CA1239415A - Amino-aminomethylcyclohexanes, useful for the preparation of their corresponding diisocyanates - Google Patents
Amino-aminomethylcyclohexanes, useful for the preparation of their corresponding diisocyanatesInfo
- Publication number
- CA1239415A CA1239415A CA000454484A CA454484A CA1239415A CA 1239415 A CA1239415 A CA 1239415A CA 000454484 A CA000454484 A CA 000454484A CA 454484 A CA454484 A CA 454484A CA 1239415 A CA1239415 A CA 1239415A
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- Canada
- Prior art keywords
- methyl
- isocyanato
- isocyanatomethyl
- mixture
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/10—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The invention describes novel diisocyanates of formulae:
The invention describes novel diisocyanates of formulae:
Description
I
This invention relates to aliphatic diisocyanates.
specifically it relates to alkyl-substituted isocyanato-isocyanatomethylcyclohexanes.
Description of the Prior Art Both aromatic and aliphatic isocyanates are known to the art. Aromatic diisocyanates such as 2,4- and 2,6-Tulane diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and mixtures of 4,4i-, 2,4'-, and 2,2'-diphenylmethane diisocyanates and polyphenyl-polyethylene polyisocyanates, aliphatic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate are known commercial products which are preferably used to prepare polyurethane plastics. The polyisocyanates are generally prepared from their corresponding amino compounds through phosgenation and subsequent thermal cleavage of the intermediately formed carbamic chlorides. Numerous organic moo- and polyisocyanates are described, for example, in the Aniline don Chemise 562 (1949), p. 75 if.
The objective of the invention at hand was to develop cycloaliphatic diisocyana-tes with the isocyanate groups having different reactivity.
Summary ox like Invention The objective of -the invention is achieved with diisocyanates of formulae:
R R
This invention relates to aliphatic diisocyanates.
specifically it relates to alkyl-substituted isocyanato-isocyanatomethylcyclohexanes.
Description of the Prior Art Both aromatic and aliphatic isocyanates are known to the art. Aromatic diisocyanates such as 2,4- and 2,6-Tulane diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and mixtures of 4,4i-, 2,4'-, and 2,2'-diphenylmethane diisocyanates and polyphenyl-polyethylene polyisocyanates, aliphatic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate are known commercial products which are preferably used to prepare polyurethane plastics. The polyisocyanates are generally prepared from their corresponding amino compounds through phosgenation and subsequent thermal cleavage of the intermediately formed carbamic chlorides. Numerous organic moo- and polyisocyanates are described, for example, in the Aniline don Chemise 562 (1949), p. 75 if.
The objective of the invention at hand was to develop cycloaliphatic diisocyana-tes with the isocyanate groups having different reactivity.
Summary ox like Invention The objective of -the invention is achieved with diisocyanates of formulae:
R R
2 NO
(I) (II) NO CHINOOK
or mixtures thereof, in which R is an alkyd group having from 1 to 12 carbon atoms.
~23~4~i Preferred are diisocyanates of formulae:
R R
(III) (IV) or mixtures thereof, in which the isocyanatomethyl group is bonded in the 2- or 4-position and the isocyanate group is in the 4- or 2-position.
The invention also relates to a process for the preparation of the above diisocyanates using dominoes of ; formulae:
SHEEHAN
No SHEEHAN
Descr~ltion of the Preferred Embodiments In formulae (I) through (VI), R is an alkyd radical having from l -to 12 carbon atoms, preferably from 1 to 4 carbon atoms, which may be branched, however, is preferably linear. Typical examples of such alkyd radicals are n-ponytail-, n-hexyl, Natalie, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl radicals, preferably the ethyl, n- and isopropyl, and n- and sec.-butyl radicals, and more preferably the methyl radical.
