Two-step and one-pot processes for preparation of aliphatic diisocyanates

Abstract

The present invention relates to using a two-step (thermolysis) or one-pot process to prepare aliphatic diisocyanates from aliphatic diamines and diaryl carbonates. Polyisocyanates can also be prepared from polyamines and diaryl carbonates. The present synthetic processes do not apply phosgene or highly toxic reagents and chloro-solvents during the entire procedure.

Claims

1. A process for preparing aliphatic biscarbamates or aliphatic polycarbamates, the process comprising a step of reacting at least one aliphatic diamine or aliphatic polyamine with diaryl carbonate in a first solvent having low polarity to produce at least one aliphatic biscarbamate or aliphatic polycarbamate, the reaction optionally using a non-metal catalyst, and the first solvent having low polarity being ether or alcohol ether.

2. The process according to claim 1, wherein the diaryl carbonate is selected from the group consisting of diphenyl carbonate, bis(2-tolyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-nitrophenyl)carbonate and bis(3,5-dimethoxyphenyl)carbonate.

3. The process according to claim 1, wherein the aliphatic diamine or aliphatic polyamine is selected from the group consisting of butanediamines, hexanediamines, dodecanediamines, cyclohexyldiamines, isophorone diamine, 4-(aminoethyl)aniline, methylenedi(cyclohexyldiamine), propane-1,2,3-triamine, diethylenetriamine, bis(hexamethylene)triamine, triethylenetetraamine, 3-aminomethyl-1,6-hexanediamine and 1,3,6-triamino-n-hexane.

4. The process according to claim 1, wherein the first solvent having low polarity is selected from the group consisting of aryl ethers, aliphatic ethers, cycloaliphatic ethers, aromatic-aliphatic ethers, aromatic alcohol ethers, aliphatic alcohol ethers and aromatic-aliphatic alcohol ethers.

5. The process according to claim 4, wherein the first solvent having low polarity is selected from the group consisting of diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diphenyl ether and anisole.

6. The process according to claim 1, wherein the step is conducted at a molar ratio of aliphatic diamine or aliphatic polyamine to diaryl carbonate of 1:2 to 1:5.

7. The process according to claim 1, wherein the step is conducted at a solute concentration of 20 to 100% by weight.

8. The process according to claim 1, wherein no catalyst is used in the step.

9. The process according to claim 1, wherein the step is conducted at a temperature from 0 to 100 C.

10. The process according to claim 1, wherein the step is conducted at a reduced pressure.

11. A process for preparing an aliphatic diisocyanate or polyisocyanate, the process comprising: a step of reacting at least one aliphatic diamine or aliphatic polyamine with diaryl carbonate in a first solvent having low polarity to produce at least one aliphatic biscarbamate or aliphatic polycarbamate, the reaction optionally using a non-metal catalyst, and the first solvent having low polarity being ether or alcohol ether; and a step of thermolyzing the aliphatic biscarbamate or aliphatic polycarbamate in a second solvent having low polarity in the absence of a metal catalyst, wherein the second solvent having low polarity is selected from the group consisting of aryl ethers, aliphatic ethers, cycloaliphatic ethers, aromatic-aliphatic ethers, aromatic alcohol ethers, aliphatic alcohol ethers and aromatic-aliphatic alcohol ethers and is the same as or different from the first solvent having a low polarity.

12. The process according to claim 11, wherein the second solvent having low polarity is a compound represented by formula (5):
R.sup.5OR.sup.6(5), wherein R.sup.3 and R.sup.6 independently represent C.sub.6-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; or a compound represented by formula (6):
R.sup.7(O(CH.sub.2).sub.2).sub.aOR.sup.8(6) wherein R.sup.7 and R.sup.8 independently represent C.sub.1-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; and a represents an integer from 1 to 3.

13. The process according to claim 12, wherein the second solvent having low polarity is diphenyl ether, anisole, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether.

14. The process according to claim 11, wherein the step is conducted at a temperature from 120 to 250 C.

15. The process according to claim 11, wherein the step is conducted at a reduced pressure.

16. A one-pot process for preparing an aliphatic diisocyanate or polyisocyanate, the process comprising a step of reacting at least one aliphatic diamine or aliphatic polyamine with diaryl carbonate in a second solvent having low polarity to produce at least one biscarbamate or polycarbamate and further thermolyzing the at least one biscarbamate or polycarbamate in the same reactor, wherein the second solvent having low polarity is selected from the group consisting of aryl ethers, aliphatic ethers, cycloaliphatic ethers, aromatic-aliphatic ethers, aromatic alcohol ethers, aliphatic alcohol ethers and aromatic-aliphatic alcohol ethers.

17. The process according to claim 16, wherein the diaryl carbonate is selected from the group consisting of diphenyl carbonate, bis(2-tolyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-nitrophenyl)carbonate and bis(3,5-dimethoxyphenyl)carbonate.

18. The process according to claim 16, wherein the aliphatic diamine or aliphatic polyamine is selected from the group consisting of butanediamines, hexanediamines, dodecanediamines, cyclohexyldiamines, isophorone diamine, 4-(aminoethyl)aniline, methylenedi(cyclohexyldiamine), propane-1,2,3-triamine, diethylenetriamine, bis(hexamethylene)triamine, triethylenetetraamine, 3-aminomethyl-1,6-hexanediamine and 1,3,6-triamino-n-hexane.

19. The process according to claim 16, wherein the second solvent having low polarity is a compound represented by formula (5):
R.sup.5OR.sup.6(5), wherein R.sup.5 and R.sup.6 independently represent C.sub.6-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; or a compound represented by formula (6):
R.sup.7(O(CH.sub.2).sub.2).sub.aOR.sup.8(6) wherein R.sup.7 and R.sup.8 independently represent C.sub.1-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; and a represents an integer from 1 to 3.

20. The process according to claim 16, wherein the second solvent having low polarity is diphenyl ether, anisole, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether.

21. The process according to claim 16, wherein the step is conducted at a molar ratio of aliphatic diamine or aliphatic polyamine to diaryl carbonate of 1:2 to 1:5.

