CN106349110A - Two-stage method and one-pot synthesis method for preparing aliphatic diisocyanate - Google Patents

Abstract

The invention relates to a two-stage method and one-pot synthesis method for preparing aliphatic diisocyanate. The two-stage method or the one-pot synthesis method is adopted for preparing aliphatic diisocyanate through aliphatic diamine and diaryl carbonic ester. Also, aliphatic polyamine and diaryl carbonic ester also can be used for preparing polyisocyanates. According to the synthesis method provided by the invention, phosgene or highly toxic reagents and a chlorinated solvent are not adopted during the whole process.

Description

Prepare the two step method of aliphatic diisocyanate and one pot be combined to method

Technical field

The present disclosure generally relates to method is combined to two step method or one pot aliphatic is prepared with diaryl carbonate by aliphatic diamine Diisocyanate, also can prepare aliphatic polyisocyante by aliphatic polyamine and diaryl carbonate.It is different from existing Industrial aliphatic diisocyanate phosgene processing procedure, the synthetic method whole process of the present invention do not adopt phosgene or hypertoxicity Reagent and chlorinated solvents.

Background technology

Isocyanates have wide range of industrial applications, for example, be used for manufacturing polymer, are especially for producing polyamine group formic acid Organic diaryl isocyanates of ester, polyurethane/urea, polyureas and related polymer and polyaryl isocyanates.

Aryl polyisocyanates and aliphatic polyisocyanate all have various purposes.Aromatic dissocyanate, such as 2,4- Toluene di-isocyanate(TDI) and 2,6- toluene di-isocyanate(TDI) (tdi) and 4,4'- methyl diphenylene diisocyanate (mdi), due to Cost and efficiency consideration, its reactivity effectiveness quickly and its in shaping polyurethane and block foam production, be Account for the major part (> 90% of isocyanates production).However, global mdi and tdi more than 350,000 tons for the total output every year Production method be still using based on phosgenation.And in recent years it has been found that aliphatic diisocyanate (adis) Product has more excellent yellowing resistance than aromatic diisocyanate product, and aliphatic diisocyanate (adis) Extensively it is concerned and obtains more applications.At present industrialized production adis is still with phosgenation for the most large processing procedure, by institute With phosgene, there is toxicity and corrosivity hydrogen chloride can be produced in producing, under the dual consideration of safety and environmental protection, nearest 30 years Between be the green processing procedures such as the non-phosgene process that is devoted to seeking manufacturing aliphatic diisocyanate (adis), preferably to accord with Closing public's ring peace needs and Workplace Safety.

From current document and patent, on the non-phosgene processing procedure of aliphatic diisocyanate (adis), also oneself sends out warp Put on display following six kinds of main processing procedure paths, comprise solid phosgene method (solid-phosgene), carbon dioxide processing procedure (co₂ Process), dimethyl carbonate processing procedure (dmc process) or (co is reacted with carbon monoxide complexed metal catalyst Carbonylation process), ester-interchange method (transesterification) and high-temperature cracking method (pyrolysis) etc. replace light The method of gas.

(1) solid-state triphosgene (triphosgene)

The research of heiner in 1987 shows (heiner eckert, barbara forster.triphosgene, a crystalline phosgene substitute.angew.chem.int.ed.engl.1987；26 (9): 894-5) with double (trichloromethyl) carbonic ester (bis (trichloromethyl) carbonate), is that the Main Ingredients and Appearance of three photooxidation methods replaces optical self-encoding hdi, the chemistry of reaction Formula is as follows:

Though this reagent is solid and has higher fusing point and relatively low volatility (or vapour pressure) during reaction, it Substantial amounts of gas chlorination hydrogen still can be produced generate, cause the corrosion failure of equipment, thus be unfavorable for commercial Application.

(2) nitro compound oxonation (carbonylation of nitro-compounds)

The research of olin company of the U.S. in 1985 shows and carries out being catalyzed directly by nitro compound in reduction and with platinum, rhodium Isocyanates are converted to, the chemical formula of reaction is as follows in the presence of carbonoxide:

However, the method is rarely seen being applied in industrial process, main cause is that isocyanates yield is too low, reacts bar Part harshness need to be carried out at high temperature under high pressure, and noble metal catalyst reclaims and is difficult.

(3) oxidation and carbonylation (oxidative carbonylation of primary amine) of mono-amine compound

In the patent that the fukuoka s of Japanese asahi company in 1984 is delivered, (jp s60-226852) is urged with palladium Change and Diamines, carbon monoxide, oxygen be converted to hdi and water, the chemical formula of reaction is as follows:

Noble metal catalyst used in reaction reclaims and is difficult, and production process can produce by-product h₂O and will reduce different The yield of cyanate with separate the problem being difficult.

(4) ester-interchange method (trans-esterification)

In the patent (ep 0327231 a1) that the thorpe d of ici company of Britain in 1988 is delivered in chlorobenzene solvent The hexamethylene diamine (hda) of aliphatic diamine class is carried out ester exchange reaction with aromatic diisocyanate mdi, obtains yield about The hdi of 40% aliphatic diisocyanate, the chemical formula of reaction is as follows:

But products collection efficiency is low, and also there is the problem being not readily separated.

(5) carbon dioxide carbonylation processing procedure method (co₂-carbonylation of aliphatic amines)

The patent (us 5451697 a) that mcghee william in monsanto company of the U.S. in 1993 et al. is delivered In, using acetonitrile solvent by hda and co₂In 0 DEG C of reaction 1.5hr synthesis amidocarbonic acid under triethylamine (tea) catalysis After ammonium salt, reuse sulfonic acid benzoyl oxide (sba) or trichlorine phosphoric acid (phosphorus oxychloride, pocl₃) dehydrant Carry out dehydration, synthesis hdi (yield about 81%) and h at -20 DEG C₂O, the chemical formula of reaction is as follows:

But the reagent (dehydrant) being used in second step still must use highly active chloride, and the pollution for environment is big And be not readily separated.Additionally, during generate h₂If fall can be reacted with the hdi of final product when o fails effectively to remove Low-yield.

(6) high-temperature cracking method (pyrolysis)

Although above-mentioned non-phosgene has improvements in security to a certain extent than the processing procedure of original tradition phosgenation, also Be exist yield poorly, speed is slow, need high temperature or the harsh reaction condition of high pressure, or during need to use precious metal catalyst Agent, leads to significantly limit the application of their practicality and commercialization.Also the therefore 20 later stages eighties in century started Carrying out Pintsch process after being extensively studied synthetic intermediate diamine carbamate (biscarbamates) again is diisocyanate Two step non-phosgene processing procedures.Obtained through after the various different types of diamine carbamate intermediate of synthesis again Pintsch process The diisocyanate obtaining, can reach higher yield.For example, intermediate can be chlorination silicomethane amido formate (chlorosilylcarbamate), urea, hexamethylene diamine base methyl formate (n, n '-dimethyl Hexane-1,6-diyldicarbamate, hdu) etc., wherein gathered around with the processing procedure of hexamethylene diamine base methyl formate (hdu) again There is more interesting advantage and by extensive numerous studies.

A () is with chlorination silicomethane amido formate as intermediate

In the patent application case (ca 1108174 a2) of union carbide company of the U.S. in 1976, synthetic method comprises Three steps: (a) is first by hda, co₂And the reaction of chlorine silicomethane generates silicomethane amido formate and hcl；B () again Carry out the displacement of silicomethane with trichloro-benzenes silane reaction；C () adds nh₃Neutralization carries out Pintsch process reaction after removing hcl Generate hdi.The chemical formula of reaction is as follows:

Although during do not use phosgene, the hcl producing not only can etching apparatus, also can carry out with hdi more simultaneously Reversible reaction forms chloromethane amide.Additionally, the side-product of chlorosilane greatly and is not readily separated for the pollution of environment.

