CA1091683A - Low-temperature storage stable liquid diphenylmethane diisocyanates - Google Patents
Low-temperature storage stable liquid diphenylmethane diisocyanatesInfo
- Publication number
- CA1091683A CA1091683A CA295,846A CA295846A CA1091683A CA 1091683 A CA1091683 A CA 1091683A CA 295846 A CA295846 A CA 295846A CA 1091683 A CA1091683 A CA 1091683A
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- CA
- Canada
- Prior art keywords
- isomer
- compound
- liquid
- percent
- weight
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
Abstract
LOW-TEMPERATURE STORAGE STABLE
LIQUID DIPHENYLMETHANE DIISOCYANATES
ABSTRACT OF THE DISCLOSURE
The instant invention is directed to novel low temperature, storage stable liquid diphenylmethane diisocy-anates and to the method of their preparation. The diisocy-anates of the instant invention are produced by reacting diphenylmethane diisocyanates having a specified 2,4'-isomer content with propylene glycol or poly-1,2-propylene ether glycols. It has been surprisingly found that the products of the instant invention are both stable and liquid at -5°C for at least 48 hours. In fact, in many instances, the products of the instant invention show no tendency to crystallize even when stored at -22°C for weeks.
LIQUID DIPHENYLMETHANE DIISOCYANATES
ABSTRACT OF THE DISCLOSURE
The instant invention is directed to novel low temperature, storage stable liquid diphenylmethane diisocy-anates and to the method of their preparation. The diisocy-anates of the instant invention are produced by reacting diphenylmethane diisocyanates having a specified 2,4'-isomer content with propylene glycol or poly-1,2-propylene ether glycols. It has been surprisingly found that the products of the instant invention are both stable and liquid at -5°C for at least 48 hours. In fact, in many instances, the products of the instant invention show no tendency to crystallize even when stored at -22°C for weeks.
Description
Mo-1697-~
~q3 ~ PU-0~1 LOW-TEMPERATURE STORAGE STABLE
LIQUID DIP~IENYLMETHANE D~ISOCYANATES
BACKGROUND OF THE INVENTION
It is well known that diisocyanates which are liquid at room temperature (i.e., about 25C) have numerous advantages over solid diisocyanates because they are easier to mix and work with. However, diisocyanates which are liquid at room temperature and which are used on a large technical scale, such as toluene diisocyanate or hexamethylene diisocyanate, are as a rule physiologically harmful due to their high vapor pressure and therefore can only be used if certain safety precautions are taken. For this reason, various attempts have been made, either to start with diisocyanates that are nor-mally liquid at room temperature and to reduce their physiological effects by certain procedures or to start with diisocyanates that are solid at room temperature and to convert these into liquid form. In both cases, however, one usually obtains either isocyanates of higher valency, i.e., tri- or polyisocyanates or higher molecular weight diisocyanates or a combination of these effects.
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 re-spectively. Attempts have already been made to liquify boththe 4,4'-diphenylmethane diisocyanate and a mixture of the 4,4'-diphenylmethane diisocyanate and a small amount of the 2,4'-isomer. Thus, for example, in U. S. Patent 3,644,457, l mol of a diphenylmethane diisocyanate is reacted with from about 0.1 to about 0.3 mols o~ poly-1,2-propylene ether glycol.
3~
While the products made according to this pa-tent have met with commercial success, they still suffer from a serious drawback.
Specifically, it has been found that these adducts generally will crystallize anywhere from 5C to as high as 25C. In fact, when supplied in commercial quantities, these adducts are generally transported in heated trucks. Additionally, in order to thaw the materials, it is generally necessary to heat them to somewhere in exc~ss of 50 to 60~C. While in warmer climates, there may not be any problem, in colder areas where the product may be stored in tanks over a period of time, this tendency to crystallize can become a very serious problem. Similar attempts to form liquid diphenylmethane diisocyanates have been described for example, in U. SO Patents 3,384,653 and 3,394,164. The attempts to liquify in both of these instances were based on the addition of, in one case, a trihydrocarbyl phosphate, and, in the other case, small amounts of phosphoric acid. In any event, the storage stability of both of these types of products is again quite good around room temperature, but as the temper-ature decreases, both types of materials tend to crystallize.