22. The process according to claim 16, wherein the step is conducted at a solute concentration of 20 to 100% by weight.

23. The process according to claim 16, wherein no catalyst is used in the step.

24. The process according to claim 16, wherein the step is conducted at a temperature from 120 to 250 C.

25. The process according to claim 16, wherein the step is conducted at a pressure from 0.01 mmHg to 760 mmHg.

26. The process according to claim 16, the reaction being completed in a period from 0.1 to 1 hour.

27. The process according to claim 11, wherein the aromatic alcohol ethers, aliphatic alcohol ethers and aromatic-aliphatic alcohol ethers are selected from the group consisting of alkylene glycol dialkyl ethers, alkylene glycol aryl alkyl ethers and alkylene glycol diaryl ethers.

28. The process according to claim 16, wherein the aromatic alcohol ethers, aliphatic alcohol ethers and aromatic-aliphatic alcohol ethers are selected from the group consisting of alkylene glycol dialkyl ethers, alkylene glycol aryl alkyl ethers and alkylene glycol diaryl ethers.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Diarylcarbornates

(2) The diarylcarbonates used in the subject application can be compounds represented by the following formula (1):

(3) ##STR00012##

(4) wherein R.sup.1 and R.sup.2 independently represent an aromatic group having 6 to 20, preferably 6 to 12 carbon atoms. When an aromatic group has two or more substituents, these substituents can be the same or different.

(5) The substituents for R.sup.1 and R.sup.2 are preferably selected from alkyl or cycloalkyl having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, etc.; arylalkyl having 7 to 15 carbon atoms, such as phenylmethyl, phenylethyl, etc.; aryl having 6 to 14 carbon atoms, such as phenyl, tolyl, etc.; alkoxyl having 1 to 12 carbon atoms, such as methoxyl, ethoxyl, propoxyl, butoxyl, trifluoromethoxyl, etc.; alkylthio having 1 to 12 carbon atoms, such as thiomethoxyl, thioethoxyl, etc.; aryloxyl having 6 to 14 carbon atoms, such phenoxyl, etc.; halogen, such as fluoro, chloro, bromo, etc.; nitro; hydroxyl; cyano; and dialkylamino, such as dimethylamino, etc.

(6) Substituted or unsubstituted R.sup.1 and R.sup.2 include, for example, phenyl, naphthalenyl, anthracenyl, tolyl, xylyl, ethylphenyl, propylphenyl, octylphenyl, nonylphenyl, dodecylphenyl, bisphenyl, methoxyphenyl, chlorophenyl, dichlorophenyl, trichlorophenyl, pentachlorophenyl, bromophenyl, dibromophenyl, tribromophenyl, pentabromophenyl, nitrophenyl, dinitrophenyl, hydroxylphenyl, cyanophenyl, dimethylaminophenyl, etc.

(7) In addition, these aryls include ortho-, meta- and para-isomers, and the substituents linked to the aryls include n-, iso, sec- and tert-isomers.

(8) In particular, diarylcarbonates having the same and unsubstituted aryl moieties can be selected from, but are not limited to, diphenyl carbonate, bis(1-naphthalenyl) carbonate, bis(2-naphthalenyl) carbonate and bis(9-anthracenyl) carbonate.

(9) Diarylcarbonates having the same aryl moieties, wherein each of the aryl moieties is substituted by at least one alkyl, can be selected from, but are not limited to, bis(2-tolyl) carbonate and bis[4-(tert-butyl)phenyl] carbonate.

(10) Diarylcarbonates having the same aryl moieties, wherein each of the aryl moieties is substituted by at least one aryl, can be selected from, but are not limited to, bis(4-bisphenylphenyl) carbonate.

(11) Diarylcarbonates having the same aryl moieties, wherein each of the aryl moieties is substituted by at least one alkoxyl, can be selected from, but are not limited to, bis(2-methoxyphenyl) carbonate and bis(3-butoxyphenyl) carbonate.

(12) Diarylcarbonates having the same aryl moieties, wherein each of the aryl moieties is substituted by at least one halogen, can be selected from, but are not limited to, bis(2-chlorophenyl) carbonate, bis(2,4-dichlorophenyl) carbonate and bis(2,4,6-trichlorophenyl) carbonate.

(13) Diarylcarbonates having the same aryl moieties, wherein each of the aryl moieties is substituted by at least one nitro, can be selected from, but are not limited to, bis(2-nitrophenyl) carbonate and bis(2,4-dinitrophenyl) carbonate.

(14) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one alkyl can be selected from, but are not limited to, 3-tolyl phenyl carbonate and 4-tolyl phenyl carbonate.

(15) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one arylalkyl can be selected from, but are not limited to, 4-phenylmethyphenyl(phenyl) carbonate.

(16) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one alkoxyl can be selected from, but are not limited to, 4-methoxyphenyl phenyl carbonate and 4-ethoxyl-1-naphthalenyl phenyl carbonate.

(17) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one alkylthio can be selected from, but are not limited to 4-methylthiophenyl phenyl carbonate.

(18) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one aryloxy can be selected from, but are not limited to, 4-pheoxyphenyl phenyl carbonate.

(19) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one halogen can be selected from, but are not limited to, 2-chlorophenyl phenyl carbonate and 4-chlorophenyl phenyl carbonate.

(20) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one nitro can be selected from, but are not limited to, 3-nitrophenyl phenyl carbonate and 2,4-dinitrophenyl phenyl carbonate.

(21) Diarylcarbonates having an unsubstituted aryl moiety and an aryl substituted by at least one hydroxyl can be selected from, but are not limited to, 3-hydroxyphenyl phenyl carbonate and 4-hydroxyphenyl phenyl carbonate.

(22) Other diarylcarbonates suitable for use in the subject application include 4-methoxyphenyl-4-nitrophenyl carbonate, 4-cyanophenyl-4-nitrophenyl carbonate, 4-thiomethoxyphenyl-4-nitrophenyl carbonate, 2-chlorophenyl-4-nitrophenyl carbonate, 2-dimethylaminophenyl phenyl carbonate, 2-bromo-4-cyano-6-nitrophenyl phenyl carbonate and pentabromophenyl-2,4,6-tribromophenyl carbonate.

(23) Among the above-mentioned diarylcarbonates, it is preferable to use diphenyl carbonate, bis(2-tolyl) carbonate, bis(4-chlorophenyl) carbonate, bis(4-nitrophenyl) carbonate and bis(3,5-dimethoxyphenyl) carbonate, and more preferable to use diphenyl carbonate.

(24) Aliphatic Diamines and Aliphatic Polyamines

(25) The term aliphatic as used herein is intended to include aliphatic or aromatic-aliphatic moieties but not to include pure aromatic moieties.

(26) Aliphatic diamines or aliphatic diamine compounds as used in the subject application comprise compounds represented by the following formula (2):
H.sub.2NR.sup.3NH.sub.2(2)

(27) Examples of R.sup.3 comprise (but are not limited to) C.sub.1-16 linear alkyl, such as methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene and dodecamethylene; C.sub.3-16 cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bis(cyclohexyl) and cyclooctyl substituted by alkyl; cycloalkyl substituted by alkyl, such as methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, pentylcyclohexyl and hexylcyclohexcyl; C.sub.3-16 cycloalkyl substituted by two (same or different) C.sub.1-6 alkyls, such as dimethylcyclohexyl and diethylcyclohexyl; cycloalkyl substituted by three alkyls, such as 1,5,5-trimethylcyclohexyl, 1,5,5-triethylcyclohexyl, 1,5,5-tripropylcyclohexyl and 1,5,5-tributylcyclohexyl. In particular, aliphatic diamine compounds are preferably selected from butanediamines (BMDA), hexanediamines (HMDA), dodecanediamines (DMDA), cyclohexyldiamines, isophorone diamine and methylenedi(cyclohexyldiamine).

(28) Aliphatic diamine compounds as used in the subject application may also comprise arylalkyldiamines, such as the compounds represented by the following formula (3):
H.sub.2NArR.sup.3NH.sub.2(3),

(29) wherein Ar represents C.sub.6-9 arylene; and

(30) R.sup.3 is defined as above.

(31) Arylalkyldiamines as used in the subject application can be those such as 4-(aminoethyl)phenylamine, etc.

(32) Aliphatic polyamine compounds as used in the subject application refer to aliphatic hydrocarbons having three or more substituent amino groups, such as the compounds represented by the following formula (4):
R.sup.4(NH.sub.2).sub.p(4),

(33) wherein R.sup.4 has the same definition of R.sup.3 as stated above; and

(34) p represents an integer of at least 3.

(35) Examples of aliphatic polyamine compounds as used in the subject application comprise propane-1,2,3-triamine, diethylenetriamine, bis(hexamethylene)triamine, triethylenetetraamine, 3-aminomethyl-1,6-hexanediamine and 1,3,6-triamino-n-hexane, etc. Aliphatic polyamine compounds as used in the subject application also comprise arylalkyl polyamines.

(36) Solvents Having Low Polarity

(37) Solvents having low polarity as recited in the subject application include a first solvent having low polarity and a second solvent having low polarity.

(38) Solvents having low polarity as used in the subject application include low-polarity solvents and nonpolar solvents familiar to persons of ordinary skill in the art, in which the boiling point is preferably between 50 C. to 250 C., such as (but not limited to) ethers or alcohol ethers.

(39) Ethers as used in the subject application are compounds having ether functionality, i.e., compounds having functionality of oxygen atom(s) bridging two moieties which are independently selected from alkyls and aryls. Ethers acting as solvents having low polarity in the subject application can be, for example, compounds represented by the following formula (5):
R.sup.5OR.sup.6(5),

(40) R.sup.5 and R.sup.6 independently represent C.sub.1-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; or

(41) R.sup.5, R.sup.6 and the oxygen atom together form a ring ether having a ring moiety.

(42) Ethers can be aryl ethers, aliphatic ethers, cycloaliphatic ethers or aromatic-aliphatic ethers. Examples of ethers include diethyl ether, anisole, diphenyl ether, tetrahydrofuran, 1,4-dioxane, etc.

(43) Solvents having low polarity as used in the subject application also include alcohol ethers, comprising aromatic alcohol ethers, aliphatic alcohol ethers or aromatic-aliphatic alcohol ethers. Examples include glycol ethers, such as alkylene glycol ethers, for example alkylene glycol dialkyl ether, alkylene glycol aryl alkyl ether and alkylene glycol diaryl ether. Examples of alkylene glycol ethers include ethylene glycol ethers, which are the compounds represented by the following formula (6):
R.sup.7(O(CH.sub.2).sub.2).sub.aOR.sup.8(6),

(44) wherein R.sup.7 and R.sup.8 independently represent C.sub.1-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; and

(45) a represents an integer from 1 to 3.

(46) Preparation of Biscarbamates and Polycarbamates

(47) Aliphatic biscarbamates or aliphatic polycarbamates are prepared from the aforementioned aliphatic diamines and diaryl carbonates in a first solvent having low polarity. This process allows efficient production and isolation of aliphatic biscarbamates or polycarbamates from aliphatic diamines or aliphatic polyamines at a low reaction temperature.

(48) The first solvent having low polarity, as stated above, can be any solvent having low polarity as defined herein and preferably diethyl ether, anisole, diphenyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc; more preferably diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc.

(49) In one embodiment of the preparation process of aliphatic biscarbamates of the subject application, a ratio of aliphatic diamine compounds to diaryl carbonates from 1:2 to 1:5, preferably from 1:2 to 1:4 and more preferably from 1:2 to 1:3 is used.

(50) In one embodiment of the preparation process of aliphatic biscarbamates of the subject application, a solute concentration from 20% to 100%, preferably 25% to 90% and more preferably 40% to 75%, such as about 50%, is used.

(51) In one embodiment of the preparation process of aliphatic biscarbamates of the subject application, no metal catalyst is involved or a non-metal catalyst (such as carboxylic acid) is optionally used, and the carboxylic acid can be selected from the group consisting of benzoic acid, p-tert-butylbenzoic acid, p-anisic acid, isobutanoic acid, propanoic acid, butanoic acid and pivalic acid. When arylalkyldiamines are used as reactants, a non-metal catalyst is preferably used.