B () is with urea (urea) as intermediate

In 1989 arco house journal of U.S. application case (ep 0408277 a2), synthetic method comprises the steps of A hda is first generated hexa-methylene two urea with isocyanate reaction by ()；B () hexa-methylene two urea reacts generation again with diethylamine Hexamethylene bis (diethyl urea)；C () last hexamethylene bis (diethyl urea) carry out Pintsch process reaction and generate hdi, instead The chemical formula answered is as follows:

h₂nconh(ch₂)₆nhconh₂+2nh(c₂h₅)₂→(c₂h₅)₂nconh(ch₂)₆nhcon(c₂h₅)₂+2nh₃

But expensive starting materials, and use poisonous dimethylbenzene and hnco.Additionally, the response speed of entirety is slow.

C () is with hexamethylene diamine base methyl formate (hdu) as intermediate

Can divide into hexamethylene diamine base methyl formate (hdu) intermediate going out synthesized by path from different material again Nitro reducing carbonyl reaction (reductive carbonylation of nitro compounds), amido oxidation carbonylation (oxidative carbonylation of amine compounds), urea element alcoholysis method (alcoholysis of urea) and carbonic acid Dimethyl ester amine-decomposing method (dimethyl carbonate ammonolysis) these four methods

1. nitro reducing carbonyl reaction (reductive carbonylation of nitro compounds)

Hispanic sergio c m in 1988 propose (sergio cenini, corrado crotti, maddalena pizzotti, francesca porta.ruthenium carbonyl catalyzed reductive carbonylation of aromatic nitro compounds.a selective route to carbamates.j org.chem.1988；53 (6): 1243-50.) in palladium (pallidium, pd) or ruthenium (ruthenium, ru) noble metal be catalyzed down by organic for 1,6-dinitrohexane itrated compound, co、ch₃Oh reaction obtain hexamethylene diamine base methyl formate (hdu) carry out again Pintsch process reaction obtain hdi with ch₃Oh, advantage is that this processing procedure reaction condition is gentle, by-product is few, but shortcoming is the recovery of precious metal catalyst, instead Answer the conversion ratio about only 1/3 of the co of thing, so having with product co₂Separate the problem being difficult, and because gas Body co2 reaction needs are more harsh and relatively costly under the reaction condition of high pressure, and the chemical formula of reaction is as follows:

2. amido oxidation carbonylation (oxidative carbonylation of amine compounds)

In the document that the fukuoka shinsuke of Japanese asahi company in 1985 is delivered (fukuoka shinsuke, masazumi chono,masashi kohno.a novel catalytic synthesis of carbamates by the oxidative alkoxycarbonylation of amines in the presence of platinum group metal and alkali metal halide or onium halide.j org.chem.1984；49 (8): 1458-60.) propose in palladium (pallidium, pd) or potassium iodide (ki) noble metal is catalyzed down hexamethylene diamine, co, o₂、ch₃Oh reaction obtains hexamethylene diamine base methyl formate (hdu) carry out Pintsch process reaction again and obtain hdi and h₂O, advantage is that this processing procedure is simple, conversion ratio and selectivity all relatively Height, but shortcoming is that side reaction thing is many, and the chemical formula of reaction is as follows:

3. urea alcoholysis method (alcoholysis of urea)

In the patent that the franz of German basf company in 1986 is delivered (us 4596678 a) propose li, ca, sn, The metallic salts such as cu are catalyzed down hexamethylene diamine, urea, ch₃Oh reaction obtains hexamethylene diamine base methyl formate (hdu) carry out Pintsch process reaction again and obtain hdi and ch₃Oh, advantage be this processing procedure hdu yield up to 90% with Hdi/ipdp/h12mdi that is upper, being widely portable to aliphatic isocyanates, but shortcoming is that the reaction procedure time is more long, The chemical formula of reaction is as follows:

4. dimethyl carbonate ammonolysis method (dimethyl carbonate ammonolysis)

In the patent that Hispanic sergio in 2003 is delivered, (us 6639101 b2) proposes to enter in alkali or alkaline earth metal Under row catalysis, hexamethylene diamine, dimethyl carbonate (dmc) reaction are obtained hexamethylene diamine base methyl formate (hdu) and carry out Pintsch process reaction obtains hdi and ch₃Oh, and by-product ch₃Oh can pass through oxidation and carbonylation (oxidative Carbonylation) again with co, o₂Reaction obtains dimethyl carbonate (dmc) and h2o reaches recyclable cycling and reutilization Purpose, advantage be this processing procedure reaction condition is gentle, environmental protection, by-product can recycle, but shortcoming is secondary anti- Answer thing many, and the chemical formula that hdu changes into the ardent solution temperature drift reaction of hdi be as follows:

Content of the invention

Therefore, the present invention provides a kind of method preparing aliphatic diamine carbamate or aliphatic polyamine carbamate, its Including making aliphatic diamine or aliphatic polyamine and diaryl carbonate react in low polar solvent, to produce at least one Plant aliphatic diamine carbamate or aliphatic polyamine carbamate as the aliphatic front glove (or first step) of system.

The present invention also provides a kind of non-phosgene synthetic method preparing aliphatic diisocyanate or aliphatic polyisocyante, It includes making aliphatic diamine or aliphatic polyamine and diaryl carbonate react in the first low polar solvent, produces fat Fat race diamine carbamate or aliphatic polyamine carbamate, and then make aliphatic diamine carbamate or many amidocarbonic acid Ester thermal cracking (thermolysis) in the second low polar solvent, to produce aliphatic diisocyanate or aliphatic polyisocyanic acid Ester, wherein said second low polar solvent is identical or different with described first low polar solvent.

The present invention also provides a kind of prepare aliphatic diisocyanate or the synthesis of aliphatic polyisocyante non-phosgene one pot Change method, it comprises to make aliphatic diamine or aliphatic polyamine and diaryl carbonate carry out in the second low polar solvent instead After aliphatic diamine carbamate or aliphatic polyamine carbamate should be generated, carry out follow-up hot tearing in same reactor Solution, to produce aliphatic diisocyanate or aliphatic polyisocyante.

Each aspect of present invention disclosed herein and each embodiment are intended to and every other disclosed state of the present invention Sample and embodiment individually combine and are combined into its all possible combination.

In this specification and claim, unless the other clear stipulaties of context, otherwise singulative " " and " described " inclusion plural number.Unless other advocate, otherwise using any and all example provided in this article or exemplary language Speech (such as " such as ") present invention only to be better described, and scope of the invention is not formed and limit.In this specification Language should not be construed as instruction any key element do not advocated be enforcement the present invention required.

Should be appreciated that any numerical range cited in this description is intended to all underranges comprising to be included in it.Example As included from the scope of " 50 DEG C to 70 DEG C " between 70 DEG C of the greatest measure of 50 DEG C of the minimum value and statement stated All of underrange (as from 58 DEG C to 67 DEG C, 53 DEG C to 62 DEG C, 60 DEG C or 78 DEG C) and comprise described two numerical value, also Comprise the minima equal to or more than 50 DEG C and the scope of the maximum equal to or less than 70 DEG C.Because disclosed Numerical range is continuous, and therefore they comprise each numerical value between minima and maximum.Unless otherwise noted, no The various numerical rangies then indicating in this description are outline values.