The following are typical examples of the dozes-antes of the invention:
1-methyl-2-isocyanatomethyl-3-isocyanato-, 1-methyl-2-isocyanatomethyl-5-isocyanato-, 1-methyl-2-isocyana-tomethyl-6-isocyanato-, 1 methyl-4-isocyanatomethyl-3-isocyanato-cyclohexane; 1-ethyl-2-isocyanatomethyl-3-:~;
I
isn't-, 1 ethy}-2-isocyanatomethyl-5-isocyanato-, l-ethyl-2-isocyanatomethyl-6-i~ocyanato-, ethyls-nato~ethyl-3-isocyanato-cyclohexane; 1-n--propyl-2-i ooze-natomethyl-3-i~ocyana~o-, 1-n-propyl-2-i~ocyanatomethyl-5-isocyanato-, l-n-propyl-2-i~ocyanatomethyl-6-isocyanato , 1-n-propyl-4-isocyanatomethyl-3-isocyanato-cyclohexaanew 1-isopropyl-2-iqocyanatomethyl-3-i~ocyanato-, 1-i~opropyl-2-i~ocyanatomethyl-4-isocyanato-, 1-isopropyl-2-isocyanato-methyl-5-isocyanato-, 1-isopropyl-2-isocyanatomethyl-6-isocyanato-, 1-i~opropyl-4-isocyanatomethyl-2-isocyanato-, ~opropyl-4-isocyanatome~hyl-3-isocyanato-cyclohexanno; 1-n-butyl-2-i~ocyanatomethyl-3-i~ocyanato-, l-n-butyl-2-isocyanatomethyl-4-isocyanato-, 1-n-butyl-2-isocyanato-methyl-5-isocyanato-, 1-n-butyl-2-i~ocyana~omethyl-6-isocyanato-, l-n-butyl-4-isocyanatomethyl-2-i~ocyanato-, 1-n-butyl-4-isocyanatomethyl-3-isocyanato-cyclohexanno, l-n-pentyl-2-isocyanatomethyl-4 isocyanato-, 1-n-pentyl-2 i30cyanatomethyl-6-isocyanato-, 1 n-pentyl-4-isocyanato-methyl-2-i ocyana~o-cyclohexane, 1-n-hexyl-2-i~ocyanato-methyl-4-isocyanato-, l-n-hexyl-2-i30cyanatomethyl-6-isocyanato-, l-n-hexyl-4 isocyanatomethyl-2-isocyanato-cyclohexane, l-n-heptyl-2-i~ocyanatomethyl-4-i~ocyanato-, 1-n-h~ptyl-2-isocyanatome~hyl-6-i~ocyanato-, Natalie-isocyanatomethyl~2-isocyanato-cyclohexane, 1-~-octyl-2-isocyanatom~thyl-4-isocyanato-, 1-n-octyl-2-isocyanato-S
methyl-6-i~ocyanato-, l n-octyl-4~isocyanatomethyl-2-isocyanato-cyclohexane; l-n-nonyl-2-i~ocyanatomethyl-4-iqocyanato~ n-nonyl-2-isocyanatome~hyl-6-i~ocyanato~
n-nonyl-A-i~ocyanatomethyl-2~ ocyanato-cyclohexane, l-n-dozily i~ocyanatomethyl-4-i30cyanato-, l-n-decyl-2-isocya-natomethyl-6 isocyana~o-, l-n-decyl-4-i~ocyanatomethyl-2-i~ocyanato-cyclohexane, l-n-undecyl-2-isocyana~omethyl-4-isocyanato~ n-undecyl-2-isocyanatomethyl-6-isocyanato-, l-n-undecyl-~-isocyanatomethyl-2-i30cyanato-cyclohhexane, l-n~dodecyl-2-isocyanatomethyl-4~isocyanato-, l-n-dodecyl-2-isocyanatomethyl-6-iqocyanato- and l-n-dodecyl~-4-isocyanato-methyl-2-i~ocyanato-cyclohexane.
Preferred are: l-ethyl-2-i~ocyanatomethyl-4-isn't-, 1-2thyl-4-isocyanatomethyl-2-i~ocyanato-cyclo-hexane, l-n-propyl-2-isocyanatomethyl-4-isocyanato- and l-n-propyl-4-i~ocyanatomethyl-2-i~ocyanato-cyclohexanee and more preferably l-methyl-2-i~ocyanatomethyl-4-isocyanato-, l-methyl-2-inocyanatomethyl-6-i~ocyanato-cyclohexanee as well a their ire mixture and l~methyl-4-isocyanatomethyl-2-i~ocyana~o-cyclohexa~e.
Demurrals corresponding to the dozes-notes cited above are used as the starting components for the preparation of the dli~ocyanate~ of the invention.
Here the following compound have proved to be particularly successful and are, therefore, preferably I
used: l-ethyl-2-a~inomethyl-4-amino-, 1-ethyl~4-amino-methyl-2~amino-cyclohexane, 1-n~propyl-2-aminomethyl-2-amino cyclohexane, l-n propyl-2-aminomethyl-4-amino- and 1-n-propyl-4 aminomethyl-2-amino-cyclohexane, and more preferably l-methyl-2-aminomethyl-4-amino-, 1-methyl-2-aminomethyl-6-amino-cyclohexane a well as their isomer mixer and l-methyl-4-aminomethyl-2-amino cyclohexane.
The dll~ocyanate3 and dominoes for these compound can be prevent in the form of isomer mixtures, mixtures of the tame immure but with different alkyd radical, or a mixture ox both types of mixture The preparation ox the novel dozes-antes can hollow the hollowing sequence, for example:
R R
: ON SHEEHAN
SIX) (Xj (XIj Pi ago I, C~2~H2 ICKY NH;2 (I) MY) Jo ..~
~3~5 The l-alkyl-2-cyanonitrobenzene~ (X) or the 1-alkyl-4-cyanonitrobenzene~ can Allah be prepared in even-tidally known procedures through the nitration of the corresponding l-~lkyl-2-cyanob2nzene~ (IX) or l-alkyl-4-cyanobenzenes, for example, in the manner described in thy (1~98), p. 2880 if. or in the Journal of American Chemical So 99 (1977), p. 6721 or suitable variant of these method.
Another method for the preparation of the alkyd-cyanonitrobenzenes cited a an example lie in the known process for exchanging the amino group in the alkyl-amino nitrobenzenes for a neural group, corresponding to Journal I (1979), p. 4003.
Thy l-alkyl-cyanonitrobenzene~ obtained in the nitration or their Homer mixtures can be reduced directly, i.e., without further purification, to l-alkyl-aminomethyl-aminobenzene~ or their isomer mixture. Similar, for example, to the process described for 2-cyanonitrotoluene in Formic peeve), Edit. Sat. 25 (1970), p. 163 (C. A. 72, ~21 101 d, 1970). The reduction of the vitro and the cyan group can be completed here in one or two ~equen',ial reaction Taipei. It it not always necessary to add ammonia.
The aromatic ring reduction of the alkali-aminomethyl-aminobenzenes I or the l-alkyl-4-aminomethyl-aminob~n Noah follows known prowesses, for example, those G
-or -I
cited in Hobnail, Methadone don organlsch~n Comma, Thea Ed., solo XI/l, (Stuttgart: Gorge Thyme Verlag, 1957~, p. 678 if., I Ferry Reaktionen don orqa~ en Saab (George Thyme V~rlag: Stuttgart, 19783, pp. 83, 90 of.;
A. E. ark doll et at, J. Amen Comma. Sock 75 (1953~, p. 1156, ye lo Lookers. (1982), pp. 603~606, Us S.
Patent 2,494,563 or German laid-open Application 21 32 547.
In order to prepare the l~alkyl-2-aminomethyl~
aminocyclohexane (~) or the l-alkyl-4-aminom~thyl amino-cyclohexane, one can alto tart directly with alkali-cyanonitrobenzenes (X).
The resulting l-alkyl aminomethyl-aminocyclo hexanes can be phosgenated in solvents either directly or as salts, preferably hydrogen chlorides. Suitable solvent are, for example: Tulane, zillion, chlorobenzene, or dichlorobenzene. A 301ution of the l-alXyl-aminomethyl-aminocyclohexane~ or a suspension of the corresponding salts is reacted accordingly at temperature of approximately 0C
to 100C, preferably from 10C to SKYE, with 1 to 6 moles pho~gene per NH2-HCl, preferably from 1 to 2.5 moles phosgene, and the intermediately formed carbamic chloride can by cleaved at temperature from 80C to 180C, prefer-ably from 120 to 160C in the l-alkyl-i30cyanato~eehyl-iRocyanatocyclohexane. The gaseous or liquid pho3g~ne is charged directly into the reaction mixture at such a rate it "
~23~
that the emerging gases primarily are composed of hydrogen chloride.
After completion of pho~genation and cleavage, the solvent it distilled off at reduced pressure, for example, from lo to lo mar. However, it may Allah be Advents to trip the hydrogen chloride or any excel phosgene which may be present Prom the doesn't solution with the aid of nitrogen or another inert gee before the solvent it distilled off.
The resulting crude l-alkyl-2- or 4-isocyanato-methyl-lsocyanatocyclohexane~ or isomer mixtures can by separated and purified by distillation at reduced prowar.
The disunites of the invention can also be Jo prepared through the thermal cleavage of the corresponding diurethane~ in the guy or liquid phase, if Nasser in the prank of c~ta.ly~t3, whereby the diurethane~ are obtained in an efficacious manner according to the process described in European Patent published application 18 583 (U. S. Patent 4, 278, 805) through the reaction of carbamate I with the l-alkyl-aminocyclohexane~ in the presence of alcohols and, if necessary, urea.
The l-alkyl-2- or 4-aminomethyl-aminocyclohexane~
and alkali- or 4-i~ocyanatomethyl-i30cyanatocylohexane~
are valuable intermediate and eed~tock~ for crop protect lion agent and plastic ~23~ 5 The dominoes are preferably converted into diisocyanat~s. Such diisocyanates are particularly well suited for the preparation of polyurethane foam, adhesives, paints, coatings, and sealants.
The following examples art intended to further explain the invention without necessarily limiting it scope.
' J
I
eye a) Preparation of an isomer mixture of l-methyl-2-cyano~4-nitrobsnzene and 1-methyl-2-cyano-6-nitrobenzene Twelve hundred part by weight concentrated sulfuric acid were cooled to -5C in a reaction flask equipped with an addition funnel, a stirrer, and a thermometer.
While stirring well, 200 weight part 2-cyanotoluene followed by 151 weight parts concentrated nitric acid between -5~C and ~5C were added drops within one hour. In order to complete the nitration, stirring continued for an additional 1.5 hour at 0C, whereupon the reaction mixture was poured onto 2000 weight part ice The precipitate way filtered off, the filtered solid was thoroughly washed with water and dried on clay.
Two hundred and eighty-two weight part of a crude isomer mixture of l-methyl-2-cyano-4- and 6-nitrobenzene were obtained at a weigh ratio of approximately 87:13 and having a melting point ox from glC to 92~C.
0 by Preparation of an isomer mixture of l-methyl-2-amino-methyl-4- and 6-aminobenzene JO
r-One hundred weigh parts of the isomer mixture of 1-methyl-2-cyano-4- and 6-nitroben~ene obtained it accordance with a) were dissolved in 800 weight part ethanol and hydrogenated at 50 bar and 80C after adding 25 weigh part Rangy nickel. Thy catalyst way filtered off after cooling to room temperature, the filtrate was concentrated at reduced pressure, and the residue way dwelled. One then obtained 76 weight parts of a mixture of l-methyl-2-aminomethyl-4- and 6-aminob~nzene in the form of an oil which qolidifiad quickly. This mixture distilled at 135C to 180C ~0.3 mar).
;
C8H12N2 (Molecular weight 136, ma spectrometer) c) Preparation of an isomer mixture of 1 methyl-2-a~ino-methyl-4- and 6-aminocyclohexane Fifty weight part of the l-methyl~2-aminomethyl-4- and 6-aminobenzene obtained in accordance with b) wore hydrogenated in 400 volume parts Dixon in thy presence of 1.5 weight parts ruthenium oxide hydrate (prepared in accordance with German Patent 2132547~ at 150C and 250 bar. After cooling to room temperature, the catalyst was filtered off, the filtrate way concentrated at a reduced prowar and the residue way detailed I, Jo Thirty two weight part of a mixture of l-methyl-2-aminome~hyl 4 and 6-aminocyclohexane were obtained.
This mixture distilled at 83C to 85C (0.4 mar).
Analy8iq: C8H18~2 (Molecular weight: 142, Miss spectrum try C El N
Calculated, % by wt. 67.55 12.75 19.69 Found, % by weight 67. 30 12 . 70 19. 60 d) Preparation of an isomer mixture of l-methyl-2-i~o-cyanatomethyl-4- and 6-isocyanatocyclohexane 301ution of 14.2 weight part of the isomer mixture of l-methyl~2-aminomethyl--4 and 6-aminocyclohexane obtained in accordance with c) in 100 weight part o-dichlorobenzQne were added drops while stirring to a mixture of 260 weight part o-dichlorobenzene and 80 weight parts phosgene cooled to 0C. Aster completion of the addition, the mixture way heated slowly to 130C
and phosgene way directed through the reaction mixture : a this temperature for 1.5 hour. Then the reaction mixture was cooled to room temperature and excess phosgene was removed by purging nitrogen into thy mixture. Then the solvent way first distilled off at 10 to 20 mar and thereupon the residue way distilled under high vacuum. Ten and one-half weight part ox a mixture of l-methyl-2-i3Oeyanatomethyl-4- and 6-i~ocyanatocyclo-hexane having a distillation range of 110C to 112C
(cay. 0.1 bar) were obtained.
Analog: Clue (Molecular weight: 194, Moe spectrometer ) Calculated, % by wt. 61.83 7.2614.42 16.47 Found, % by White 7.5014.40 16.00 Example 2 a) Preparation of l-methyl-4-cyano-2-nitrobenzene Two hundred and forty weight parts of concentrated sulfuric acid were cooled to -5C in a reaction flask equipped with an addition funnel, stirrer, and thermos-eater. While stirring well, 40 weight parts Sweeney-Tulane way added in portions and then 25 volume parts concentrated nitric acid between -5C and ~5~C was added drops. In order to complete the nitration, eke mixture was stirred for an additional two hours a 09C
I
and the reaction Myra way then poured onto 400 weight part ice. The precipitate way filtered off, the filtered material way thoroughly washed with water and air-dried.
The product (50.9 weight parts) way 1-methyl-4-cyano-2-nitrobenzene having a melting point ox from 105C to 106C.
Preparation of l-methyl 4-aminomethyl-2-aminobenzene Sixty weigh part of the l-methyl-4-cyano-2-~itro-Bunsen obtained in accordance with a) were dissolved in ~00 weigh part ethanol and, after adding 20 weight part Rangy nickel, hydrogenated at 10 bar and 60~C
until no further hydrogen way consumed After adding 8 volume parts 3 percent ammonia solution, the hydrogen lion way again undertaken at 10 bar and 60C. After cooling to room temperature, the catalyst was filtered off and the filtrate way concentrated at reduced`
pressure. The residue was distilled under a high vacuum. Thirty-two and one-tenth weight part l-methyl-4-aminom~thyl-2-aminobenzene wore obtained, having a distillation range of from 130C Jo 135C (0.3 mar).
, C H N
Calculated, % by we. OWE 8.88 20.57 Found, % by wt. 70.80 9..00 19.90 I Preparation of l-methyl-4~aminomethyl-2-aminocyclohexane Twenty weight part of the l-methyl-4-aminomethyl~2-aminobenzene obtained in accordance with b) were hydrogenated in 150 volume part Dixon in the presence of 0.5 weight part ruthenium oxide hydrate (prepared in accordance with German Patent 2132547~ at 150C and 250 bar. After cooling to room temperature, the catalyst way filtered off, the filtrate way concentrated at reduced prowar, and the rudely way distilled.
Fourteen and four-tenths weight part methyl aminomethyl-2-aminocyclohexane were obtained having a boiling point of from 60C to 63C (0~04 mar).
Annul C8H18N2 (molecular weight: 142~ mast Jo ~pec~rometry) .
C H
Jo Calculated, % by wt. 67.55 12.75 19.69 I-: 20 Found, % by White 12.60 lg~.90 I
d) Preparation of l-methyl-4-i~ocyanatomeehyl-2-isocyanato-eyclohexane A solution of 9.1 weight part of the 1-methyl-4-a~ino-methyl-~-aminocyclohexan0 obtained in accordance with c) in 75 weight parts o~dichlorobenzene were added drops while mixing to a mixture of 150 weight parts ode-chlorobenzene and 55 weight part pho~gene cooled to 0C. After completion ox this addition, the mixture way Wylie heated to 130C and phosgene way directed into Jo 10 the reaction mixture at this temperature for 15 hour.
I;
I: Then the reaction mixture way cooled to room tempera-lure, and the excel phosgene was separated by using nitrogen. Thereupon, the solvent way distilled off at from 10 to 20 mar and the residue way distilled under high vacuum. Two and four tenth weight parts l-methyl-4-isocyanatomethyl-2-i~ocyanatocyclohexane having a boiling point of 9BC Jo 102~C (0.4 mar) were obtained.
Analysis Clown molecular weight: 194~ maws Bp~c~ome~cry ) Jo ï . ~,~ Us Jo
(I) (II) NO CHINOOK
or mixtures thereof, in which R is an alkyd group having from 1 to 12 carbon atoms.
~23~4~i Preferred are diisocyanates of formulae:
R R
(III) (IV) or mixtures thereof, in which the isocyanatomethyl group is bonded in the 2- or 4-position and the isocyanate group is in the 4- or 2-position.
The invention also relates to a process for the preparation of the above diisocyanates using dominoes of ; formulae:
SHEEHAN
No SHEEHAN
Descr~ltion of the Preferred Embodiments In formulae (I) through (VI), R is an alkyd radical having from l -to 12 carbon atoms, preferably from 1 to 4 carbon atoms, which may be branched, however, is preferably linear. Typical examples of such alkyd radicals are n-ponytail-, n-hexyl, Natalie, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl radicals, preferably the ethyl, n- and isopropyl, and n- and sec.-butyl radicals, and more preferably the methyl radical.