(52) In the subject application, aliphatic biscarbamates can be efficiently prepared from aliphatic diamines and efficiently isolated at a low reaction temperature. For example, the reaction for producing biscarbamates is conducted at a temperature from 0 C. to 100 C., preferably from 15 C. to 100 C., more preferably from 15 C. to 60 C., such as from 15 C. to 25 C. or from room temperature to 60 C. In the preparation process of aliphatic biscarbamates of the subject application, after the reaction is completed, the target aliphatic biscarbamates precipitate from the reaction mixture and are collected. In the collection step, the reaction mixture is cooled to room temperature, or the temperature of the reaction mixture is controlled at about 40 C. or below, preferably from about 40 C. to about 0 C. and more preferably from about 30 C. to about 10 C. so that the aliphatic biscarbamates can precipitate from the reaction mixture and the precipitated aliphatic biscarbamates can be isolated by a separation means, such as filtration or centrifugation, and collected.

(53) The thus-produced reaction mixture can be treated to isolate and collect the aliphatic biscarbamates. For example, the reaction mixture can be distilled to separate the reaction medium, carboxylic acids and phenolic compounds from the reaction mixture so that the residual solid substance can be directly collected; or the solid substance can be subjected to a further treatment, such as being washed by a solvent or being recrystallized, to isolate and collect aliphatic biscarbamates.

(54) If necessary, after the filtration of aliphatic biscarbamates, the mother liquid can be subjected to a further treatment as mentioned above to advantageously recover more residual aliphatic biscarbamates from the mother liquid.

(55) Upon filtration or centrifugation, distillation or washing with a solvent (such as toluene) can be optionally conducted to remove byproduct phenolic compounds and reaction medium from the mother liquid. In addition, after adding sufficient amounts of diaryl carbonates, amine compounds and optional catalysts into the mother liquid, the mother liquid can be reused in the preparation process of aliphatic biscarbamates of the subject application.

(56) Even though the biscarbamates obtained by the process of the subject application exhibit a purity sufficient to be directly used in subsequent applications, recrystallization, if necessary, can be conducted to further refine the aliphatic biscarbamates. Solvents suitable for recrystallization include (but are not limited to) aromatic hydrocarbons (such as benzene, toluene and xylene), aliphatic alcohols (such as ethanol and n-butanol), ethers (such as bis(n-propyl) ether), esters (such as ethyl acetate, isobutyl acetate and cyclohecyl acetate) and ketones (such as methyl isobutyl ketone and cyclohexanone).

(57) Two-Step Preparation Process for Diisocyanates or Polyisocyanates

(58) The subject application also provides a non-phosgene thermolysis process for aliphatic diisocyanates or aliphatic polyisocyanates, comprising a step of thermolysis of aliphatic biscarbamates or aliphatic polycarbamates in a second solvent having low polarity.

(59) The second solvent having low polarity used in the subject application, as stated above, can be any solvent having low polarity as defined herein. The first solvent having low polarity and the second solvent having low polarity can be the same or different. The second solvent having low polarity is preferably anisole, diphenyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc.

(60) In one embodiment of the subject application, the biscarbamates obtained by the process of the subject application are subject to thermolysis in a second solvent having low polarity, which has a higher boiling point, to obtain diisocyanates. It is found that when the solvents having low polarity as defined herein are used, the removal of phenol (which is produced during heating) can be accelerated, while the formation of byproduct carbodiimides via dimerization of isocyanate products can be alleviated. The two effects are necessary for ensuring aliphatic products of HDI, IPDI, etc. transformed from precursor biscarbamates of HDI, DDI, IPDI, etc. at a high yield during the thermolysis process.

(61) In the examples of the subject application, the thermolysis reaction means to convert aliphatic biscarbamates or aliphatic polycarbamates to corresponding diisocyanates (such as HDI, DDI, IPDI) or polyisocyanates and aromatic hydroxy compounds (such as phenol). In addition, upon the thermolysis reaction, diisocyanate or polyisocyanate products can be easily isolated from aromatic hydroxy compounds (such as phenol).

(62) The second solvent having low polarity as used for the thermolysis reaction in the two-step process is preferably selected from those having a higher boiling point; for example, the compounds represented by formula (5) as stated above as ethers, where R.sup.5 and R.sup.6 independently represent C.sub.6-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; or the compounds represented by either formula (5) or formula (6) where the boiling point is not less than the temperature for conducting the thermolysis reaction.

(63) In another embodiment, the second solvent having low polarity as used for the thermolysis reaction in the two-step process has a higher boiling point than that of the first solvent having low polarity.

(64) The temperature for thermolysis reaction is one sufficient to allow the biscarbamates or polycarbamates to thermolyze and depends on pressure, solvents, etc., such as a temperature ranging from 100 C. to 250 C. or 150 C. to 240 C. The pressure for the reaction can be a reduced pressure or a normal pressure, such as a pressure between 0.01 mmHg and 760 mmHg. When the byproduct phenol is constantly removed, the temperature for reaction can be a lower one.

(65) There is no specific limitation of the time for reaction. Normally, the time for reaction is at most 3 hours, preferably from 0.5 to 2 hours and more preferably from 0.5 to 1 hour. In certain examples, when the process is conducted with a continuous or running system, the time for thermolysis reaction is significantly reduced to dozens of minutes or minutes for completion of the reaction.

(66) One-Pot Process for Preparation of Diisocyanates or Polyisocyanates

(67) The subject application also provides a non-phosgene one-pot process for aliphatic diisocyanates or aliphatic polyisocyanates, the process comprising reacting aliphatic diamine compounds or aliphatic polyamine compounds with diaryl carbonates followed by a thermolyzing step in the same reactor to prepare aliphatic diisocyanates or aliphatic polyisocyanates.

(68) According to the aforementioned two-step process, the biscarbamates obtained in the first step have a sufficiently high purity, so the steps of synthesizing isocyanates and thermolyzing biscarbamates in the two-step process could be directly combined. Upon selecting suitable reaction conditions and solvents, diisocyanates or polyisocyanates can be obtained at a similar yield and purity to that obtained in the two-step process. The reaction conditions for the one-pot process for preparation of diisocyanates or polyisocyanates are generally the same as those used in the two-step process, but the former provides an advantage over the latter due to the elimination of the isolation step of biscarbamates or polycarbamates, thereby saving time and energy.

