-2119 .
.
~ . :
.
.
. . .
. , .
-~
.~
: . ; ......... :
-.~ 78~ 3 to be blended is of the type which forms liquid products i with diphenylmethane diisocyana-te ~such as those described in U.S. Patents 3,644,457; 4,115,429 and 4,118,411), as little as 10% by weight (based on the weight of the tetra-alkylcyclobutanediol and other hydroxy functional materials)of the tetraalkylcyclobutanediol can be used. Where the hydroxy func-tional material does not normally form a li~uid product with diphenylmethane diisocyanate, the tetraalkyl-cyclobutanediol should constitute at least 50% by weight 10 of the mixture of the tetraalkylcyclobutanediol with other hydroxy functional materials. It is generally preferred, however, to use the tetraalkylcyclobutane alone.
The products of the process can be used for all sorts of different polyaddition reactions in the lacquer and 15 plastics industry. For example, they may be used in the production of polyurethane foams or polyurethane elastomers which are in turn useful for the preparaiion of cushions or cast gear wheels, respectively. The invention is further illustrated by the following Example.
EXAMPLE
E~AMPLE 1 About 850 g of 4,4'-diphenylmethane diisocyanate (97% 4,4'-MDI and 3% 2,4'-MDI) are melted and mixed a~
about 58 to 73C with about 85.9 g of 2,2,4,4-tetramethyl-25 cyclobutanediol with stirring for about 3 hours. The resulting product hadan NCO value of 25%. The viscosity was 367 cPs at 25C.
Although the invention has been described in considerable detail in the foregoing, it is to be understood 30 that such detail is solely for the purpose of illustration and that many variations can be made by those skilled in the art without departing from the spirit and scope of the invention except as set forth in the claims.
Mo-2119 .. ..... . . ... . . . ... .. _ , ......... . ~ .. , .... ... _ ......
Most short chain diols, such as 1,4- and 1,3-butane-diol, ethylene glycol, and the like when reacted with diphenylmethane diisocyanate result in solids at room temperature. In contrast, the instant li~uid modified 10 diphenylmethane diisocyanate remains a liquid at 25C.
The process of the instant invention may also be used to increase the hard block concentration via the prepolymer of the RIM formulation instead of increasing the butanediol concentration in the polyol side which leads to mixing 15 problems. Heat sag values are specially improved when the instant prepolymers are used. ;
The liquid diisocyanates which can be prepared according to the invention, preferably from 4,4'- and/cr 2,4'-diphenylmethane diisocyanate, have a very low viscosity 20 and can therefore be processed very easily. For example, they can be cast or metered through pumps. Additionally, they have a very low vapor pressure and are therefore less physiologically harmful.
The process may be carried out by introducing the 25 2,2,4,4-tetraalkylcyclobutanediol into the diisocyanate at temperatures of about 40 to about 120C with stirring. The isocyanate content of the products of the process amounts to about 20% by weight NCO to about 30~ by weight NCO, and preferably 21 to 27%.
2,2,4,4-tetraalkylcyclobutanediols wherein each alkyl group, which may be the same or different, contains from 1 to 7 carbon atoms are preferably used. The presently preferred compound is 2,2-,4,4-tetramethylcyclobutanediol.
It is also possible to blend the tetraalkylcyclo-35 butanediol of the present invention with other hydroxy functional materials. If the hydroxyl functional material Mo-2119 .
.
~ . :
.
.
. . .
. , .
-~
.~
: . ; ......... :
-.~ 78~ 3 to be blended is of the type which forms liquid products i with diphenylmethane diisocyana-te ~such as those described in U.S. Patents 3,644,457; 4,115,429 and 4,118,411), as little as 10% by weight (based on the weight of the tetra-alkylcyclobutanediol and other hydroxy functional materials)of the tetraalkylcyclobutanediol can be used. Where the hydroxy func-tional material does not normally form a li~uid product with diphenylmethane diisocyanate, the tetraalkyl-cyclobutanediol should constitute at least 50% by weight 10 of the mixture of the tetraalkylcyclobutanediol with other hydroxy functional materials. It is generally preferred, however, to use the tetraalkylcyclobutane alone.
The products of the process can be used for all sorts of different polyaddition reactions in the lacquer and 15 plastics industry. For example, they may be used in the production of polyurethane foams or polyurethane elastomers which are in turn useful for the preparaiion of cushions or cast gear wheels, respectively. The invention is further illustrated by the following Example.
EXAMPLE
E~AMPLE 1 About 850 g of 4,4'-diphenylmethane diisocyanate (97% 4,4'-MDI and 3% 2,4'-MDI) are melted and mixed a~
about 58 to 73C with about 85.9 g of 2,2,4,4-tetramethyl-25 cyclobutanediol with stirring for about 3 hours. The resulting product hadan NCO value of 25%. The viscosity was 367 cPs at 25C.
Although the invention has been described in considerable detail in the foregoing, it is to be understood 30 that such detail is solely for the purpose of illustration and that many variations can be made by those skilled in the art without departing from the spirit and scope of the invention except as set forth in the claims.
Mo-2119 .. ..... . . ... . . . ... .. _ , ......... . ~ .. , .... ... _ ......