It is therefore an object of this invention to pro-vide improved liquid organic diisocyanates which are liquid and stable at temperatures lower than room temperature. A
further object of this invention is to provide organic di-isocyanates which remain liquid even on prolonged storage at low temperatures.
DESCRIPTION OF THE INVENTION
The instant invention is therefore directed to novel diisocyanate compounds which are both stable and liquid at -5C for at least 48 hours which diisocyanate compound com-prises the reaction product of a diphenylmethane diisocyanate f;~l containin~ at least l5~ by weight o~ the 2,4'-isomer with either propylene glycol or a poly-1,2-propylene ether g]ycol. The materials are reacted in an NCO/OH ratio of from about 3 : 1 to about 15 : 1, preferably from about 3 : 1 to about 10 : 1 and most preferably from about 3 : 1 to about 6 : 1. It has been found that when the most preferable NCO/OH ratio is used, novel diisocyanate compounds are obtained which are both stable and liquid at -22C for twelve (12) weeks.
The glycol and the isocyanate can be reacted at tem-peratures ranging anywhere from room temperature (i.e., about 25) up to 125C. Preferably, the reaction temperature is from room temperature to about 90C and most preferably, from about 40C to about 80C.
In general, the diphenylmethane diisocyanates usable according to the instant invention must contain at least 15 percent by weight of the 2,4'-isomer. While theoretically, there is no upper limit to the amount of 2,4'-isomer which could be present in the isocyanate, as a practical matter, due to a~aila~ility in the present day isocyanate market, it is generally not possible to have the 2,4'-isomer content in excess of 70 percent. Thus, as a practical rule, the diphenyl-methane diisocyanates used according to the instant invention will contain from about 15 to about 70 percent by weight of the 2,4'-isomer with the balance being the 4,4'-isomer and
~q3 ~ PU-0~1 LOW-TEMPERATURE STORAGE STABLE
LIQUID DIP~IENYLMETHANE D~ISOCYANATES
BACKGROUND OF THE INVENTION
It is well known that diisocyanates which are liquid at room temperature (i.e., about 25C) have numerous advantages over solid diisocyanates because they are easier to mix and work with. However, diisocyanates which are liquid at room temperature and which are used on a large technical scale, such as toluene diisocyanate or hexamethylene diisocyanate, are as a rule physiologically harmful due to their high vapor pressure and therefore can only be used if certain safety precautions are taken. For this reason, various attempts have been made, either to start with diisocyanates that are nor-mally liquid at room temperature and to reduce their physiological effects by certain procedures or to start with diisocyanates that are solid at room temperature and to convert these into liquid form. In both cases, however, one usually obtains either isocyanates of higher valency, i.e., tri- or polyisocyanates or higher molecular weight diisocyanates or a combination of these effects.
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 re-spectively. Attempts have already been made to liquify boththe 4,4'-diphenylmethane diisocyanate and a mixture of the 4,4'-diphenylmethane diisocyanate and a small amount of the 2,4'-isomer. Thus, for example, in U. S. Patent 3,644,457, l mol of a diphenylmethane diisocyanate is reacted with from about 0.1 to about 0.3 mols o~ poly-1,2-propylene ether glycol.
3~
While the products made according to this pa-tent have met with commercial success, they still suffer from a serious drawback.
Specifically, it has been found that these adducts generally will crystallize anywhere from 5C to as high as 25C. In fact, when supplied in commercial quantities, these adducts are generally transported in heated trucks. Additionally, in order to thaw the materials, it is generally necessary to heat them to somewhere in exc~ss of 50 to 60~C. While in warmer climates, there may not be any problem, in colder areas where the product may be stored in tanks over a period of time, this tendency to crystallize can become a very serious problem. Similar attempts to form liquid diphenylmethane diisocyanates have been described for example, in U. SO Patents 3,384,653 and 3,394,164. The attempts to liquify in both of these instances were based on the addition of, in one case, a trihydrocarbyl phosphate, and, in the other case, small amounts of phosphoric acid. In any event, the storage stability of both of these types of products is again quite good around room temperature, but as the temper-ature decreases, both types of materials tend to crystallize.