(69) In the one-pot process for the preparation of diisocyanates or polyisocyanates, the second solvent having lower polarity is used, preferably one having a higher boiling point, such as the compounds represented by formula (5) as stated above as ethers, where R.sup.5 and R.sup.6 independently represent C.sub.6-9 alkyl, C.sub.6-9 aryl or C.sub.6-12 arylalkyl; or the compounds represented by either formula (5) or formula (6) where the boiling point is not less than the temperature for conducting the thermolysis reaction.

(70) The temperature for reaction in the one-pot process is one sufficient to allow biscarbamates or polycarbamates to form and thermolyze and depends on pressure, solvents, etc., such as a temperature ranging from 120 C. to 250 C., such as 240 C. The pressure for the reaction can be a reduced pressure or a normal pressure, such as a pressure from 0.01 mmHg to 760 mmHg. When the byproduct phenol is constantly removed, the temperature for reaction can be a lower one.

(71) There is no specific limitation of the time for reaction. Normally, the time for reaction is at most 3 hours, preferably from 0.5 to 2 hours and more preferably from 0.5 to 1 hour. In certain examples, the time for conducting thermolysis reaction can be significantly reduced to dozens of minutes or minutes. For example, under a reduced pressure, the time for reaction can be 0.1 to 1 hour or 10 to 25 minutes.

(72) Preparation of Polyurea

(73) The subject application also provides a process of preparing polyurea directly from the aliphatic biscarbamates or polycarbamates with an amine compound or a mixture of amine compounds. In particular, polyurea can be prepared in a polar solvent by reacting the aliphatic biscarbamates or polycarbamates of the subject application with an amine compound or a mixture of amine compounds.

(74) The amine compounds suitable for preparing the polyurea in the subject application can be selected from, but are not limited to, the group consisting of aliphatic or aromatic diamines having a long or short chain, which may be ether diamines, such as 1,8-diamino-3,6-dioxaoctane; long-chained polyether diamines, such as polyethoxylated or polypropoxylated diamines (D-2000); aliphatic diamines, such as 1,6-hexanediamine (1,6-HDA); cyclic aliphatic diamines, such as isophorone diamine (IPDA) and H.sub.12MDA (hydrogenated MDA); and aromatic diamines, such as 4,4-diaminodiphenylmethane (MDA).

(75) Polar solvents suitable for use in the preparation of polyurea include, but are not limited to, N,N-dimethylacetamide (DMAc), N-methyl-pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and tetramethylene sulfone (TMS), etc.

(76) The temperature for reaction normally ranges from about 60 C. to about 200 C., preferably about 60 C. to about 160 C. and more preferably about 60 C. to about 100 C. The pressure for the reaction can be a reduced pressure, a normal pressure or an elevated pressure.

(77) There is no specific limitation of the time for reaction. Normally, the time for reaction is from 0.001 to 100 hours, preferably from 0.005 to 50 hours and more preferably from 0.1 to 10 hours.

EXAMPLES

(78) The invention of the subject application has been clearly and substantially described above and can be further illustrated by certain examples as provided below. These examples are provided merely for the purpose of illustration. Unless indicated otherwise, the examples are not intended to limit the claimed scope of the invention.

Example 1

Synthesis of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC)

(79) Hexanediamine (HMDA, 6.0 g, 51.7 mmol) and diphenyl carbonate (DPC, 22.67 g, 106 mmol) were introduced into a 500 mL triple-neck flask containing 100 mL of ethylene glycol diethyl ether, and the mixture was stirred by a magnetic stirrer at room temperature. Nitrogen gas was introduced into the flask, while one neck of the flask was equipped with a thermometer and the other neck was connected to a condenser containing flowing water, where the top of the condenser was connected with an oil seal. The reaction was conducted for 2 hours. When the result of IR analysis indicated that 4,4-diaminodiphenylmethane and monocarbamate intermediates no longer existed, the reaction was deemed complete.

(80) After completion of the reaction, the reaction mixture was constantly stirred and the temperature of the reaction mixture was slowly lowered to room temperature. Precipitation of a white crystalline product was observed. Then, suction filtration was applied to isolate the product, and the product was dried in an oven under vacuum at 80 C. for 6 hours. White solid crystalline products were collected (17.53 g). 1H-NMR (200 MHz, d6-dimethyl sulfoxide) (ppm): 1.31 (s, 4H, NHCH.sub.2CH.sub.2CH.sub.2), 1.45 (s, 4H, NHCH.sub.2CH.sub.2), 3.04 (s, 4H, NHCH.sub.2), 7.06-7.36 (m, 10H, -Ph-), 7.73 (br s, 2H, NH). Yield: 98%. Melting point: 126.6 C.

Comparative Example 1

(81) Based on the method disclosed in the patent (EP 2275405 A1) of Shinohata and Miyake under Asahi Kasei Chemicals Corp. (Japan), hexanediamine (HDA, 2.1 mol) was fed to a tank containing diphenyl carbonate (DPC, 6.3 mol) continuously at a rate of 200 g/hour and at 50 C., and excess phenol (10.5 mol) was used as a reaction solvent to conduct the reaction. 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) was obtained at a yield of 99.5% and subsequent thermolysis was conducted at about 180 C. The whole procedure of the process took an unduly long time (several days or even ten or so days). A simulated batchwise process was conducted based on the ratio of the reagents as disclosed in Asahi patent, where hexanediamine (HMDA, 6.0 g, 51.7 mmol) and diphenyl carbonate (DPC, 33.18 g, 155.1 mmol) were introduced into a 500 mL triple-neck flask containing 24.4 g of phenol (258.5 mmol). Upon stirring at 50 C., phenol in the reaction flask could not completely dissolve hexanediamine and diphenyl carbonate and the mixture was opaque and turbid. No further reaction was possible.

(82) Then, the temperature was raised to 80 C. and 14.78 g of phenol was introduced simultaneously. Although the solid could be completely dissolved, the result of IR analysis at 16 hours showed that diphenyl carbonate and carbamate intermediates were still present in the reaction mixture, which means that the reaction was not finished.

(83) Hsueh-Yung Chen et al. disclosed in their article (Hsueh-Yung Chen, Wen-Chen Pan, Chao-Hsing Lin, Chun-Ying Huang. Synthesis and trans-ureation of N,N-diphenyl-4,4-methylenediphenylene biscarbamate with diamines: a non-isocyanate route (NIR) to polyureas. J Polym Res 2012; 19: 9754.) using non-metal catalysts in the synthesis of biscarbamates; the full text is incorporated by reference herein. In particular, benzoic acid was introduced into the reactants and the final ratio between the raw materials HMDA/DPC/benzoic acid was 1/3/0.2 (51.7 mmol/155.1 mmol/10.3 mmol). After being stirred at 80 C. for 16 hours, the reaction mixture was slowly cooled to room temperature with continuous stirring. Precipitation of white crystalline products was observed. The product was isolated by suction filtration. Then, the thus-obtained product was washed with toluene (50 mL) and dried in an oven under vacuum at 80 C. for 6 hours. White solid crystalline products were collected and analyzed, and the result showed that 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) was obtained at a yield of 51.9% accompanied with 39.7% of urea byproduct.

Example 2

Synthesis of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) with different solvents

(84) Phenol, toluene, methylcyclohexane, 1-bromopropane, ethylene glycol diethyl ether (1,2-diethoxyethane, EGDEE) were chosen as reaction solvents. The procedure and analysis as stated in Example 1 were conducted, where the conditions for synthesis were shown in Table 1. Results showed that ethylene glycol diethyl ether, a solvent having low polarity, was the best solvent, providing 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) at a highest yield of 90.3% accompanied with a lowest amount of 8.54% of byproduct urea.

(85) TABLE-US-00001 TABLE 1 Effect on yield of product in the synthesis of HMBPC in view of solvents Solute concentration Reaction Yield of Yield Composition Solvent (wt. %) conditions biscarbamates of urea HMDA/ Phenol 50% 80 C./16 hr 51.9% 39.7% DPC/ Toluene 25% 80 C./2 hr 85.2% 10.4% Benzoic acid Methylcyclohexane 25% 100 C./2 hr 86.1% 10.9% 1/3/0.2 1-bromopropane 25% 45 C./2 hr 88.0% 11.5% Ethylene glycol 25% 45 C./2 hr 90.3% 8.54% diethyl ether

Example 3

Synthesis of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) with different amounts of diphenyl carbonate (DPC)

(86) The same procedure and analysis done in Example 1 were repeated, but the amounts of diphenyl carbonate (DPC) shown in Table 2 were used. When the amount of diphenyl carbonate (DPC) were increased to 4-fold of HMDA (in mole), a highest yield of 95% of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) and a lowest yield of 2.04% of byproduct urea were obtained.

(87) TABLE-US-00002 TABLE 2 Effect on yield of product in the synthesis of HMBPC in view of the ratio of HMDA to DPC in ethylene glycol diethyl ether Solute concentration Reaction Yield of Yield of Composition (wt. %) conditions biscarbamates urea HMDA/DPC/ 25% 25 C./2 hr 95% 2.01% benzoic acid 1/4/0.2 HMDA/DPC/ 25% 25 C./2 hr 90.3% 8.54% benzoic acid 1/3/0.2

Example 4

Synthesis of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) with different amounts of solute concentrations

(88) The same procedure and analysis done in Example 1 were repeated, but the solute concentrations shown in Table 3 were used. When the solute concentration (weight percent) was increased, the yield of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) also increased, while the byproduct urea also increased. When the solute concentration was raised to 50%, a highest yield of 97.3% of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) and a lowest amount of 1.49% of byproduct urea were obtained.

(89) TABLE-US-00003 TABLE 3 Effect on yield of product in the synthesis of HMBPC in view of solute concentrations in ethylene glycol diethyl ether Solute concentration Reaction Yield of Yield of Composition (wt. %) conditions biscarbamates urea HMDA/ 100% 100 C./2 hr 97.2% 4.01% DPC/ benzoic acid 1/4/0.2 HMDA/ 50% 45 C./2 hr 97.3% 1.49% DPC/ benzoic acid 1/4/0.2 HMDA/ 25% 25 C./2 hr 95% 2.04% DPC/ benzoic acid 1/4/0.2

Example 5

Synthesis of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) in the absence of benzoic acid catalyst

(90) The same procedure and analysis done in Example 1 were repeated, but the amounts of diphenyl carbonate (DPC) and benzoic acid shown in Table 4 were used. In the cases that benzoic acid catalyst was not used, the byproduct urea was not formed even though the amount of diphenyl carbonate (DPC) decreased. When the amount of diphenyl carbonate (DPC) was decreased such that HMDA/DPC=1/2.05, a highest yield of 98% of 1,6-hexamethylene-bis(phenyl carbamates) (HMBPC) was obtained without generation of any urea byproduct during the reaction.

(91) TABLE-US-00004 TABLE 4 Effect on yield of product in the synthesis of HMBPC in the absence/presence of benzoic acid catalyst in ethylene glycol diethyl ether Solute concentration Reaction Yield of Yield of Composition (wt. %) conditions biscarbamates urea HMDA/ 25% 25 C./2 hr 90.3% 8.54% DPC/ benzoic acid 1/3/0.2 HMDA/DPC 25% 25 C./2 hr 92.2% 0% 1/3 HMDA/DPC 25% 25 C./2 hr 95% 0% 1/2.65 HMDA/DPC 25% 25 C./2 hr 93% 0% 1/2.2 HMDA/DPC 25% 15 C./2 hr 98% 0% 1/2.05

Example 6

Synthesis of Diphenyl N,N-alkenylbiscarbamates under different diamines

(92) The same procedure and analysis done in Example 1 were repeated, but the diamines shown in Table 5 were used. When a ratio of diamine/DPC of 1/2.05 and a solute concentration of 25% were utilized, corresponding diphenyl N,N-alkenylbiscarbamates were obtained with respect to each diamine in a yield over 85%.