Claims (9)
1. A process for the production of diisocyanate compounds which are both stable and liquid at room temperature, comprising reacting a diphenylmethane diisocyanate with a 2,2,4,4-tetraalkyleyclobutanediol at a temperature of from about 40°C to about 120°C in such a ratio as to yield a product having a weight percent NCO
value of from 20 to 30%.
value of from 20 to 30%.
2. The process of Claim 1, wherein said 2,2,4,4-tetraalkylcyclobutanediol is of the formula:
wherein R, which may be the same or different, contains from 1 to 7 carbon atoms.
wherein R, which may be the same or different, contains from 1 to 7 carbon atoms.
3. The process of Claim 2, wherein said 2,2,4,4-tetraalkylcyclobutanediol is 2,2,4,4-tetramethylcyclobutane-diol.
4. The process of Claim 2, wherein the percent NCO
value of the product is from 21 to 27%.
value of the product is from 21 to 27%.
5. The process of Claim 1, wherein a eoncentrate is formed and subsequently diluted with diisocyanate to the claimed NCO value.
6. The process of Claim 1, wherein the reaction temperature is 40 to 100°C.
7. The process of Claim 6, wherein said reaetion temperature is 45 to 80°C.
8. The process of Claim 7, wherein said reactio.n temperature is 50 to 60°C.
Mo-2119
Mo-2119
9. Diisocyanate compounds having an NCO content of from 20 to 30%, which are both stable and liquid at room temperature, prepared by reacting a diphenylmethane diisocyanate with a 2,2,4,4-tetraalkylcyclobutanediol at a temperature of from about 40°C to about 120°C.
Mo-2119
Mo-2119
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26655581A | 1981-05-22 | 1981-05-22 | |
| US266,555 | 1988-11-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1178603A true CA1178603A (en) | 1984-11-27 |
Family
ID=23015063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000399666A Expired CA1178603A (en) | 1981-05-22 | 1982-03-29 | 2,2,4,4-tetraalkyl-1,3-cyclobutanediol modified diphenylmethane diisocyanate |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0066130A1 (en) |
| JP (1) | JPS57197254A (en) |
| CA (1) | CA1178603A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581388A (en) * | 1984-01-14 | 1986-04-08 | Bayer Aktiengesellschaft | Process for the production of urethane-modified polyisocyanate using an oxyalkylated bisphenol |
| US4587322A (en) * | 1984-02-18 | 1986-05-06 | Bayer Aktiengesellschaft | Process for the production of urethane-modified polyisocyanate compositions using a hydantoin having two hydroxyl alkyl substituents |
| US4677136A (en) * | 1985-07-23 | 1987-06-30 | Bayer Aktiengesellschaft | Process for the production of polyisocyanate compositions containing urea and/or biuret groups, the polyisocyanate compositions obtained by this process, and their use for the production of plastics by the isocyanate polyaddition process |
| US4707502A (en) * | 1985-08-01 | 1987-11-17 | Bayer Aktiengesellschaft | Process for the production of urethane-modified polyisocyanate preparations, the polyisocyanate preparations obtainable by this process and their use in the production of plastics based on polyisocyanates |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2521526B1 (en) * | 2009-11-20 | 2019-07-03 | DENTSPLY SIRONA Inc. | Dental materials using 2,2,4,4-tetramethyl-1,3-cyclobutanediol |
| CN108699214A (en) | 2016-02-23 | 2018-10-23 | 伊士曼化工公司 | Isocyanate-modified hard thermoplastic polymer composition |
| EP3420012A4 (en) | 2016-02-23 | 2019-10-23 | Eastman Chemical Company | Isocyanate-modified rigid thermoplastic polymer compositions |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1012929A (en) * | 1961-10-10 | 1965-12-08 | Union Carbide Corp | Improvements in and relating to polyurethanes |
| 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 |
| US3856830A (en) * | 1971-12-23 | 1974-12-24 | Atlas Chem Ind | Polymerizable urethane compounds |
| US4118411A (en) * | 1977-02-09 | 1978-10-03 | Mobay Chemical Corporation | Low-temperature storage stable liquid diphenylmethane diisocyanates |
-
1982
- 1982-03-29 CA CA000399666A patent/CA1178603A/en not_active Expired
- 1982-05-12 EP EP82104091A patent/EP0066130A1/en not_active Withdrawn
- 1982-05-20 JP JP57084113A patent/JPS57197254A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4581388A (en) * | 1984-01-14 | 1986-04-08 | Bayer Aktiengesellschaft | Process for the production of urethane-modified polyisocyanate using an oxyalkylated bisphenol |
| US4587322A (en) * | 1984-02-18 | 1986-05-06 | Bayer Aktiengesellschaft | Process for the production of urethane-modified polyisocyanate compositions using a hydantoin having two hydroxyl alkyl substituents |
| US4677136A (en) * | 1985-07-23 | 1987-06-30 | Bayer Aktiengesellschaft | Process for the production of polyisocyanate compositions containing urea and/or biuret groups, the polyisocyanate compositions obtained by this process, and their use for the production of plastics by the isocyanate polyaddition process |
| US4707502A (en) * | 1985-08-01 | 1987-11-17 | Bayer Aktiengesellschaft | Process for the production of urethane-modified polyisocyanate preparations, the polyisocyanate preparations obtainable by this process and their use in the production of plastics based on polyisocyanates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57197254A (en) | 1982-12-03 |
| EP0066130A1 (en) | 1982-12-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |