POLYCARBAMATES, PROCESS FOR PREPARING POLYCARBAMATES, AND PROCESS FOR PREPARING POLYISOCYANATES

Abstract: Polycarbamates of a polyisocyanate and secondary alcohols are disclosed. These carbamates are characterized in being readily pyrolyzed to form the corresponding polyisocyanate and alcohol with low formation of tars and other by-products. Thus, these polycarbamates can be pyrolyzed under relatively mild conditions, and in the absence of solvent and catalyst.

Description: POLYCARBAMATES, PROCESS FOR PREPARING POLYCARBAMATES, AND PROCESS FOR PREPARING POLYISOCYANATES This invention relates to a process for preparing polyisocyanates such as are useful, for example, in making polyurethane polymers. Polyisocyanates are commonly used in various applications, the most common of which is the preparation of polyurethane polymers. The most commercially important of these are aromatic polyisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and the so-called polymeric MDI products which are usually formed as by-products in MDI production. However, certain aliphatic polyisocyanates are also used commercially, such as hexamethylene diisocyanate, isophorone diisocyanate and hydrogenated MDI (H 12 MDI). On a commercial scale, polyisocyanates are almost universally produced by reacting the corresponding polyamine with phosgene. For example, TDI is produced by reacting phosgene with toluene diamine. Several problems are associated with this process, the most significant of which is that large quantities of phosgene must be handled Phosgene is highly toxic, and its handling requires special care to prevent exposure to workers. HCI is produced in the reaction of the phosgene and the polyamine, and must be neutralized or otherwise removed. The phosgene and HCI also engage in various side reactions, producing unwanted chlorinated by-products which affect the quality and purity of the product polyisocyanates. Thus, a process by which polyisocyanates can be prepared without using phosgene would be highly desirable Several non-phosgene routes to polyisocyanates have been developed One such route involves the preparation of an n-alkyl biscarbamate, which is subsequently pyrolyzed to form the corresponding polyisocyanate and alcohol. The biscarbamate is generally prepared by one of two methods. The first such method involves the oxidative carbonylation of an amine with carbon monoxide, oxygen and an alcohol such as ethanol or methanol, to form the corresponding ethyl- or methylcarbamate. The other method involves a reductive carbonylation of a nitro compound with carbon monoxide and an alcohol such as ethanol or methanol to form the corresponding ethyl- or methylcarbamate. See, for example, WO 86-05179. In these processes, the ethyl- or methyl polycarbamates are pyrolyzed at high temperatures and under reduced pressures. At these temperatures, the polyisocyanates often polymerize as they form, producing tars and other by-products. For this reason, and because these carbamates are often crystalline, a solvent is required as a diluent The use of a solvent in the pyrolysis adds costs in recovering the product polyisocyanate from the solvent. To a lesser extent, the high temperature required further increases the cost of these processes. Thus, it would be desirable to provide a route to make polyisocyanates through a polycarbamate intermediate, wherein the pyrolysis of the polycarbamate can be conducted in the absence of solvent, and preferably at moderate temperatures. In one aspect this invention is a polycarbamate as represented by the structure (I) wherein b is a number of two or more, R is an organic radical with a valence equal to b, Y is a group having at least two carbon atoms, and Z is an aliphatic or aromatic group containing at least one carbon atom. In another aspect, this invention is a process for preparing a polyisocyanate, comprising pyrolyzing the polycarbamate of the first aspect under reduced pressure and at a temperature of 150 to 270°C, to form the corresponding polyisocyanate and alcohol. In a third aspect, this invention is a process for preparing a polyisocyanate, comprising forming a polycarbamate of the first aspect, and then pyrolyzing the polycarbamate under reduced pressure and at a temperature of 150 to 270°C, to form the corresponding polyisocyanate and alcohol. In a fourth aspect, this invention is a process for preparing a polycarbamate comprising reacting a polycarbamate represented by the structure (II) wherein A is C e linear alkyl with a secondary alcohol represented by the structure Z-CH(OH)-Y, at an elevated temperature such that the polycarbamate represented by structure (I) and an alcohol of the structure A-OH are formed, and wherein the alcohol A-OH is removed from the product polycarbamate continuously or intermittently as it forms. Unexpectedly, the polycarbamate of this invention can be pyrolyzed to form the corresponding polyisocyanate under surprisingly mild conditions, compared to those required to pyrolyze ethyl- or methyl polycarbamates. Thus, the pyrolysis can be conducted at lower temperatures than required to pyrolyze ethyl- or methyl polycarbamate, and also can be conducted neat and without solvent. In addition, the polycarbamates can be pyrolyzed in the substantial absence of solvent with greatly reduced formation of tar and other by-products, compared to those formed in the neat pyrolysis of ethyl- or methyl polycarbamates. Since no solvents are needed, the isolation of the isocyanate and the alcohol can be greatly simplified. : The polycarbamate of this invention is a compound represented by the structure wherein b is a number of two or more, R is a organic radical with a valence equal to b, Y is a a group having at least two carbon atoms, and Z is an aliphatic or aromatic group containing at least one carbon atom. • 5 In structure (I), "b" is preferably a number from two to four, more preferably from two to three, most preferably two. "R" is preferably a hydrocarbon radical, which may be aliphatic, alicyclic, or aromatic. Suitable aliphatic hydrocarbon radicals include straight chain or branched hydrocarbons having from two, preferably from 4 carbon atoms, to 20, preferably 12, more 20 preferably 8 carbon atoms. Most preferred are linear hydrocarbon diradicals having from 4 to 8 carbon atoms. Examples of such include tetramethylene, pentamethylene, hexamethylene, and octamethylene diradicals. Suitable alicyclic hydrocarbon radicals include monocyclic and polycyclic hydrocarbons, preferably monocyclic hydrocarbons having from 6 to 16 carbon atoms. Among these preferred alicyclic hydrocarbon radicals are cyclohexane, alkyl-substituted 25 cyclohexane, isophorone dialkyl-substituted cyclohexane, mono- or dihalo-substituted cyclohexane, cyclooctane, alkyl-substituted cyclooctane, dialkyl-substituted cyclooctane, mono- or dihalo-substituted cyclooctane, bis(cyclohexyl)alkanes such as methylene bis(cyclohexane) and propylidene bis(cyclohexane), and like radicals. Suitable aromatic polyradicals include polyradicals of benzene, toluene and other monoalkyl benzenes, o-, p-, and m-xylene and 30 other dialkyl benzenes, diphenylalkanes such as diphenyl methane and 2,2-diphenylpropane, and halogenated aromatics. Most preferred R radicals are hexamethylene, phenylene, diphenylmethane, toluene, cyclohexane, xylenyl, methylcyclohexane, isophorone and dicyclohexylmethane radicals. 35 in structure (I), exemplary "2" groups include linear or branched alkyl, cycloalkyl, alkoxy-substituted alkyl, benzyl, phenyl or other aromatic group, which may be substituted, and like groups. Preferred Z groups include C 1 -C4 straight chain alkyl, C3-C6 branched alkyl, alkyl ether, phenyl and benzyl. More preferably, the Z group is methyl, ethyl, C3-C6 secondary alkyl, C4-C6 tertiary alkyl, phenyl or benzyl. Exemplary Y groups include those having from 2 to 20, preferably 3 to 6 carbon atoms, and are represented by the structure -CR1R2R3 wherein R 1 and R2 are hydrogen, C C6 alkyl, aromatic, benzyl, alkoxy or phenoxy and R3 is C Cβ alkyl, aromatic, benzyl, alkoxy, phenoxy or dialkylamine. R 1 is preferably hydrogen, C β alkyl or phenyl. R2 is preferably Ci-Cβ alkyl, phenyl or C1-C alkoxy. If R1 and R2 are both hydrogen, R3 may be C ε alkyl, phenyl, alkoxy, phenoxy or dialkylamine, but in that case it is preferred that 3 is C1-C4 alkoxy or phenoxy, more preferably methoxy or ethoxy. Otherwise, R3 is preferably C1-C4 alkyl, phenyl or C C 2 alkoxy, more preferably methyl, ethyl, methoxy or ethoxy. Of particular interest are Y groups in which R 1 and R 2 are hydrogen and R3 is ethoxy or methoxy; R 1 and R 2 are hydrogen and R 3 is methyl, ethyl or phenyl; R > is hydrogen and R2 and R 3 are each methyl, ethyl or phenyl; R 1 is hydrogen, 2 is methyl, ethyl or phenyl and R3 is methoxy or ethoxy; R 1 and R 2 are both methyl, ethyl or phenyl and R 3 is methoxy or ethoxy; and R 1 , R2 and R 3 are all methyl or ethyl. The polycarbamate of this invention can be prepared in a transesterification reaction involving a polycarbamate as represented by the structure and an alcohol having the structure Z-CH(OH)-Y, wherein R, b, Y, and Z are as defined before and A is C1-C4 linear alkyl, preferably ethyl or methyl. The transesterification reaction is conducted at an elevated temperature. In general, a temperature from 50 to 250°C can be used, with faster reaction occurring at higher temperatures. As the reaction proceeds, an alcohol corresponding to the formula A-OH is produced. In order to drive the transesterification to completion, it is preferred to remove the alcohol A-OH from the product as the alcohol is formed. A simple way to accomplish this is to vent alcohol vapors. For this reason, it is preferred to conduct the reaction at a temperature above the boiling point of the alcohol A-OH. The preferred temperature also depends on whether a catalyst is used to enhance the rate of the transesterification reaction. When a catalyst is used, it is preferred to use a moderate temperature, that is from 50 to 150°C. When no catalyst is used, a temperature of from 100 to 250°C is preferred. The transesterification reaction may be run in the presence of a diluent. The diluent advantageously has a boiling point in the temperature range at which the transester- ification reaction is conducted, and the reaction is conducted under reflux conditions. The diluent may be any liquid in which the starting and product polycarbamates do not undesirably react. Suitable such diluents include aromatic solvents such as toluene and benzene, ethyl acetate, methylene chloride, acetone, and preferably the alcohol A-OH such as is formed during the transesterification reaction. Preferred solvents are those such as toluene, benzene and ethyl acetate which facilitate removal of the alcohol A-OH from the reaction mixture. As mentioned before, a catalyst may be used in the transesterification reaction. Suitable catalysts include organometallic catalysts such as organotin, organotitanium, organomercury, organobismuth and similar compounds, with organotin compounds and titanium (IV) compounds being preferred. Suitable organotin compounds include those commonly employed as polyurethane catalysts, including, for example, tin octoate and dialkyl tin dialkanoates such as dimethyltin dilaurate and dibutyltin dilaurate. A suitable titanium (IV) compound is titanium (IV) isopropoxide. Conventional transesterification catalysts such as acids and bases can also be used. Exemplary acids include toluene sulfonic acid, sulfuric acid, and methanesulfonic acid. Exemplary bases include trialkyl amines and alkali metal alkoxides such as sodium or potassium methoxide. The transesterification is conducted by contacting the polycarbamate starting material with the alcohol Z-CH(OH)-Y and heating them to a temperature as described above. An excess of the alcohol is preferably used in order to drive the reaction to completion. The catalyst, if used, is advantageously present in an amount from 0.01 to 5, preferably 0.1 to 1 weight percent, based on the weight of the starting polycarbamate. Product alcohol A-OH is preferably removed from the reaction mixture as it is formed, in order to drive the equilibrium towards the product polycarbamate. The alcohol Z-CH(OH)-Y can also be replenished as it is consumed, for the same reason. Depending on the temperature used, the reaction proceeds to 90 percent or higher yield in a period of 1 to 30 hours. After the reaction, it is preferred to work up the product polycarbamate by stripping off volatile impurities and removing residual catalyst and starting polycarbamate though a suitable technique such as solvent extraction or recrystallization. The starting polycarbamate can itself be prepared in an oxidative or reductive carbonylation of a polyamine of the formula R-NH2t>, wherein R and b are as defined before. Such processes are described, for example, in Japanese Patent (Kokai) Nos. 57-158746-48, 57- 70855, 57-185253, and 57-188557. The oxidative carbonylation is advantageously carried out using carbon monoxide, oxygen and an ethanol (to make the polyethylcarbamate) or methanol (to make the polymethylcarbamate). The reductive carbonylation is advantageously carried out using carbon monoxide and methanol or ethanol, preferably in the presence of a ruthenium catalyst. In either case, the carbonylation is carried out at an elevated temperature and pressure in the presence of an excess of the methanol or ethanol. A third process for preparing the starting polycarbamate is to oxidatively carbonylate a monoamine or reductive carbonylate a mononitro compound using ethanol or methanol to form a monocarbamate, followed by a coupling of the monocarbamate to form a polycarbamate. This method is particularly suitable for preparing polyaromatic carbamates. For example, a monocarbamate prepared from aniline or nitrobenzene can be coupled via condensation with an aldehyde or ketone to form an alkylene bis- or poly(phenyl carbamate). 1 o In such case, the monocarbamate is preferably the methyl or ethyl carbamate of aniline, and the ketone is preferably formaldehyde. The polycarbamate of this invention can then be pyrolyzed to form the corresponding polyisocyanate. A significant advantage of this invention is that the pyrolysis of these polycarbamates is readily accomplished without the need for solvent or catalyst. In 5 addition, the polycarbamates of this invention form fewer polymeric and tarry by-products upon pyrolysis than do corresponding n-alkyl polycarbamates. The polycarbamates of this invention are advantageously decomposed into the corresponding polyisocyanate and alcohol by heating at a temperature from 130°C, preferably from 150°C, more preferably from 175°C, to 300°C, preferably to 270°C, more preferably to 20 250°C, most preferably to 230°C. It is preferred to select a temperature at which the alcohol and the polyisocyanate, which are formed in the pyrolysis, are distilled as they are formed so that an equilibrium between the carbamate and polyisocyanate is not created. It is especially preferred that the temperature be such that both the alcohol and the polyisocyanate, which are formed in the reaction, distill from the reaction mixture as they are formed. 25 A subatmospheric pressure is preferred in the pyrolysis reaction, preferably from 0.01 to 50 and especially from 0.1 to 5.0 torr, since this facilitates distillation of the alcohol and the polyisocyanate from the reaction mixture. Although a solvent is not required during the pyrolysis step, one may be used if required. Any solvent can be used which dissolves the polycarbamate, is inert during the 30 pyrolysis and is thermally stable at the temperature used in the pyrolysis reaction. Examples of such solvents include diphenyl oxide, alkylbenzenes, dialkylbenzenes, and secondary alcohols. In a preferred method, the polycarbamate is first heated to a relatively mild temperature, preferably 50 to 100 C C, and maintained at that temperature until the alcohol no longer distills off. This initial heating step is preferably done under vacuum. During this step, a 35 polymeric residue often forms which is believed to contain allophanates and/or polyurethanes. This polymeric residue is then pyrolyzed at higher temperatures, as described above, to recover the polyisocyanate and additional alcohol. The resulting polyisocyanate can be distilled or otherwise purified if needed. The polyisocyanate prepared in accordance with this invention is useful to prepare polyurethanes, polyureas, polyisocyanu rates, polyamides, polyimides and like polymers. Process for preparing these types of polymers from polyisocyanates are well-known and described, for example, in U.S. Patent Nos. 4,876,019, 4,929,646 and 5,010,1 17, all incorporated herein by reference. Examples The following examples are provided to illustrate the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise 0 indicated. Example 1 Into a Parr reactor equipped with a vapor phase outlet and a liquid inlet were placed 31.47 parts diphenylmethane dimethyl biscarbamate (MDI dimethyl biscarbamate) and 15 200 parts 1-methoxy-2-propanol. The mixture was heated to about 220°Cwith stirring to initiate the transesterification reaction. As the reaction proceeded, about 13 parts per hour of methanol-rich vapor phase was bled from the reactor, and 13 parts per hour of 1-methoxy-2- propanol were added. After about 5 hours, the MDI dimethyl biscarbamate was totally consumed. The product mixture contained 93.4 percent of the MDI di(1-methoxy isopropyl) 20 biscarbamate, and 5.6 percent of an MDI methyl(l-methyoxyisopropyl) biscarbamate. Example 2 Into a suitable flask equipped with a condenser were placed 68.4 parts diphenylmethane diethyl biscarbamate (MDI diethyl biscarbamate), 180 parts 1-methoxy-2- 25 propanol and 0.5 part dibutyltin dilaurate. The resulting mixture was heated to a temperature ranging from 125 to 145°C. Methanol was removed from the system as the reaction proceeded. After 72 hours, no MDI diethyl biscarbamate remained. The contents of the reaction flask were concentrated and 81.8 parts of MDI di(1-methoxy isopropanol) biscarbamate were obtained. 30 Example 3 Example 2 was repeated, except that the starting biscarbamate was 62.8 parts of MDI dimethyl biscarbamate. The product contained 80.3 parts of MDI di(1-methoxy isopropanol) biscarbamate. 35 Example 4 Example 2 was again repeated, this time substituting 0.9 g titanium (IV) isopropoxide for the dibutyltin dilaurate. After 72 hours reaction, 79.5 parts of MDI di(1- methoxy isopropanol) biscarbamate were obtained. Example 5 Into a distillation flask equipped with a heating mantle was charged a mixture of 18.8 g 1-methoxy-2-propanol and 43.2 g of a biscarbamate as represented by the structure (MDI di(1-methoxy isopropanol) biscarbamate): The mixture was heated under full vacuum to a temperature of less than 100°C, and 22.6 grams of the 2-hydroxy-3-methoxypropane distilled off. This distillate was recovered in a cold trap. The material remaining in the distillation flask had a resinous appearance and appeared to include an allophanate or polyurethane formed from the biscarbamate. In a second stage, the distillation flask was then heated to a temperature of 180 to 220°C, and a mixture of isocyanates and 1-methoxy-2-propanol began to distill. The temperature of the distillate was 140 to 180°C. The isocyanates condensed separately from the 1-methoxy-2- -propanol and were recovered in a condensation flask upstream of the cold trap where the 1- methoxy-2-propanol was condensed. The isocyanates distilled from this had an NCO content of 22.4 percent, representing approximately 48 percent MDI and 52 percent of the monocarbamate. The distillation was continued until the distillation flask was empty except for a tarry residue which did not further decompose or distill. This residue was recovered and found to weigh 1.6 g, which represented 4 percent of the initial mixture of biscarbamate and 2- hyd roxy-3-methoxypropane. A total of 21.3 g of a crystalline polyisocyanate containing 22 percent NCO groups was recovered. Atotal of 39.5 grams of 1-methoxy-2-propanol was recovered. This amount represented over 100 percent of theoretical, but upon examination it was seen that some MDI was present in the alcohol. The isocyanates (20 g) recovered from the preceding pyrolysis were pyrolyzed a second time under the same conditions. The distillate obtained from this second pyrolysis had an NCO content of 32 percent, representing approximately 92 percent MDI and 8 percent monocarbamate. A tarry residue weighing only 0.3 g remained in the pyrolysis flask. Examples 6-7 and Comparative Sample A A series of MDI bi sea rba mates was pyrolyzed using the apparatus described in Example 5. In all cases, the pyrolysis was run under the same conditions as described in Example 5. The weight of the starting biscarbamate, the recovered isocyanates, the recovered alcohol and tarry residue were as reported in Table 1. TABLE 1 WT. WT. WT. Sample MDI WT. TAR, g BISCARBAMATE, ISOCYANATE, ALCOHOL No. BISCARBAMATE (%)© g g 9 6 Di-3,3-dimethyl-2- 75.2 33.7 33.2 4.5 (5.9%) butyl 7 Di-1-methoxy-2- 27.8 13.0 13.2 0.7 (2.5%) propyl A* Diethyl 30.2 5.3 10.2 13.7 (45.4%) ©Based on the weight of the MDI biscarbamate starting material. * - Not an example of the invention. As can be seen from the data in Table 1, the biscarbamates of this invention (Samples 6 and 7) formed minimal tar when pyrolyzed in the absence of solvent. On the other hand, almost half of the MDI diethylbiscarbamate formed a tarry residue under these conditions. Example 8 TDI di-1-methoxy-2-propyl biscarbamate (48.4 g), having the structure was pyrolyzed in an apparatus similar to that described in Example 8, at 180-250°C under 1 mm Hg vacuum. A distillate was collected at 150-160°C, weighing 34.5 g and having an NCO content of 17.2 percent. In a separate dry ice trap, 12.9 g of 1-methoxy-2-propanol was collected. The NCO content of the distillate indicated that it was predominantly the monocarbamate of TDI. The pyrolysis flask contained 0.85 g of tar, representing 1.8 percent of the weight of the starting material. The distillate was then pyrolyzed again under the same conditions. This time, two distillates were collected-one at 75-85°C (predominantly TDI) and one at 165-175°C (predominantly the monocarbamate). The polymeric tar in the flask weighed less than 1 percent of the weight of starting material. Example 9 H 12 MDI di-1-methoxy-2-propyl biscarbamate (107.0 g) was pyrolyzed underthe same conditions used in Example 5. The products of this pyrolysis were 41.9 g of a polyisocyanate having an NCO content of 26.6 percent, 55.1 g of 1-methoxy-2-propanol and 9.7 g tarry residue.

Claims: 1. A polycarbamate as represented by the structure wherein b is a number of two or more, R is an organic radical with a valence equal to b, Y is a group having at least two carbon atoms, and Z is an aliphatic or aromatic group containing at least one carbon atom. 2. The polycarbamate of claim 1 wherein Z is a C C 4 straight chain alkyl, C3-C6 branched alkyl, methoxy- or ethoxy-substituted C 1 -C4 alkyl, phenyl or benzyl group, and Y is represented by the structure -CR 1 R 2 R3 wherein R 1 and R2 are independently hydrogen, Ci-Cε alkyl, aromatic, benzyl, alkoxy or phenoxy and R 3 is CrCε alkyl, aromatic, benzyl, alkoxy, phenoxy or dialkylamine. 3. The polycarbamate of claim 2 wherein R1 and R 2 are hydrogen, and R 3 is Ci- C 4 alkoxy or phenoxy. 4. The polycarbamate of claim 3 wherein b is 2 and R istolylene, dicyclohexylmethane or a diphenylmethane diradical. 5. The polycarbamate of claim 4 wherein R1 is hydrogen; R is methyl, ethyl or phenyl; R3 is methoxy or ethoxy; and Z is methyl or ethyl. 6. A process for preparing a polyisocyanate, comprising pyrolyzing a polycarbamate represented by the structure wherein b is a number of two or more, R is an organic radical with a valence equal to b, Y is a group having at least two carbon atoms, and Z is an aliphatic or aromatic group containing at least one carbon atom, under reduced pressure and at a temperature of 150 to 270°C, to form the corresponding polyisocyanate and alcohol. 7. The process of claim 6 which is conducted in the substantial absence of a solvent. 8. A process comprising reacting a first polycarbamate represented by the structure wherein A is C β linear alkyl, b is a number of two or more and R is an organic radical with a valence equal to b, with a secondary alcohol represented by the structure Z-CH(OH)-Y, wherein Y is a group having at least two carbon atoms, and Z is an aliphatic or aromatic group containing at least one carbon atom, at an elevated temperature such that a second polycarbamate represented by structure and an alcohol of the structure A-OH are formed, and wherein the alcohol A-OH is removed from the product polycarbamate continuously or intermittently as it forms. 9. The process of claim 14 wherein said elevated temperature is from 100°C and 250°C, and no organometallic catalyst is present. 10 The process of claim 14 wherein Z is a C 1 -C 4 straight chain alkyl, C3-C6 branched alkyl, methoxy- or ethoxy-substituted Cι-C 4 alkyl, phenyl or benzyl group, and Y is represented by the structure -CR 1 R 2 R3 wherein R 1 and R 2 are independently hydrogen, CrCδ alkyl, aromatic, benzyl, alkoxy or phenoxy and R 3 is C C6 alkyl, aromatic, benzyl, alkoxy, phenoxy or dialkylamine.

Inventors: DAI SHENGHONG A, NGUYEN HONG-ANH, NORMAN CHESTER R, DAI, SHENGHONG, A., NGUYEN, HONG-ANH, NORMAN, CHESTER, R.
Applicants: DOW CHEMICAL CO, THE DOW CHEMICAL COMPANY
Application year: 1995
Main classification: C07C271
IPC codes: C07B61, C07C263, C07C265, C07C269, C07C271