It is therefore an object of this invention to pro-vide improved liquid organic diisocyanates which are liquid and stable at temperatures lower than room temperature. A
further object of this invention is to provide organic di-isocyanates which remain liquid even on prolonged storage at low temperatures.
DESCRIPTION OF THE INVENTION
The instant invention is therefore directed to novel diisocyanate compounds which are both stable and liquid at -5C for at least 48 hours which diisocyanate compound com-prises the reaction product of a diphenylmethane diisocyanate f;~l containin~ at least l5~ by weight o~ the 2,4'-isomer with either propylene glycol or a poly-1,2-propylene ether g]ycol. The materials are reacted in an NCO/OH ratio of from about 3 : 1 to about 15 : 1, preferably from about 3 : 1 to about 10 : 1 and most preferably from about 3 : 1 to about 6 : 1. It has been found that when the most preferable NCO/OH ratio is used, novel diisocyanate compounds are obtained which are both stable and liquid at -22C for twelve (12) weeks.
The glycol and the isocyanate can be reacted at tem-peratures ranging anywhere from room temperature (i.e., about 25) up to 125C. Preferably, the reaction temperature is from room temperature to about 90C and most preferably, from about 40C to about 80C.
In general, the diphenylmethane diisocyanates usable according to the instant invention must contain at least 15 percent by weight of the 2,4'-isomer. While theoretically, there is no upper limit to the amount of 2,4'-isomer which could be present in the isocyanate, as a practical matter, due to a~aila~ility in the present day isocyanate market, it is generally not possible to have the 2,4'-isomer content in excess of 70 percent. Thus, as a practical rule, the diphenyl-methane diisocyanates used according to the instant invention will contain from about 15 to about 70 percent by weight of the 2,4'-isomer with the balance being the 4,4'-isomer and
2,2'-isomer and/or various ~DI dimers (the 2,2'-isomer and any dimer are generally present only in trace amounts, i.e., less than 1 percent by weight). Preferably, the 2,4'-isomer content is fro~l about 20 to about 65 percent by weight and most prefer-ably from about 40 to about 65 percent by weight.
30 The liquid diisocyanates which can be prepared ac-cording to the instant invention have a relatively low vis-9~
cosity and can therefore be worked up very easily, e.g., they can be cast or metered through pumps. In addition, they have a very low vapor pressure and are therefore substantially physiologically harmless Since the reaction can generally 5 be carried out at relatively low temperatures, the diisocyanate structure of the product of the process is completely preserved.
Allophanate formation by the reaction of the resulting urethane groups with the isocyanate group to produce a polyisocyanate ap-parently does not take place to any large degree. This is true 10 even when forming the reaction product at a temperature of 125C.
In addition to propylene glycol, the poly-1,2-propy-lene ether glycols usable in the instant invention include essen-tially any ranging from a molecular weight of 134 (i.e. di-15 propylene glycol) up to molecular weights of about 2000.Specific examples include dipropylene glycol, tripropylene glycols, and various polypropylene glycols.
The process of the instant invention may be carried out by introducing the glycols into the diisocyanate at tem-20 peratures of from room temperature up to about 125C with stir-ring~ Alternatively, the diisocyanate can be introduced into the glycols. The isocyanate content o~ the products of the process generally amounts to from as low as about 10 percent to as high as about 30 percent.
The products o the process can be used for all types of different polyaddition reactions in the lacquer and plastics industries, e.g. for the production of polyurethane foams or polyurethane elastomers which are in turn useful for the preparation of cushions or gear wheels respectively. Because o~ their low Er~ezing point, the materials can be transported and stored at reasonably cold temperatures. In fact, it will be clear from the examples which follow, many of the products of the instant invention do not freeze when stored at -22C
for 12 weeks. Yet a further advantage of the reaction products of the instant invention resides in the fact that even if the products should freeze, they will readily thaw at room temper-ature. This is completely different from the materials dis-closed in U. S. Patent 3,644,457, which upon freezing, must be heated to in excess of 50C.
The invention is further illustrated by the follow-ing examples in which all parts are by weight unless otherwise specified.
.3Lt3~
EXAMPLES
In these eight examples, the diphenylmethane di-isocyanate, having the isomer ratio specified in Table I
were charged to a reactor and heated to 50C. Tripropylene glycol was then added at such a rate that the temperature did not exceed 60C (in some i~stances, cooling was required).
The amount of tripropylene glycol added was such that the NCO/OH ratio was about 4.9 in each instance. After all the tripropylene glycol was added, the reaction mixture was maintained at 60C for about three hours. Samples were then analyzed for viscosity and NCO content and then stored in a freezer for 48 hours at -5C. After the 48 hours storage, the samples were removed from the freezer. Results are set forth in Table I.
TABLE I
Isomer Storage Example Ratio NCO/OH % NCO Viscosity Stability After No. 4,4'/2,4' Ratioby Wt. cps @25C 48 Hours @ -5C
1 100/04.9 22.7 604Completely Solid 2 92/84.9 23.1 656Completely Solid
30 The liquid diisocyanates which can be prepared ac-cording to the instant invention have a relatively low vis-9~
cosity and can therefore be worked up very easily, e.g., they can be cast or metered through pumps. In addition, they have a very low vapor pressure and are therefore substantially physiologically harmless Since the reaction can generally 5 be carried out at relatively low temperatures, the diisocyanate structure of the product of the process is completely preserved.
Allophanate formation by the reaction of the resulting urethane groups with the isocyanate group to produce a polyisocyanate ap-parently does not take place to any large degree. This is true 10 even when forming the reaction product at a temperature of 125C.
In addition to propylene glycol, the poly-1,2-propy-lene ether glycols usable in the instant invention include essen-tially any ranging from a molecular weight of 134 (i.e. di-15 propylene glycol) up to molecular weights of about 2000.Specific examples include dipropylene glycol, tripropylene glycols, and various polypropylene glycols.
The process of the instant invention may be carried out by introducing the glycols into the diisocyanate at tem-20 peratures of from room temperature up to about 125C with stir-ring~ Alternatively, the diisocyanate can be introduced into the glycols. The isocyanate content o~ the products of the process generally amounts to from as low as about 10 percent to as high as about 30 percent.
The products o the process can be used for all types of different polyaddition reactions in the lacquer and plastics industries, e.g. for the production of polyurethane foams or polyurethane elastomers which are in turn useful for the preparation of cushions or gear wheels respectively. Because o~ their low Er~ezing point, the materials can be transported and stored at reasonably cold temperatures. In fact, it will be clear from the examples which follow, many of the products of the instant invention do not freeze when stored at -22C
for 12 weeks. Yet a further advantage of the reaction products of the instant invention resides in the fact that even if the products should freeze, they will readily thaw at room temper-ature. This is completely different from the materials dis-closed in U. S. Patent 3,644,457, which upon freezing, must be heated to in excess of 50C.
The invention is further illustrated by the follow-ing examples in which all parts are by weight unless otherwise specified.
.3Lt3~
EXAMPLES
In these eight examples, the diphenylmethane di-isocyanate, having the isomer ratio specified in Table I
were charged to a reactor and heated to 50C. Tripropylene glycol was then added at such a rate that the temperature did not exceed 60C (in some i~stances, cooling was required).
The amount of tripropylene glycol added was such that the NCO/OH ratio was about 4.9 in each instance. After all the tripropylene glycol was added, the reaction mixture was maintained at 60C for about three hours. Samples were then analyzed for viscosity and NCO content and then stored in a freezer for 48 hours at -5C. After the 48 hours storage, the samples were removed from the freezer. Results are set forth in Table I.
TABLE I
Isomer Storage Example Ratio NCO/OH % NCO Viscosity Stability After No. 4,4'/2,4' Ratioby Wt. cps @25C 48 Hours @ -5C
1 100/04.9 22.7 604Completely Solid 2 92/84.9 23.1 656Completely Solid
3 84/16 4.9 22.8 664 Liquid*
4 76/24 4.9 22.8 695 Liquid 68/32 4.9 22.6 840 Liquid 6 60/40 4.9 22.5 850 Liquid 7 43/57 4.9 22.8 720 Liquid 8 35/65 4.9 22.8 690 Liquid *After an additional 24 hours at -5C, traces of crystals could be observed, but the product was still liquid.
1~3;~ti~33 In order to establish the outstanding storage stabil-ity at even lower temperatures, the products of Examples 6, 7 and 8 were stored in a freezer for 12 (twelve) weeks at -22C.
After this period of time, none of the products crystallized.
After bringing the products back to room temperature, viscosities and ~ NCO were rechecked and found to be unchanged.
-The process of Examples 1 through 8 was followed except that NCO/OH ratios were varied as set forth in Table II while the isomer ratio was kept constant. Tripropylene glycol was again used. Results are set forth in Table II.
After bringing the products back to room temperature, viscosities and % NCO were rechecked and found to be unchanged.
TABLE II
Storage Isomer Stability ExampleRatio NCO/OH % NCO Viscosity After 48 No. 4,4'/2,4' RatioBy Wt.cps @ 25C Hours @ -5C
9 35/65 3.3 18.810,050 Liquid 2010 35/65 4.9 22.8690 Liquid 11 35/65 10.0 28.170 Liquid 12 35/65 15.0 29.735 Liquid The products of Examples 9 through 12 were then stored in a freezer for twelve (12) weeks at -22C. After this period of time, the products of Examples 9 and 10 re-mained liquid while the products of Examples 11 and 12 had crystallized.
The process of Examples 9 through 12 was followed using an NCO/OH ratio of about 4.9, but using various reaction temperatures, and heated for the time specified in Table III.
The temperature times of reaction and results were as set forth in Table III.
TABLE III
Viscos- Storage Isomer ity Stability Example Ratio Reaction % NCO cps After 48 No. 4,4'/2,4' Temp. &/Time Hr. By Wt. @ 25C Hours @ -5C
13 35/65 Rt(25C)/14 Hr. 23.2 760 Liquid 14 35/65 50/8 Hr. 23.1 700 Liquid 35/65 60/3 Hr. 22.8 ~690 Liquid 16 35/65 100/1 Hr. 22.9 840 Liquid 17 35/65 120/0.5 Hr. 22.8 960 Liquid After storage in a freezer for 12 (twelve) weeks at -22C, none of the products had crystallized.
The process of Examples 1 through 8 was repeated using various ~CO/OH ratios, various propylene glycols and an isomer ratio of 35/65 (4,4'/2,4'). The variables were as set forth in Table IV.
- TABLE IV
Storage Viscos- Stability ity After
1~3;~ti~33 In order to establish the outstanding storage stabil-ity at even lower temperatures, the products of Examples 6, 7 and 8 were stored in a freezer for 12 (twelve) weeks at -22C.
After this period of time, none of the products crystallized.
After bringing the products back to room temperature, viscosities and ~ NCO were rechecked and found to be unchanged.
-The process of Examples 1 through 8 was followed except that NCO/OH ratios were varied as set forth in Table II while the isomer ratio was kept constant. Tripropylene glycol was again used. Results are set forth in Table II.
After bringing the products back to room temperature, viscosities and % NCO were rechecked and found to be unchanged.
TABLE II
Storage Isomer Stability ExampleRatio NCO/OH % NCO Viscosity After 48 No. 4,4'/2,4' RatioBy Wt.cps @ 25C Hours @ -5C
9 35/65 3.3 18.810,050 Liquid 2010 35/65 4.9 22.8690 Liquid 11 35/65 10.0 28.170 Liquid 12 35/65 15.0 29.735 Liquid The products of Examples 9 through 12 were then stored in a freezer for twelve (12) weeks at -22C. After this period of time, the products of Examples 9 and 10 re-mained liquid while the products of Examples 11 and 12 had crystallized.
The process of Examples 9 through 12 was followed using an NCO/OH ratio of about 4.9, but using various reaction temperatures, and heated for the time specified in Table III.
The temperature times of reaction and results were as set forth in Table III.
TABLE III
Viscos- Storage Isomer ity Stability Example Ratio Reaction % NCO cps After 48 No. 4,4'/2,4' Temp. &/Time Hr. By Wt. @ 25C Hours @ -5C
13 35/65 Rt(25C)/14 Hr. 23.2 760 Liquid 14 35/65 50/8 Hr. 23.1 700 Liquid 35/65 60/3 Hr. 22.8 ~690 Liquid 16 35/65 100/1 Hr. 22.9 840 Liquid 17 35/65 120/0.5 Hr. 22.8 960 Liquid After storage in a freezer for 12 (twelve) weeks at -22C, none of the products had crystallized.
The process of Examples 1 through 8 was repeated using various ~CO/OH ratios, various propylene glycols and an isomer ratio of 35/65 (4,4'/2,4'). The variables were as set forth in Table IV.
- TABLE IV
Storage Viscos- Stability ity After
5 Example NCO/OH %NCO cps 48 Hours No. Glycol Used Ratio By Wt. @ 25C @ -5~C
18 1,2-Propylene Gly- 4.924.8 710 Liquid col MW 76 19 Dipropylene Glycol 4.923.9 810 Liquid Tripropylene Gly-col MW 192 4.9 22.9690 Liquid 21 Polypropylene Gly-col A~g. MM 150 4.9 23.7655 Liquid : 15 22 Polypropylene Gly-~ col Avg. MM 446 4.9 20.0920 Liquid : : 23 Polypropylene Gly-;~ col Avg. MW 1000 4.914.7 2080 Liquid 24 Polypropylene Gly-~: 20 col Avg. MW 2000 4.910.0 3260 Liquid Polypropylene Gly~
col Avg. MW 1000 1021.6 190 Liquid 26 Polypropylene Gly-col Avg. MM 2000 1016.7 500 Liquid : 25 27 Polypropylene Gly-: col Avg. MW 2000 1520.4 190 Liquid The products of Examples 18 through 22, 25, 26 and 27 were then stored in a freezer for twelve (12) weeks at -22C. After this period of time, the products of Examples 18 through 22 remained liquid, while the products of Examples 25, 26 and 27 had crystallized.
It is to be understood that the foregoing examples are given for the purpose of illustration and that various other materials within the definition of the claims could be used. Although the invention has been described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations PU-041 ~9~
~ 3~ ~ 3 can be made therein by those skilled in the art without de-parting from the spirit and scope of the invention except as it may be limited by the claims.
18 1,2-Propylene Gly- 4.924.8 710 Liquid col MW 76 19 Dipropylene Glycol 4.923.9 810 Liquid Tripropylene Gly-col MW 192 4.9 22.9690 Liquid 21 Polypropylene Gly-col A~g. MM 150 4.9 23.7655 Liquid : 15 22 Polypropylene Gly-~ col Avg. MM 446 4.9 20.0920 Liquid : : 23 Polypropylene Gly-;~ col Avg. MW 1000 4.914.7 2080 Liquid 24 Polypropylene Gly-~: 20 col Avg. MW 2000 4.910.0 3260 Liquid Polypropylene Gly~
col Avg. MW 1000 1021.6 190 Liquid 26 Polypropylene Gly-col Avg. MM 2000 1016.7 500 Liquid : 25 27 Polypropylene Gly-: col Avg. MW 2000 1520.4 190 Liquid The products of Examples 18 through 22, 25, 26 and 27 were then stored in a freezer for twelve (12) weeks at -22C. After this period of time, the products of Examples 18 through 22 remained liquid, while the products of Examples 25, 26 and 27 had crystallized.
It is to be understood that the foregoing examples are given for the purpose of illustration and that various other materials within the definition of the claims could be used. Although the invention has been described in detail for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations PU-041 ~9~
~ 3~ ~ 3 can be made therein by those skilled in the art without de-parting from the spirit and scope of the invention except as it may be limited by the claims.
Claims (22)
1. A diisocyanate compound which is both stable and liquid at -5°C for at least 48 hours, comprising the reaction product of:
(a) a diphenylmethane diisocyanate containing at least 15 percent by weight of the 2,4'-isomer, and (b) a material selected from the group consist-ing of propylene glycol and poly-1,2-propylene ether glycols.
(a) a diphenylmethane diisocyanate containing at least 15 percent by weight of the 2,4'-isomer, and (b) a material selected from the group consist-ing of propylene glycol and poly-1,2-propylene ether glycols.
2. The compound of Claim 1 wherein said diphenyl-methane diisocyanate comprises (a) from about 15 to about 70 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
3. The compound of Claim 2, wherein said diphenyl-methane diisocyanate comprises:
(a) from about 20 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
(a) from about 20 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
4. The compound of Claim 3, wherein said diphenyl-methane diisocyanate comprises:
(a) from about 40 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
(a) from about 40 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
5. The compound of Claim 2, wherein components (a) and (b) are used in such quantities that the NCO/OH ratio is from about 3:1 to about 15:1.
6. The compound of Claim 5, wherein said ratio is from about 3:1 to about 10:1.
7. The compound of Claim 6, wherein said ratio is from about 3:1 to about 6:1.
8. The compound of Claim 2, wherein said poly-1,2-propylene ether glycols have molecular weights of from 134 to about 2000.
9. The compound of Claim 1, wherein components (a) and (b) are used in such quantities that the NCO/OH ratio is from about 3:1 to about 15:1.
10. The compound of Claim 9, wherein said ratio is from about 3:1 to about 10:1.
11. The compound of Claim 10, wherein said diphenyl-methane diisocyanate comprises:
(a) from about 20 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
(a) from about 20 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
12. The compound of Claim 10, wherein said ratio is from about 3:1 to about 6:1.
13. The compound of Claim 12, wherein said diphenyl-methane diisocyanate comprises (a) from about 40 to about 65 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
14. The compound of Claim 12, wherein said poly-1,2-propylene ether glycols have molecular weights of from 134 to about 2000.
15. The compound of Claim 9, wherein said poly-1,2-propylene ether glycols have molecular weights of from 134 to about 2000.
16. A process for the production of diisocyanate compounds which are both stable and liquid at -5°C for at least 48 hours which comprises reacting:
(a) a diphenylmethane diisocyanate containing at least 15 percent by weight of the 2,4'-isomer, and (b) a material selected from the group consist-ing of propylene glycol and poly-1,2-propylene ether glycols.
(a) a diphenylmethane diisocyanate containing at least 15 percent by weight of the 2,4'-isomer, and (b) a material selected from the group consist-ing of propylene glycol and poly-1,2-propylene ether glycols.
17. The process of Claim 16, wherein said components (a) and (b) are reacted at a temperature of from room temper-ature to about 125°C.
18. The process of Claim 17, wherein said diphenyl-methane diisocyanate comprises (a) from about 15 to about 70 percent by weight of the 2,4'-isomer, and the balance being (b) the 4,4'-isomer.
19. The process of Claim 18, wherein components (a) and (b) are used in such quantities that the NCO/OH ratio is from about 3:1 to about 15:1.
20. The process of Claim 19, wherein said poly-1,2-propylene ether glycols have molecular weights of from 134 to about 2000.
21. The process of Claim 20, wherein said components (a) and (b) are reacted at a temperature of from room tempera-ture to about 90°C.
22. The process of Claim 21, wherein said components (a) and (b) are reacted at a temperature of from about 40°C to about 80°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US766,997 | 1977-02-09 | ||
| US05/766,997 US4118411A (en) | 1977-02-09 | 1977-02-09 | Low-temperature storage stable liquid diphenylmethane diisocyanates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091683A true CA1091683A (en) | 1980-12-16 |
Family
ID=25078168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA295,846A Expired CA1091683A (en) | 1977-02-09 | 1978-01-27 | Low-temperature storage stable liquid diphenylmethane diisocyanates |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4118411A (en) |
| JP (1) | JPS5398942A (en) |