(93) TABLE-US-00005 TABLE 5 Carbonylation on diamines for the preparation of N,N-alkenylbiscarbamates in ethylene glycol diethyl ether Yiled of Yield of Composition Products biscarbamates urea T.sub.m ( C.) T.sub.d ( C.) BMDA/DPC (1/2.05) BMBPC 89% 0% 162 162.8 HMDA/DPC (1/2.05) HMBPC 98% 0% 126.6 147.4 DMDA/DPC (1/2.05) DMBPC 98% 0% 122.5 181.6 4-(aminomethyl)aniline/ 4-TABPC 85% 0% 170.8 171.8 DPC/benzoic acid (1/4/0.2)

Structures of Diamines and N,N-alkenylbiscarbamates

(94) ##STR00013##

Example 7

Synthesis of 1,12-dodecamethylene diisocyanate (DDI) via thermolysis

(95) 1,12-dodecamethylene-bis(phenyl carbamate) (DMBPC, 27.78 g, 67.78 mmol) was introduced into a 500 mL triple-neck flask containing 250 g of diphenyl ether (the solute concentration was thus 10%), and the mixture was stirred by a magnetic stirrer upon heating from room temperature. Nitrogen gas was introduced into the flask, while one neck of the flask was equipped with a thermometer and the other neck was connected to a condenser containing flowing water, where the top of the condenser was connected with an oil seal. The reaction was conducted for 0.5 hour when the temperature reached 240 C. When the result of IR analysis indicated that 1,12-dodecamethylene-bis(phenyl carbamate) and intermediate monocarbamate no longer existed, the reaction was terminated.

(96) After the reaction was terminated, the reaction mixture was continuously stirred and cooled to 100-150 C., and diphenyl ether was isolated via a vacuum pump from the product 1,12-dodecamethylene diisocyanate (DDI). It was observed that DDI was in transparent liquid form and the yield was 84%. The DDI was further treated by anhydrous methanol to block NCO groups, dried in a vacuum oven at 80 C. for 6 hours and analyzed to evaluate purity: 1H-NMR (200 MHz, d6-dimethylsulfoxide) (ppm) 1.21 (s, 8H, NHCH2CH2CH2CH2-), 1.36 (s, 4H, NHCH2CH2CH2CH2-), 2.92 (s, 4H, NHCH2CH2CH2CH2-), 3.52 (s, 6H, CH3COONH), 7.08 (m s, 2H, NH). Yield of DDI: 84%; recovery of phenol: 100%; recovery of diphenyl ether: 85%.

Synthesis of Diisocyanates from Diphenyl N,N-Alkenylbiscarbamates Via Thermolysis

(97) The same procedure and analysis done in Example 7 were repeated but the diphenyl N,N-alkenylbiscarbamates shown in Table 6 were used, and the corresponding diisocyanates also shown in Table 6 were obtained. When a solute concentration of 10% was applied, the products DDI and 4-IBPI were obtained in a yield of 84%.

(98) TABLE-US-00006 TABLE 6 Diisocyanates prepared from biscarbamates via thermolysis in diphenyl ether solution Solute concentration Reaction Yield of Recovery of Biscarbamate Product (wt. %) conditions diisocyanate phenol BMBPC 1,4-butamethylene 10% 240 C./2 hr 58% 100% diisocyanate (BDI) HMBPC 1,6-hexamethylene 10% 240 C./2 hr 76% 100% diisocyanate (HDI) DMBPC 1,12-dodecamethylene 25% 240 C./0.5 hr 84% 100% diisocyanate (DDI) 4-TABPC 1-isocyanate-4- 5% 240 C./1 hr 84% 100% (isocyanatomethyl) benzene

Example 9

Preparation of 1,12-dodecamethylene diisocyanate (DDI) via one-pot process

(99) Dodecanediamine (DMDA, 10 g, 50 mmol) and diphenyl carbonate (DPC, 21.9 g, 102.5 mmol) were introduced into a 500 mL triple-neck flask containing 96 g of diphenyl ether (the solute concentration was thus 25%), and the mixture was stirred by a magnetic stirrer at room temperature. Nitrogen gas was introduced into the flask, while one neck of the flask was equipped with a thermometer and the other neck was connected to a condenser containing flowing water, where the top of the condenser was connected with an oil seal. The reaction was conducted for 2 hours. When the result of IR analysis indicated that dodecanediamine and the intermediate monocarbamate no longer exist, the reaction was deemed finished. The reaction mixture was subsequently heated upon stirring with a magnetic stirrer in the same triple-neck flask, where nitrogen gas was introduced into the flask, one neck of the flask was equipped with a thermometer, the other neck was connected to a condenser containing flowing water, and the top of the condenser was connected with an oil seal. The reaction was conducted for 0.5 hour when the temperature reached 240 C. When the result of IR analysis indicated that 1,12-dodecamethylene-bis(phenyl carbamate) and the intermediate monocarbamate no longer existed, the reaction was terminated.

(100) After the reaction was terminated, the reaction mixture was continuously stirred and cooled to 100-150 C., and diphenyl ether was isolated via a vacuum pump from the product 1,12-dodecamethylene diisocyanate (DDI). It was observed that DDI was in transparent liquid form and the yield was 80%. The DDI was further treated by anhydrous methanol to block NCO groups, dried in a vacuum oven at 80 C. for 6 hours and analyzed to evaluate purity: 1H-NMR (200 MHz, d6-dimethylsulfoxide) (ppm): 1.21 (s, 8H, NHCH2CH2CH2CH2-), 1.36 (s, 4H, NHCH2CH2CH2CH2-), 2.92 (s, 4H, NHCH2CH2CH2CH2-), 3.52 (s, 6H, CH3COONH), 7.08 (m s, 2H, NH). Yield of DDI: 84%; recovery of phenol: 100%; recovery of diphenyl ether: 85%.

Example 10

Preparation of Diisocyanates Via One-Pot Process

(101) The same procedure and analysis proceeded in Example 9 were repeated but the diamines as shown in Table 7 were used, where the corresponding biscarbamates derived from the diamines were further thermolyzed in the same reactor to obtain the diisocyanates as shown in Table 7. When a solute concentration of 10% was applied, a product isophorone diisocyanate (IPDI) was obtained in a yield of 86%.