Diaryl carbonate

Diaryl carbonate used in the inventive method is the compound being represented by following formula (1):

Wherein r¹And r²Represent the aromatic group with 6 to 20 carbon atoms, and former for having 6 to 12 carbon The aromatic group of son.In the case that aryl has two or more substituent groups, these substituent groups can mutually the same or Different from each other.

r¹And r²In the substituent group that can contain be selected from the alkyl or cycloalkyl with 1 to 12 carbon atom, such as first Base, ethyl, propyl group and butyl；There is the aralkyl of 7 to 15 carbon atoms, such as benzyl and phenethyl；Have 6 To the aryl of 14 carbon atoms, such as phenyl and tolyl；There is the alkoxyl of 1 to 12 carbon atom, such as methoxy Base, ethyoxyl, propoxyl group, butoxy and trifluoromethoxy；There is the thioalkoxy group of 1 to 12 carbon atom, for example Sulfur methoxyl group and sulfur ethyoxyl；There is the aryloxy group of 6 to 14 carbon atoms, such as phenoxy group；Halogen, such as fluorine, Chlorine and bromine；Nitro；Hydroxyl；Cyano group；And dialkyl amino, such as dimethyl amido.

The r being substituted and being unsubstituted¹And r²Including such as phenyl, naphthyl, anthryl, tolyl, xylyl, second Base phenyl, propyl group phenyl, octyl phenyl, nonyl phenyl, dodecylphenyl, biphenyl, methoxyphenyl, chlorphenyl, Dichlorobenzene base, trichlorophenyl, five chlorophenyl, bromophenyl, dibromo phenyl, tribromo phenyl, penta-bromophenyl, nitrobenzophenone, Dinitrophenyl, hydroxy phenyl, cyano-phenyl and dimethyl amido phenyl.

Additionally, these aryl include o-, m- and to isomer, and connect to the substituent group of aryl include just, different, second And the 3rd isomer.

Particularly, the diaryl carbonate having aryl that is mutually the same and being unsubstituted is selected from (but not limited to) hexichol Base carbonic ester, two -1- naphthyl carbonic esters, two -2- naphthyl carbonic esters and two -9- anthryl carbonic esters.

There is mutually the same and the aryl of at least one alkyl replacement of respectively hanging oneself diaryl carbonate and be selected from (but not limited to) Double (2- tolyl) carbonic esters and double [4- { tributyl } phenyl] carbonic ester.

The diaryl carbonate with aryl that is mutually the same and replacing through at least one aryl respectively may include (but not limited to) Double (4- biphenyl phenyl) carbonic ester.

There is mutually the same and the aryl of at least one alkoxyl replacement of respectively hanging oneself diaryl carbonate be selected from (but not limiting In) double (2- methoxyphenyl) carbonic esters and double (3- butoxy phenyl) carbonic ester.

There is mutually the same and the aryl of at least one halogen atom replacement of respectively hanging oneself diaryl carbonate be selected from (but not Be limited to) double (2- chlorphenyl) carbonic ester, double (2,4 dichloro benzene base) carbonic ester and double (2,4,6- trichlorophenyl) carbonic ester.

There is mutually the same and the aryl of at least one nitro replacement of respectively hanging oneself diaryl carbonate and be selected from (but not limited to) Double (2- nitrobenzophenone) carbonic esters and double (dinitrophenyl group) carbonic ester.

There is the aryl being unsubstituted and the diaryl carbonate of the aryl replacing through at least one alkyl is selected from (but not limiting In) 3- tolyl benzol carbonate and 4- tolyl benzol carbonate.

There is the aryl being unsubstituted and the diaryl carbonate of the aryl replacing through at least one aralkyl may include (but not It is limited to) 4- Benzylphenyl (phenyl) carbonic ester.

There is the aryl being unsubstituted and the diaryl carbonate of the aryl replacing through at least one alkoxyl is selected from (but not It is limited to) 4- methoxyphenyl benzol carbonate and 4- ethyoxyl -1- naphthylphenyl carbonic ester.

Have the aryl being unsubstituted and through at least one thioalkoxy group replace aryl diaryl carbonate be selected from (but It is not limited to) 4- methyl thio phenyl benzol carbonate.

There is the aryl being unsubstituted and the diaryl carbonate of the aryl replacing through at least one aryloxy group may include (but not It is limited to) 4- Phenoxyphenyl benzol carbonate.

Have the aryl being unsubstituted and through at least one halogen atom replace aryl diaryl carbonate be selected from (but It is not limited to) 2- chlorphenyl benzol carbonate and 4- chlorphenyl benzol carbonate.

There is the aryl being unsubstituted and the diaryl carbonate of the aryl replacing through at least one nitro is selected from (but not limiting In) 3- nitrobenzophenone benzol carbonate and dinitrophenyl group benzol carbonate.

There is the aryl being unsubstituted and the diaryl carbonate of the aryl replacing through at least one hydroxyl is selected from (but not limiting In) 3- hydroxy phenyl benzol carbonate and 4- hydroxy phenyl benzol carbonate.

Be applied to the inventive method other diaryl carbonates include such as 4- methoxyphenyl -4'- nitrophenyl carbonate, 4- cyano-phenyl -4'- nitrophenyl carbonate, 4- sulfur methoxyphenyl -4'- nitrophenyl carbonate, 2- chlorphenyl -4'- nitro Benzol carbonate, 2- dimethyl amido phenyl carbonic ester, 2- bromo- 4- cyano group -6- nitrobenzophenone benzol carbonate and pentabromo- Phenyl -2', 4', 6'- tribromo benzol carbonate.

In above-mentioned diaryl carbonate, using diphenyl carbonate, double (2- tolyl) carbonic ester, double (4- chlorobenzene Base) carbonic ester, double (4- nitrobenzophenone) carbonic ester and double (3,5- Dimethoxyphenyl) carbonic ester, and more using diphenyl Carbonic ester.

Aliphatic diamine and aliphatic polyamine

Aliphatic or mixed virtue aliphatic are covered in the definition system of " aliphatic " the second word described in present invention full text, but do not comprise Pure aromatic series.

Aliphatic diamine compound used in the inventive method comprises the compound for example being represented by following formula (2):

h₂n-r³-nh₂(2)

r³Example may include (but not limited to) c_1-16Straight-chain alkyl, such as methylene, dimethylene, trimethylene, four Methylene, pentamethylene, hexa-methylene, eight methylene or ten dimethylenes；c_3-16Cyclic hydrocarbon radical, such as cyclopenta, ring Hexyl, suberyl, cyclooctyl, double (cyclohexyl) or the cyclooctyl replacing through alkyl；The cyclic hydrocarbon radical replacing through alkyl, all As methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl, butylcyclohexyl, penta Butylcyclohexyl or hexyl cyclohexyl；Through identical or different c_1-6The dibasic c of alkyl_3-16Cyclic hydrocarbon radical, such as diformazan basic ring Hexyl, diethyl butylcyclohexyl；The cyclic hydrocarbon radical replacing through trialkyl, such as 1,5,5- trimethylcyclohexyl, 1,5,5- triethyl groups Cyclohexyl, 1,5,5- tripropyl cyclohexyl or 1,5,5- tributyl cyclohexyl.Special speech, the compound of aliphatic diamine For butanediamine (bmda), hexamethylene diamine (hmda), dodecamethylene diamine (dmda), cyclohexylamine, isophorone diamine and stretch Methyldicyclohexyl diamidogen.

Aliphatic diamine compound used in the inventive method also comprises aralkyl diamidogen, the such as compound of following formula (3):

h₂n-ar-r³-nh₂(3)

Wherein ar represents c_6-9Stretch aryl, r³Literary composition as defined above is described.Aralkyl diamidogen used by the present invention is, for example, 4- (amido ethyl) aniline etc..