| BE (1) | BE863752A (en) |
| CA (1) | CA1091683A (en) |
| DE (1) | DE2804375A1 (en) |
| FR (1) | FR2380309A1 (en) |
| GB (1) | GB1572781A (en) |
| IT (1) | IT1104604B (en) |
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| DE3042821A1 (en) * | 1980-11-13 | 1982-06-09 | Bayer Ag, 5090 Leverkusen | METHOD FOR SEALING CONSTRUCTIONS |
| US4321333A (en) * | 1981-04-16 | 1982-03-23 | The Upjohn Company | Polyurethane prepared from polyisocyanate blend |
| CA1178603A (en) * | 1981-05-22 | 1984-11-27 | William E. Slack | 2,2,4,4-tetraalkyl-1,3-cyclobutanediol modified diphenylmethane diisocyanate |
| DE3216363A1 (en) * | 1982-05-03 | 1983-11-03 | Basf Ag, 6700 Ludwigshafen | METHOD FOR GLUING LIGNOCELLULOSE-CONTAINING RAW MATERIALS WITH A PRAEPOLYMER BASED ON A URETHANE-MODIFIED DIPHENYLMETHANDIISOCYANATE MIXTURE |
| US4383070A (en) * | 1982-05-27 | 1983-05-10 | Mobay Chemical Corporation | Storage stable polyurethane compositions |
| FR2545083B1 (en) * | 1983-04-29 | 1987-07-17 | Ugine Kuhlmann | LIQUID COMPOSITION, CONTAINING DIPHENYLMETHANE STRUCTURED DIISOCYANATES, AND PROCESS FOR PRODUCING THE SAME |
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| CA2117741A1 (en) * | 1993-10-28 | 1995-04-29 | Michael F. Hurley | Rim process utilizing isocyanates based upon 2,4'-and 4,4'- diphenylmethane diisocyanate |
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| US6844390B2 (en) * | 2001-04-09 | 2005-01-18 | Eastman Chemical Company | Modified alkyd compositions comprising polyol latex compositions and processes of making them |
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| KR20090077010A (en) * | 2006-11-01 | 2009-07-13 | 다우 글로벌 테크놀로지스 인크. | Polyurethane compositions and articles prepared therefrom, and methods for making the same |
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| 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 |
| KR20120050412A (en) | 2009-06-18 | 2012-05-18 | 다우 글로벌 테크놀로지스 엘엘씨 | Color-stable, halogen-free flame retardant compositions |
| CN102686665B (en) * | 2009-11-12 | 2014-04-02 | 科腾聚合物美国有限责任公司 | Thermoplastic polyurethane block copolymer compositions |
| DE102011089783A1 (en) * | 2011-12-23 | 2013-06-27 | Bayer Materialscience Aktiengesellschaft | Low viscosity reactive polyurethane compositions |
| WO2021204618A1 (en) | 2020-04-07 | 2021-10-14 | Covestro Deutschland Ag | Cold-stable nco prepolymers, method for the preparation and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3362979A (en) * | 1964-01-02 | 1968-01-09 | Jefferson Chem Co Inc | Mixtures of methylene-bridged polyphenyl polyisocyanates |
| US3394164A (en) * | 1965-10-24 | 1968-07-23 | Upjohn Co | Stabilized methylenebis-(phenyl isocyanate) compositions |
| US3394165A (en) * | 1965-10-24 | 1968-07-23 | Upjohn Co | Stabilized methylenebis-(phenyl isocyanate) compositions |
| 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 |
| NL178871C (en) * | 1972-09-26 | Ici Ltd | PROCESS FOR PREPARING A LIQUID DIPHENYLMETHANE DIISOCYANATE PRODUCT AND FOR PREPARING OR MANUFACTURING A POLYURETHANE USING SUCH ISOCYANATE PRODUCT. |
-
1977
- 1977-02-09 US US05/766,997 patent/US4118411A/en not_active Expired - Lifetime
-
1978
- 1978-01-27 CA CA295,846A patent/CA1091683A/en not_active Expired
- 1978-02-02 DE DE19782804375 patent/DE2804375A1/en not_active Withdrawn
- 1978-02-07 JP JP1203578A patent/JPS5398942A/en active Pending
- 1978-02-07 IT IT47947/78A patent/IT1104604B/en active
- 1978-02-08 BE BE184990A patent/BE863752A/en not_active IP Right Cessation
- 1978-02-09 GB GB5235/78A patent/GB1572781A/en not_active Expired
- 1978-02-09 FR FR7803698A patent/FR2380309A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB1572781A (en) | 1980-08-06 |
| US4118411A (en) | 1978-10-03 |
| JPS5398942A (en) | 1978-08-29 |
| IT1104604B (en) | 1985-10-21 |
| FR2380309A1 (en) | 1978-09-08 |
| BE863752A (en) | 1978-08-08 |
| DE2804375A1 (en) | 1978-08-10 |
| FR2380309B1 (en) | 1984-11-23 |
| IT7847947A0 (en) | 1978-02-07 |
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