(102) Table 7: One-Pot, Two-Stage NPR Process for the Preparation of Diisocyanates

(103) TABLE-US-00007 Solute Recovery of concentration Reaction Yield of Recovery diphenyl Product (wt. %) conditions diisocyanates of phenol ether 1,6-hexamethylene 5% 240 C./ 70% 100% 85% diisocyanate (HDI) 1 hr 1,12-dodecamethylene 25% 240 C./ 80% 100% 100% diisocyanate (DDI) 0.5 hr isophorone 10% 240 C./ 86% 100% 90% diisocyanate (IPDI) 1 hr

(104) Structures of Diisocyanate Products

(105) ##STR00014##

(106) The examples above clearly indicate that aliphatic diisocyanates can be prepared under a high yield by a process involving a non-phosgene route (NPR), where aliphatic diphenyl N,N-alkenylbiscarbamates act as reaction intermediates and are thermolyzed in mild reaction conditions and, in particular, in the absence of catalyst during the procedure.

(107) In the preparation of biscarbamates, the yield of the product from carbonylation of diamines with diphenyl carbonate is highly affected by polarity of solvents. When a non-polar solvent (such as toluene or methylcyclohexane) is used, the rate of carbonylation is slower. On the other hand, when a solvent having high polarity (such as N-methyl-2-pyrrolidone (NMP) or N,N-dimethylacetamide (DMAc)) is used, the rate of carbonylation significantly increases but the amount of the byproduct urea also increases. For example, it was observed that using N-methyl-pyrrolidone in the preparation of biscarbamates at 80 C. only provided a yield of 52%, and the amount of the byproduct urea resulting from a further reaction of biscarbamates and amines significantly increased. Therefore, the inventors choose to use a solvent having low polarity (such as ethers or alcohol ethers) in the preparation of biscarbamates. It is preferred to use ethylene glycol diethyl ether (EGDEE) as a reaction solvent since the reaction can be completed within 2 hours at 25 to 40 C. and no urea byproduct is produced. In addition, biscarbamates can be obtained at a high purity by simple filtration after cooling the bulk to 25 C. for precipitation. The liquid mixture can be refined so that ethylene glycol diethyl ether (EGDEE) can be recovered up to an extent of 93% and reused in carbonylation in the preparation of biscarbamates.

(108) Ethylene glycol diethyl ether (EGDEE) possesses a low dipole moment (310.sup.6 Debye) and can well dissolve the mixture of amines and diphenyl carbonate at room temperature. In addition, the synthesis involving carbonylation can be conducted at 60 C. while the formation of the byproduct urea at a higher temperature can be prevented.

(109) In the thermolysis of diphenyl N,N-alkenylbiscarbamates for the preparation of aliphatic diisocyanates, non-polar hydrocarbon solvents such as n-dodecane (dipole moment=0) and several alkyl lubrication oils (dipole moment=0) were evaluated, which exhibit poor efficiency. Further analysis by HPLC indicated that the product contains oligomers such as isocyanurates. The result means that aliphatic diisocyanates are unstable in the solution (where n-dodecane acts as the solvent) when the temperature is over 200 C. during the synthesis procedure and oligomer byproducts are likely to be produced. On the other hand, using solvents having high polarity such as phenyl benzoate or dipolar solvents such as tetramethylene sulfone for thermolysis also yields poor result. In addition to the formation of deep yellow byproducts, the formation of trimers and carbodiimides seems to consume the desired product diisocyanates, resulting in an undesirably low yield.

(110) The inventors found that solvents having low polarity, such as diphenyl ether, are preferable ones to be used in the thermolysis. Hence, it is disclosed to use solvents having low polarity in the thermolysis of aliphatic biscarbamates. Diphenyl ether is one of the suitable solvents since all aliphatic isocyanates can be isolated therefrom and phenol can be completely recovered. The reaction time is also significantly shortened. The result means that the incompatibility between the aromatic solvent, diphenyl ether (DPE), and aliphatic isocyanates is beneficial to bring the effect of azeotropic distillation and thereby aliphatic isocyanates can be isolated from the mixture. Moreover, no metal catalyst is used during the entire procedure.

(111) Finally, the inventors design a novel one-pot and non-phosgene process based on the NPR route where step 1 involves preparing biscarbamates and step 2 involves thermolysis. For instance, 1,12-dodecanediamine (DMDA) could be carbonylated with diphenyl carbonate (DPC) in a diphenyl ether (DPE) solvent at 60 C. to prepare biscarbamates. At a solid content of 25%, the yield of biscarbamates (DMBPC) was nearly 100% while no urea byproduct was formed based on the analysis of infrared spectroscopy and HPLC. The solution was then directly heated to 240 C. for about 0.5 hours and the formation of 1,12-dodecamethylene diisocyanate and the disappearance of biscarbamates (DMBPC) were monitored by infrared spectroscopy. Finally, diphenyl ether (DPE) solvent was completely removed by distillation. The final product, 1,12-dodecamethylene diisocyanate (DDI, diisocyanate), could be isolated and the yield reached 80%, while the recovery of phenol also reached 100%. In comparison with the two-step process, one-pot NPR process is simpler while the product can be obtained at a comparable yield. This one-pot NPR process was also successfully applied to the preparation of isophorone diisocyanate from isophorone diamine at a yield reaching 86%.

(112) In the subject invention, the non-phosgene route (NPR) processes in the preparation of aliphatic diisocyanate adopt several key principles in green chemistry and are well suited for the preparation of all aliphatic diisocyanates. Toxic carbonylation agents such as phosgene and metal catalysts are also avoided. In view of the advantages in safety and pollution, the non-phosgen route processes in the subject invention can replace current phosgen processes which are unsafe and toxic and can be applied in mass production of aliphatic diisocyanates at an industrial scale.

(113) A person of ordinary skill in the art of the subject invention should understand that variations and modification may be made to the teaching and the disclosure of the subject invention without departing from the spirit and scope of the subject application. Based on the contents above, the subject application intends to cover any variations and modification thereof with the proviso that the variations or modifications fall within the scope as defined in the appended claims or their equivalents.