Aliphatic polyamine compound used in the inventive method means the aliphatic hydrocarbon of the amido with three or more, Can be for example the compound being represented by following formula (4):

r⁴(nh₂)_p(4)

r⁴It is as defined above and state r³, the positive integer of p representative at least 3.

Aliphatic polyamine example used in the inventive method is propane -1,2,3- triamine, two stretch second triamine, double (six methylenes Base) triamine, three stretch second tetramine, 3- aminomethyl -1,6- hexamethylene diamine and 1,3,6- tri- amido normal hexane etc..In the inventive method Aliphatic polybasic amines used also comprise aralkyl polyamine.

Low polar solvent

" low polar solvent " described in present invention literary composition comprises the first low polar solvent and the second low polar solvent.

As the low polar solvent being applied to the present invention, comprise to know that those skilled in the art known is suitable in technical field that the present invention belongs to When low polarity and nonpolar solvent, its boiling point between 50 DEG C to 250 DEG C, for example may include (but not limited to) ether or Alcohol ether.

Ethers used in the present invention is the compound with ether functional group, that is, has the oxygen connecting two alkyl or aryls The compound of the functional group of atom.In the inventive method, the ether of be used as low polar solvent may be, for example, to be represented by following formula (5) Compound:

r⁵-o-r⁶(5)

r⁵With r⁶Independently represent c_1-9Alkyl, c_6-9Aryl or c_6-12Aralkyl；Or

r⁵With r⁶And oxygen atom together forms ring structure cyclic ethers.

Ethers can be aryl ether, aliphatic ether, ring grease ether or mixed virtue fat ether, example comprise diethyl ether, methyl phenyl ethers anisole, diphenyl ether, Oxolane, 1,4- dioxanes etc..

Used in the inventive method can be also alcohol ether as low polar solvent, comprise aryl alcohol ether, aliphatic alcohol ether or mixed virtue fat Alcohol ether, example is glycol ethers (glycol ether), such as alkane glycol ethers, such as alkane glycol dioxane ether, alkane glycol aralkyl Ether or alkane glycol two aryl oxide.One example of alkane glycol ethers is glycol ether, and it is to be the compound being represented by following formula (6):

r⁷-(o-(ch₂)₂-)_aor⁸(6)

r⁷With r⁸Independently represent c_1-9Alkyl, c_6-9Aryl or c_6-12Aralkyl；And

A represents 1 to 3 integer.

The example of formula (6) compound may include glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, three second two Diethylene glycol dimethyl ether etc..

Manufacture diamine carbamate and many amido formates

Aliphatic diamine carbamate or aliphatic polyamine carbamate are by aforesaid aliphatic diamine and diaryl carbon Acid esters reacts preparation in the first low polar solvent.The method can be at a lower reaction temperature by aliphatic diamine or aliphatic Polyamine effectively manufactures and isolates aliphatic diamine carbamate or many amido formates.

First low polar solvent system is as it was previously stated, can be any low polar solvent defined in the present invention.It is two Ether, methyl phenyl ethers anisole, diphenyl ether, oxolane, 1,4- dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, diethyl Glycol dimethyl ether, TRIGLYME etc.；More diethyl ether, oxolane, 1,4- dioxanes, ethylene glycol bisthioglycolate Methyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether etc..

In an embodiment of the aliphatic diamine carbamate manufacture method of the present invention, using the aliphatic of 1:2 to 1:5 The mole ratio of diamine compound and diaryl carbonate；Aliphatic diamine compound and two virtues using 1:2 to 1:4 The mole ratio of base carbonic ester；And more using aliphatic diamine compound and the diaryl carbonate of 1:2.0 to 1:3.0 Mole ratio.

In an embodiment of the aliphatic diamine carbamate manufacture method of the present invention, the solute using 20 to 100% is dense Degree；Using 25 to 90% solute concentration；More using 40 to 75% solute concentration, and more use About 50% solute concentration.

In the aliphatic diamine carbamate manufacture method of the present invention, any metallic catalyst can be not related to, or select Property use non-metallic catalyst, such as carboxylic acid, described carboxylic serials are selected from benzoic acid, to tributyl benzoic acid, right Anisic acid, isopropylformic acid., the group of propanoic acid, butanoic acid and pivalic acid composition.When being used aralkyl diamidogen as reactant, Then using non-metallic catalyst.

According to the present invention, can effectively be manufactured by aliphatic diamine at a lower reaction temperature and the double amidocarbonic acid of fractionation of fatty race Ester, such as carry out producing the reaction of diamine carbamate at a temperature of 0 to 100 DEG C, be 15 to 100 DEG C, more For 15 to 60 DEG C, such as 15 to 25 DEG C or room temperature are to 60 DEG C.According to aliphatic diamine carbamate in the present invention Manufacture method, after completion of the reaction, make in aimed aliphatic race diamine carbamate reaction mixture precipitate and received Collection.In collection step, make the temperature of reactant mixture be cooled to room temperature, or be controlled to about 40 DEG C or less than 40 DEG C, It is about 40 DEG C to about 0 DEG C, more about 30 DEG C to about 10 DEG C, so that aliphatic diamine carbamate autoreaction Precipitate in mixture, and carry out the aliphatic diamine carbamate of precipitation separation by separate modes such as filtration or centrifugations And collected.

Produced reactant mixture can be processed to separate and collect aliphatic diamine carbamate.For example, can mat So that the reaction medium in reactant mixture, carboxylic acid and phenolic compounds reaction mixture is separated, and directly collect surplus Remaining solid matter, or wash solid matter with solvent, or so that it is recrystallized, to separate and to collect the double amidocarbonic acid of aliphatic Ester.

If necessary, mother solution can be made after filtering adipose race diamine carbamate to stand above-mentioned another process, advantageously to reclaim Remaining more aliphatic diamine carbamates in mother solution.

Filter or centrifugation after, optionally remove as by-product generation by distillation or wash with solvent (such as toluene) Phenolic compounds and the reaction medium from mother solution, and add the diaryl carbonate of necessary amounts, amines in mother solution And after selective catalyst, in the reusable manufacture method in the aliphatic diamine carbamate of the present invention of mother solution.

Although the diamine carbamate purity that manufactures in the process of the present invention be enough to directly carry out follow-up application, if necessary, also Further corps race diamine carbamate can be carried out by applying recrystallization.The solvent being applied to recrystallization includes (but not limiting In) aromatic hydrocarbon (such as benzene, toluene and dimethylbenzene)；Aliphatic alcohol (such as ethanol and n-butyl alcohol)；And ether (such as di-n-propyl ether)； Ester (such as ethyl acetate and isobutyl acetate and acetic acid cyclohexyl ester)；And ketone (such as methyl iso-butyl ketone (MIBK) and Ketohexamethylene).

Two step method manufactures isocyanates or polyisocyanates

The present invention also provides a kind of hot tearing preparing aliphatic diisocyanate or the synthesis of aliphatic polyisocyante non-phosgene Solution, it includes making aliphatic diamine carbamate or aliphatic polyamine carbamate thermal cracking in the second low polar solvent Step.

The second low polar solvent system used in the present invention is as it was previously stated, can be any low polarity defined in the present invention Solvent.First low polar solvent and the second low polar solvent can be identical or different person.Second low polar solvent is more Methyl phenyl ethers anisole, diphenyl ether, diethylene glycol dimethyl ether, TRIGLYME etc..

The one concrete aspect of the present invention is to obtain the present invention by second low polar solvent with higher The diamine carbamate obtaining carries out pyrolysis to produce diisocyanate.Find the low polarity being defined using the present invention Solvent can accelerate removing of the phenol producing in heating, and slow down the carbonization caused by isocyanate product dimerization simultaneously The formation of diimine by-product.This two effects are for guaranteeing in thermal cracking processing procedure with high yield by hdi, ddi, ipdi Deng diamine carbamate formed hdi, ipdi etc. aliphatic product be necessity person.

Pyrolysis in the embodiment of the present invention should be in same step by aliphatic amine carbamate or aliphatic polyamine Carbamate forms corresponding diisocyanate (hdi, ddi, ipdi) or polyisocyanates and aromatic hydroxy compound (phenol) Reaction, and can be easily by diisocyanate or polyisocyanic acid ester products and aromatic hydroxy compound after heat scission reaction (phenol) separates.

The second low polar solvent being used in the heat scission reaction of two step method, is boiling point the higher person, for example formula (5) In the compound representing, r⁵With r⁶Independently represent c_6-9Alkyl, c_6-9Aryl or c_6-12The ether compound of aralkyl； Or the compound mid-boiling point that formula (5) or formula (6) represent is not less than the reaction temperature person carrying out thermal cracking.

Another specific embodiment is low compared with first in the boiling point of the second low polar solvent that used of heat scission reaction of two step method Polar solvent is high.

The reaction temperature of thermal cracking is enough to make diamine carbamate or many amido formates that the temperature of heat scission reaction to occur, Depending on factors such as pressure, solvents, for example, can be 100 to 250 DEG C, such as 150～240 DEG C.Reaction pressure can be for subtracting Pressure or normal pressure, such as between 0.01mmhg and 760mmhg.In the situation being removed by-product phenol at any time Under, reaction temperature can be relatively low.

There is not special restriction to the response time.In generally at most 3 hours response time, be 0.5 hour to 2 hours, And more 0.5 hour to 1 hour.In certain embodiments, when being carried out with continuous or flowing thermal splitting system, instead Shorten a lot between seasonable, or even several minutes can be shorten to and can complete to several tens minutes.

Change legal system for one pot and make diisocyanate or polyisocyanates

The present invention also provides a kind of prepare aliphatic diisocyanate or the synthesis of aliphatic polyisocyante non-phosgene one pot Change method, after methods described comprises to make aliphatic diamine compound or aliphatic polyamine and diaryl carbonate be reacted, The step carrying out follow-up thermal cracking in same reactor is to prepare aliphatic isocyanates or aliphatic polyisocyante.

According to aforementioned two step method of the present invention, the diamine carbamate obtained by first step because having sufficiently high purity, And the step of the step of synthesizing isocyanate in two step method and thermal cracking isocyanates can be combined, and select suitable reaction Condition and solvent, thus obtain and obtained close yield and purity diisocyanate or polyisocyanates with two step method.One pot Change legal system and make diisocyanate or the reaction condition of polyisocyanates is generally identical with two step method, but advantage be to save by Diamine carbamate or the isolated step out of many amido formates, can time-consuming and energy cost.

Change the second low polar solvent manufacturing used in diisocyanate or polyisocyanates method in one pot, for boiling Point the higher person, such as in the compound that formula (5) represents, r⁵With r⁶Independently represent c_6-9Alkyl, c_6-9Aryl or c_6-12 The ether compound of aralkyl；Or the compound mid-boiling point that formula (5) or (6) represent is not less than the reaction temperature carrying out thermal cracking Person.

One pot of reaction temperature changing reaction is enough to forming diamine carbamate or many amido formates and bringing it about hot tearing The temperature of solution reaction, depending on factors such as pressure, solvents, for example, can be 120 to 250 DEG C, such as 240 DEG C.Reaction Pressure can be decompression or normal pressure, such as between 0.01mmhg and 760mmhg.By by-product phenol at any time by In the case of removing, reaction temperature can be relatively low.

There is not special restriction to the response time.In generally at most 3 hours response time, be 0.5 hour to 2 hours, And more 0.5 hour to 1 hour.In certain embodiments, the thermal cracking time can shorten to several minutes to several tens minutes, The response time for example can be shortened under reduced pressure for 0.1 hour to 1 hour, or 10 to 25 minutes.

Manufacture polyureas

According to the present invention, can be direct with amines or its mixture by aliphatic diamine carbamate or many amido formates Prepare polyureas.In the presence of polar solvent, make aliphatic diamine carbamate or the polyamines obtaining by said method Carbamate to manufacture polyureas with amines or its mixture reaction.

It is applied to the group preparing the amines system of polyureas of the present invention selected from aliphatic series or aromatics short chain and alkyldiamine composition, Including ether diamine, such as 1,8- bis- amido -3,6- dioxaoctane, and long-chain polyether diamidogen, such as polyethoxylated or poly- Propoxylation diamidogen (d-2000)；Aliphatic diamine, such as 1,6- hexamethylene diamine (1,6-hda), 4,4'- bis- amido diphenyl-methane (mda)；Cyclic aliphatic diamidogen, such as isophorone diamine (ipda) or h₁₂Mda (hydrogenation mda)；Aromatic diamine, Such as 4,4'- bis- amido diphenyl-methane (mda)；And long-chain polyether diamidogen, such as polyethoxylated or poly- propoxylation diamidogen.

Be applied to polyureas constructed in accordance the polar solvent turning urea method include dimethyl acetylamide (dmac), N- rnethyl-pyirolidin ketone (nmp), dimethyl sulfoxide (dmso) or sulfolane (tms) etc..

Reaction temperature typically in the range of about 60 DEG C to about 200 DEG C, in the range of about 60 DEG C to about 160 DEG C, and more In the range of about 60 DEG C to about 100 DEG C.Reaction pressure can be decompression, normal pressure or high pressure.

There is not special restriction to the response time.In generally 0.001 hour to 100 hours response time, be 0.005 Hour to 50 hours, and more 0.1 hour to 10 hours.

Specific embodiment

It is generally described the present invention, can obtain by reference to some particular instances and further appreciate that, the example such as described is at this It is for illustration purposes only in literary composition and provide and unless specified otherwise herein, be otherwise not intended to restrictive.

Embodiment

Example 1

Synthesis n, n'- hexamethylene diamine carbamate (hmbpc)

Hexamethylene diamine (hmda, 6.0g, 51.7mmol), diphenyl carbonate (dpc, 22.67g, 106mmol) are added Add in the 500ml three-necked bottle containing 100ml ethylene glycol diethyl ether.Use magnetic stirring bar stirring mixture at room temperature. One neck of described bottle is equipped with thermometer and loads nitrogen, and another neck connects to the condenser equipped with water, described condensation The upper end of device is connected with oil sealing.Reaction carries out 2 hours.When ir analysis instruction do not exist 4,4'- bis- amido diphenyl-methane and During monoamine carbamate intermedium, terminate reaction.

After the completion of reaction, continue stirring reaction mixture and make temperature be slowly dropped to room temperature.Observe that white crystalline product sinks Form sediment.Then application suction filtration is to obtain product.And be dried 6 hours at 80 DEG C in vacuum drying oven.Collect white solid Body crystallized product (17.53g) (1h-nmr (200mhz, d6- dimethyl sulfoxide) δ (ppm): 1.31 (s, 4h, -nhch2ch2ch2-),1.45(s,4h,-nhch2ch2-),3.04(s,4h,-nhch2-),7.06-7.36(m,10h, -ph-),7.73(br s,2h,-nh-).Yield is 98%, and fusing point is 126.6 DEG C.

Comparative example 1

The patent (ep 2275405a1) that shinohata according to Japanese asahi and miyake is delivered, will at 50 DEG C Hexamethylene diamine (hda, 2.1mol) in the way of continuous feed (200g/hr) enters equipped with diphenyl carbonate (dpc, 6.3mol) Cell body, in and be used the phenol (10.5mol) of excess to react as under reaction dissolvent, obtain that yield is 99.5% six are sub- After methanediamine base methyl formate (hdu), carry out the thermal cracking next at about 180 DEG C immediately.Whole processing procedure consumes very much When about need a couple of days even more than ten days.Simulation asahi amount of reagent under carry out batch phenol (phenol) reaction by oneself two Amine (hmda, 6.0g, 51.7mmol), diphenyl carbonate (dpc, 33.18g, 155.1mmol) add to containing In the 500ml three-necked bottle of 24.4g phenol (258.5mmol).Find the phenol in reaction bulb in stirring reaction at 50 DEG C And completely hexamethylene diamine and diphenyl carbonate cannot be completely dissolved and assume nebulousurine shape and cannot be carried out reacting.

Though reaction temperature is brought up to 80 DEG C and add again and can be completely dissolved after 14.78g phenol simultaneously, react 16hr Shi Faxian ir analysis result shows and still suffers from diphenyl carbonate and monoamine carbamate intermedium, represents that reaction is not complete Terminate.

Article that Chen Xueyong et al. delivers (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-metallic catalyst during narration synthesis diamine carbamate, it is complete Literary composition is expressly incorporated herein as reference.Benzoic acid is imported in reactant so that final proportioning raw materials hmda/dpc/ benzene first Acid=1/3/0.2 (51.7mmol/155.1mmol/10.3mmol), at 80 DEG C, stirring reaction, after 16 hours, continues stirring Reactant mixture and make temperature be slowly dropped to room temperature.Observe that white crystalline product precipitates.Then application suction filtration is to obtain Obtain product.With the obtained product of toluene (50ml) washing, filter, and be dried 6 hours at 80 DEG C in vacuum drying oven. Obtain after collecting white crystalline solid product analysis hexamethylene diamine base methyl formate (hdu) that yield is 51.9% with The urea of 39.7% by-product.

Example 2

Synthesize n, n'- hexamethylene diamine carbamate using differential responses solvent

Using phenol, toluene, hexahydrotoluene, 1- N-Propyl Bromide, ethylene glycol diethyl ether (1,2-diethoxyethane, egdee) Deng as reaction dissolvent, carry out and example 1 identical program and analysis.Synthesis condition is summarized in table 1.Result shows, The ethylene glycol diethyl ether of low polar solvent is optimum selection.Can get the hexamethylene diamine base that highest yield is 90.3% Methyl formate (hdu) and the urea of minimum 8.54% by-product.

Table 1: different low polar solvents effect for its yield in hmbpc synthesis

Example 3

Using different amounts of diphenyl carbonate (dpc) synthesizing hexamethylene two amido methyl formate (hmbpc)

In addition to the amount of diphenyl carbonate (dpc) is changed as shown in table 2, carry out and example 1 identical journey Sequence and analysis.Can be learnt by table 2, except when the amount of diphenyl carbonate (dpc) increases to 4 times of mda mole number When, can get hexamethylene diamine base methyl formate (hdu) that highest yield is 95% and minimum 2.04% by-product Urea.

Table 2: the different effects to hmbpc yield for the dpc ratio in ethylene glycol diethyl ether (egdee)

Example 4

Using different amounts of solute concentration (solutes concentration) synthesizing hexamethylene two amido methyl formate (hmbpc)

Amount except the solute concentration percentage by weight (solutes concentration) of whole system is carried out as shown in table 3 Beyond change, carry out and example 1 identical program and analysis.Can be found by following table, when with solute concentration weight percent The yield of raising hexamethylene diamine base methyl formate (hdu) of ratio also and then increases, but the urea of by-product also and then increases Plus, when solute concentration percentage by weight continues to increase to 50%, can get the hexa-methylene two that highest yield is 97.3% Amidocarbonic acid methyl ester (hdu) and the urea of minimum 1.49% by-product.

Table 3: the different effects to hmbpc yield for the solute concentration in egdee

Example 5

Benzoic acid is not used as catalyst synthesizing hexamethylene two amido methyl formate (hmbpc)

In addition to the amount of benzoic acid presence or absence and diphenyl carbonate (dpc) is changed as shown in table 4, enter Row and example 1 identical program and analysis.Can be found by table 4 below, when not using benzoic acid catalyst, with diphenyl The reduction of the amount of carbonic ester (dpc) does not also produce by-product urea.Amount with diphenyl carbonate (dpc) is down to During hmda/dpc=1/2.05, can get hexamethylene diamine base methyl formate (hdu) that highest yield is 98% and And the generation of by-product urea in course of reaction can be prevented.

Table 4: the no effect to hmbpc yield for the catalyst (benzoic acid) in egdee

Example 6

Diamidogen using different structure synthesizes diphenyl alkyl diamine carbamate (diphenyl n,n’-alkenylbiscarbamates)

In addition to the diamidogen using different structure as shown in table 5, carry out and example 1 identical program and analysis.By Table 5 can be learnt, as variant structural fatty race diamidogen/dpc=1/2.05 and solute concentration percentage by weight=25%, all Can get in the middle of the diphenyl alkyl diamine carbamate (diphenyl n, n '-alkenylbiscarbamates) of yield ＞ 85% Body.

Table 5: the effect to diamine carbamate yield for the carbonylation of different diamine structures in egdee

Example 7

Using thermal cracking synthesis 1,12- ten dimethylene diisocyanate (1,12-dodecamethylene diisocyanate, ddi)

Ten dimethylene two amido methyl formate (dmbpc, 27.78g, 67.78mmol) is added to containing 250g bis- In the 500ml three-necked bottle of phenylate.Now solute concentration percentage by weight=10%.Persistently overheating magnetic is stirred at room temperature Mix excellent stirring mixture.One neck of described bottle is equipped with thermometer and loads nitrogen, and another neck connects to equipped with water Condenser, the upper end of described condenser is connected with oil sealing.Reaction carries out 0.5 hour reaching 240 DEG C.When ir analysis refers to Show when there is not ten dimethylene two amido methyl formate and monoamine carbamate intermedium, terminate reaction.

After the completion of reaction, continue cooling stirring to when 100～150 DEG C using vacuum pumps by diphenyl ether and product 1,12- 12 Methylene diisocyanate (1,12-dodecamethylene diisocyanate, ddi) separates.Observe transparent liquid ddi Yield be 84%.It is then used by the methanol after eliminating water ddi to be carried out after nco end-blocking and 80 in vacuum drying oven 6 hour purification is dried at DEG C and carries out the analysis of purity.(1h-nmr (200mhz, d6- dimethyl sulfoxide) δ (ppm): 1.21 (s,8h,-nhch2ch2ch2ch2-),1.36(s,4h,-nhch2ch2ch2ch2-),2.92(s,4h, -nhch2ch2ch2ch2-),3.52(s,6h,ch3coo-nh-),7.08(m s,2h,-nh-).Ddi yield is 84%, and phenol recovery rate is 100% and the diphenyl ether response rate is 85%.

Example 8

Diphenyl alkyl two amido formate (diphenyl n, n '-alkenylbiscarbamates) heat using different structure Cracking synthesis diisocyanate

Except diphenyl alkyl two amido formate (diphenyl n, n '-alkenylbiscarbamates) using different structure Beyond acquisition as shown in table 6 various diisocyanate, carry out and example 7 identical program and analysis.Can by table 6 Learn, when solute concentration percentage by weight=10%, ddi and 4-ibpi all can get the product that yield is 84%.

Table 6: manufacture thermal cracking diamine carbamate in hexichol ethereal solution and manufacture diisocyanate

Example 9

Change method (one-pot) preparation 1,12- ten dimethylene diisocyanate (1,12-dodecamethylene using one pot diisocyanate,ddi)

Lauryl amine (dmda, 10g, 50mmol), diphenyl carbonate (dpc, 21.9g, 102.5mmol) are added To the 500ml three-necked bottle containing 96g diphenyl ether.Now solute concentration percentage by weight=25% uses magnetic at room temperature Stirring rod stirring mixture.One neck of described bottle is equipped with thermometer and loads nitrogen, and another neck connects to equipped with water Condenser, the upper end of described condenser is connected with oil sealing.Reaction carries out 2 hours.When ir analysis instruction does not have ten When diamidogen and monoamine carbamate intermedium, terminate reaction.Persistently overheating immediately use magnetic stirring bar stirring mixture.Institute A neck stating bottle is equipped with thermometer and loads nitrogen, and another neck connects to the condenser equipped with water, described condenser Upper end be connected with oil sealing.Reaction carries out 0.5 hour reaching 240 DEG C.When ir analysis instruction does not have ten dimethylenes When two amido methyl formates and monoamine carbamate intermedium, terminate reaction.

After the completion of reaction, continue cooling stirring to when 100～150 DEG C using vacuum pumps by diphenyl ether and product 1,12- 12 Methylene diisocyanate (1,12-dodecamethylene diisocyanate, ddi) separates.Observe transparent liquid ddi Yield be 80%.It is then used by the methanol after eliminating water ddi to be carried out after nco end-blocking and 80 in vacuum drying oven 6 hour purification is dried at DEG C and carries out the analysis of purity.(1h-nmr (200mhz, d6- dimethyl sulfoxide) δ (ppm): 1.21 (s,8h,-nhch2ch2ch2ch2-),1.36(s,4h,-nhch2ch2ch2ch2-),2.92(s,4h, -nhch2ch2ch2ch2-),3.52(s,6h,ch3coo-nh-),7.08(m s,2h,-nh-).Ddi yield is 84%, and phenol recovery rate is 100% and the diphenyl ether response rate is 85%.

Example 10

Diphenyl alkyl two amido formate (diphenyl n, n '-alkenylbiscarbamates) heat using different structure Cracking synthesis diisocyanate

Except being directly synthesized out diphenyl alkyl two amido formate using the diamidogen of different structure under one pot of change After (diphenyl n, n '-alkenylbiscarbamates), with to carry out thermal cracking synthesis as shown in table 7 various two different Beyond cyanate, carry out and example 9 identical program and analysis.Can be found by table 7 below, when solute concentration weight percent Than=10% when, can get isophorone diisocyanate (isophorone diisocyanate, ipdi) that yield is 86% and produce Thing.

7: one pots of table is changed two benches npr legal system and is made diisocyanate

As examples detailed above clearly states, the approach (npr) through non-phosgene uses aliphatic n, n '-diphenyl alkyl diamidogen Carbamate (diphenyl n, n '-alkenylbiscarbamates) carries out thermal cracking for reaction intermediate, in a mild condition With during do not use and aliphatic diisocyanate manufactured with high yield under the premise of catalyst.

First, during preparing diamine carbamate (biscarbamates), amine and diphenyl carbonate carry out the product of carbonylation Rate substantially be subject to highly affected using the polarity of solvent.With non-polar solven, such as toluene or hexahydrotoluene, carbonylation Speed more slow.During using highly polar solvent such as nmp or dmac, the carbonylation rate of amine is substantially accelerated, But also increase the degree that urea by-product is formed simultaneously.Observed for example in n- N-methyl 2-pyrrolidone N-prepare diamine carbamate Yield at 80 DEG C only 52%, and the urea by-product further reacting from amido formate and amine then dramatically increases. Therefore, prepare diamine carbamate using low polar solvent (such as ethers or alcohol ethers).Example be using second two Diethylene glycol diethyl ether (egdee), as Solvents Solvent, can complete and no urea by-product in 25～40 DEG C of rapid preparations in 2 hours Generation.Highly purified diamine carbamate can be obtained simply by filtration separation after being naturally cooling to 25 DEG C of precipitations Product.And mixture liquid then through carry out refined ethylene glycol diethyl ether (egdee) solvent recovery can be reached 93%, and For in the carbonylation preparing diamine carbamate (biscarbamates) next time.

Ethylene glycol diethyl ether (egdee), at room temperature just can be complete in addition to having low dipole moment (3 × 10-6debye) CL amine and the mixture of diphenyl carbonate, and just smoothly complete the synthesis of carbonylation at 60 DEG C, and simultaneously permissible Prevent to avoid to cause the formation of urea by-product because of high temperature.

Via n, the thermal cracking of n '-diphenyl alkyl two amido formate (diphenyl n, n '-alkenylbiscarbamates) Method prepare aliphatic diisocyanate pyrolysis when, nonpolar hydrocarbon solvent such as n-dodecane (dipole moment=0) and several The test result performance that alkyl lubricating oil (dipole moment=0) has carried out thermal cracking is slightly worse.Further analyze through hplc and send out Now wherein main product is the such as isocyanuric acid ester of the product containing oligomerization species.This result shows, n-dodecane is in fat The building-up process of fat race isocyanates exists when temperature > 200 DEG C when aliphatic diisocyanate be unstable in this solution, easily There is the generation of oligomer by-product.On the other hand, sub- in highly polar solvent such as phenol benzoate and dipolar solvents such as four Methyl sulfone is when the solvent as thermal cracking it has also been found that the result performed poor.In addition to having the formation of buff by-product, The formation also having trimer and carbodiimides also appears to all to consume original product diisocyanate and causes yield too low.

Inventor find the low polarity suitably being found solvent as diphenyl ether be the selection in heat scission reaction. In the selection of the solvent of aliphatic diamine carbamate thermal cracking, carry out thermal cracking from low polar solvent.From ours The selection result determines that diphenyl ether (dpe) is the one of better suited solvent, because it can separate all aliphatic two Carbimide .s Ester, and phenol can be recovered completely, and it is significantly shorter the response time.This result shows aromatic hexichol Ether (dpe) solvent and the incompatible formation being beneficial to azeotropic distillation effect of aliphatic diisocyanate, and then can be by fat Fat (cyclo) aliphatic diisocyanates are separated from mixture.Additionally, completely not using metallic catalyst in whole process.

Finally, the present invention is according to the preparation of the diamine carbamate of original first step and the thermal cracking of subsequent second stage Npr process, futuramic one pot change method non-phosgene path processing procedure.For example, using dmda (1,12- ten two Amine) carry out carbonylation preparation double amidocarbonic acid at 60 DEG C with diphenyl carbonate (dpc) under diphenyl ether (dpe) solvent Ester.When under 25% solids content, dmbpc diamine carbamate can be confirmed from its infrared spectrum with hplc Yield is about 100% and does not have the formation of by-product.Then by solution directly heat to 240 DEG C about 0.5 hour, during Through infrared spectroscopy monitor 1, the disappearance being formed with dmbpc diamine carbamate of the sub- diisocyanate of 12- 12, finally Diphenyl ether (dpe) solvent is kept completely separate out through distillation.Final 1,12- ten dimethylene diisocyanate (ddi, c₁₂ Diisocyanate) can be separated and yield is up to 80%, and phenol recovery rate is also 100%.Compared to two original steps In method, the npr process of one pot of change is more simple, and can obtain the product of suitable yield.The mistake of this one pot of change Journey has also been applied successfully to the method that isophorone diamine prepares isophorone diisocyanate, and yield reaches 86%.

The preparation method of the aliphatic diisocyanate in the non-phosgene path (npr) according to the present invention, employs several keys Green Chemistry principle, and be applied to all of aliphatic diisocyanate of production, and do not use the poisonous carbonyl as phosgene Base reagent and metallic catalyst.Because having the advantages that high security and low stain, the non-phosgene path side of the present invention Method may replace phosgene manufacturing method thereof dangerous and hypertoxic at present, and is applicable to industrial mass production aliphatic two isocyanide Acid esters.

Those who familiarize themselves with the technology should show and be apparent from, and under without departing substantially from scope of the invention or spirit, the structure of the present invention can be made Go out various modifications and change.In view of above it is intended to the present invention covers modification and the change of the present invention, its restrictive condition is institute The modification such as state and change is in claims below and its category of equivalent.

Claims (26)

1. a kind of method preparing aliphatic diamine carbamate, methods described comprises to make at least one aliphatic diamine or fat Race's polyamine and diaryl carbonate react in the first low polar solvent generation at least one diamine carbamate or The step of many amido formates, uses non-metallic catalyst to described reaction selectivity, and described first low polarity is molten Agent is ether or alcohol ether.

2. method according to claim 1, wherein said diaryl carbonate system is selected from diphenyl carbonate, double (2- Tolyl) carbonic ester, double (4- chlorphenyl) carbonic ester, double (4- nitrobenzophenone) carbonic ester and double (3,5- dimethoxy benzenes Base) carbonic ester composition group.

3. method according to claim 1, wherein said aliphatic diamine or aliphatic polybasic amine system be selected from butanediamine, Hexamethylene diamine, dodecamethylene diamine, cyclohexylamine and isophorone diamine, 4- (amido ethyl) aniline, stretch methyl bicyclic oneself Base diamidogen, propane -1,2,3- triamines, two stretch second triamine, double (hexa-methylene) triamine, three stretch second tetramine, 3- amido Methyl isophthalic acid, 6- hexamethylene diamine and 1, the group of 3,6- tri- amido normal hexane compositions.

4. method according to claim 1, wherein said first low polar solvent system is selected from aryl ether, aliphatic ether, ring Fat ether, mixed virtue fat ether, the group of aryl alcohol ether, aliphatic alcohol ether or mixed virtue lipidol ether compound composition.

5. method according to claim 4, wherein said first low polar solvent system be selected from diethyl ether, oxolane, Isosorbide-5-Nitrae-dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, TRIGLYME, Diphenyl ether and the group of methyl phenyl ethers anisole composition.

6. method according to claim 1, wherein said step tie up to the aliphatic diamine compound of 1:2 to 1:3 with Carry out under the mole ratio of diaryl carbonate.

7. method according to claim 1, wherein said step ties up to and carries out under 20 to 100% solute concentration.

8. method according to claim 1, wherein said step does not use catalyst.

9. method according to any one of claim 1 to 8, described step is carried out at a temperature of 0 to 100 DEG C.

10. method according to any one of claim 1 to 8, described step is carried out under the pressure of decompression.

A kind of 11. methods preparing aliphatic diisocyanate or polyisocyanates, methods described comprises to make according to claim 1 The aliphatic diamine carbamate manufactured by method to any one of 10 or many amido formates are in the second low polarity The step carrying out thermal cracking in solvent further, wherein said second low polar solvent system be selected from aryl ether, aliphatic ether, Ring grease ether, mixed virtue fat ether, the group of aryl alcohol ether, aliphatic alcohol ether or mixed virtue lipidol ether compound composition, and with described First low polar solvent is identical or different.

12. methods according to claim 11, wherein said second low polar solvent is the compound with formula (5):

r⁵-o-r⁶(5)

Wherein r⁵With r⁶Independently represent c_6-9Alkyl, c_6-9Aryl or c_6-12Aralkyl；

Or be the compound with formula (6):

r⁷-(o-(ch₂)₂-)_aor⁸(6)

Wherein r⁷With r⁸Independently represent c_1-9Alkyl, c_6-9Aryl or c_6-12Aralkyl；And

A represents 1 to 3 integer.

13. methods according to claim 12, wherein said second low polar solvent is diphenyl ether, methyl phenyl ethers anisole, diethyl Glycol dimethyl ether or TRIGLYME.

14. methods according to any one of claim 11 to 13, described step is entered at a temperature of 120 to 250 DEG C OK.

15. methods according to any one of claim 11 to 13, described step is carried out under the pressure of decompression.

A kind of 16. one pot of change method preparing aliphatic diisocyanate or polyisocyanates, methods described is included in the second low pole Property solvent in, make at least one aliphatic diamine or aliphatic polyamine and diaryl carbonate react generation at least one Plant diamine carbamate or many amido formates, and carry out the step of heat scission reaction in same reactor further Suddenly, wherein said second low polar solvent system is selected from aryl ether, aliphatic ether, ring grease ether, mixed virtue fat ether, aryl alcohol The group of ether, aliphatic alcohol ether or mixed virtue lipidol ether compound composition.

17. methods according to claim 16, wherein said diaryl carbonate system is selected from diphenyl carbonate, double (2- tolyl) carbonic ester, double (4- chlorphenyl) carbonic ester, double (4- nitrobenzophenone) carbonic ester and double (3,5- dimethoxys Phenyl) carbonic ester composition group.

18. methods according to claim 16, wherein said aliphatic diamine or aliphatic polybasic amine system be selected from butanediamine, Hexamethylene diamine, dodecamethylene diamine, cyclohexylamine, isophorone diamine, 4- (amido ethyl) aniline, stretch methyl bicyclic oneself Base diamidogen, propane -1,2,3- triamines, two stretch second triamine, double (hexa-methylene) triamine, three stretch second tetramine, 3- amido Methyl isophthalic acid, 6- hexamethylene diamine and 1, the group of 3,6- tri- amido normal hexane compositions.

19. methods according to claim 16, wherein said second low polar solvent is the compound with formula (5)

r⁵-o-r⁶(5)

Wherein r⁵With r⁶Independently represent c_6-9Alkyl, c_6-9Aryl or c_6-12Aralkyl

Or be the compound with formula (6):

r⁷-(o-(ch₂)₂-)_aor⁸(6)

Wherein r⁷With r⁸Independently represent c_1-9Alkyl, c_6-9Aryl or c_6-12Aralkyl；And

A represents 1 to 3 integer.

20. methods according to claim 16, wherein said second low polar solvent is diphenyl ether, methyl phenyl ethers anisole, diethyl Glycol dimethyl ether or TRIGLYME.

21. methods according to claim 16, wherein said step tie up to the aliphatic diamine compound of 1:2 to 1:5 with Carry out under the mole ratio of diaryl carbonate.

22. methods according to claim 16, wherein said step ties up to and carries out under 20 to 100% solute concentration.

23. methods according to claim 16, wherein said step does not use catalyst.

24. methods according to any one of claim 16 to 22, its lie in carry out at a temperature of 120 to 250 DEG C double The heat scission reaction of amido formate.

25. methods according to any one of claim 16 to 22, it lies in the pressure of 0.01mmhg to 760mmhg Carry out under power.

26. methods according to any one of claim 16 to 22, it is complete that it lies in the time of 0.1 hour to 1 hour Become reaction.