The following are typical examples of the dozes-antes of the invention:
1-methyl-2-isocyanatomethyl-3-isocyanato-, 1-methyl-2-isocyanatomethyl-5-isocyanato-, 1-methyl-2-isocyana-tomethyl-6-isocyanato-, 1 methyl-4-isocyanatomethyl-3-isocyanato-cyclohexane; 1-ethyl-2-isocyanatomethyl-3-:~;
I
isn't-, 1 ethy}-2-isocyanatomethyl-5-isocyanato-, l-ethyl-2-isocyanatomethyl-6-i~ocyanato-, ethyls-nato~ethyl-3-isocyanato-cyclohexane; 1-n--propyl-2-i ooze-natomethyl-3-i~ocyana~o-, 1-n-propyl-2-i~ocyanatomethyl-5-isocyanato-, l-n-propyl-2-i~ocyanatomethyl-6-isocyanato , 1-n-propyl-4-isocyanatomethyl-3-isocyanato-cyclohexaanew 1-isopropyl-2-iqocyanatomethyl-3-i~ocyanato-, 1-i~opropyl-2-i~ocyanatomethyl-4-isocyanato-, 1-isopropyl-2-isocyanato-methyl-5-isocyanato-, 1-isopropyl-2-isocyanatomethyl-6-isocyanato-, 1-i~opropyl-4-isocyanatomethyl-2-isocyanato-, ~opropyl-4-isocyanatome~hyl-3-isocyanato-cyclohexanno; 1-n-butyl-2-i~ocyanatomethyl-3-i~ocyanato-, l-n-butyl-2-isocyanatomethyl-4-isocyanato-, 1-n-butyl-2-isocyanato-methyl-5-isocyanato-, 1-n-butyl-2-i~ocyana~omethyl-6-isocyanato-, l-n-butyl-4-isocyanatomethyl-2-i~ocyanato-, 1-n-butyl-4-isocyanatomethyl-3-isocyanato-cyclohexanno, l-n-pentyl-2-isocyanatomethyl-4 isocyanato-, 1-n-pentyl-2 i30cyanatomethyl-6-isocyanato-, 1 n-pentyl-4-isocyanato-methyl-2-i ocyana~o-cyclohexane, 1-n-hexyl-2-i~ocyanato-methyl-4-isocyanato-, l-n-hexyl-2-i30cyanatomethyl-6-isocyanato-, l-n-hexyl-4 isocyanatomethyl-2-isocyanato-cyclohexane, l-n-heptyl-2-i~ocyanatomethyl-4-i~ocyanato-, 1-n-h~ptyl-2-isocyanatome~hyl-6-i~ocyanato-, Natalie-isocyanatomethyl~2-isocyanato-cyclohexane, 1-~-octyl-2-isocyanatom~thyl-4-isocyanato-, 1-n-octyl-2-isocyanato-S
methyl-6-i~ocyanato-, l n-octyl-4~isocyanatomethyl-2-isocyanato-cyclohexane; l-n-nonyl-2-i~ocyanatomethyl-4-iqocyanato~ n-nonyl-2-isocyanatome~hyl-6-i~ocyanato~
n-nonyl-A-i~ocyanatomethyl-2~ ocyanato-cyclohexane, l-n-dozily i~ocyanatomethyl-4-i30cyanato-, l-n-decyl-2-isocya-natomethyl-6 isocyana~o-, l-n-decyl-4-i~ocyanatomethyl-2-i~ocyanato-cyclohexane, l-n-undecyl-2-isocyana~omethyl-4-isocyanato~ n-undecyl-2-isocyanatomethyl-6-isocyanato-, l-n-undecyl-~-isocyanatomethyl-2-i30cyanato-cyclohhexane, l-n~dodecyl-2-isocyanatomethyl-4~isocyanato-, l-n-dodecyl-2-isocyanatomethyl-6-iqocyanato- and l-n-dodecyl~-4-isocyanato-methyl-2-i~ocyanato-cyclohexane.
Preferred are: l-ethyl-2-i~ocyanatomethyl-4-isn't-, 1-2thyl-4-isocyanatomethyl-2-i~ocyanato-cyclo-hexane, l-n-propyl-2-isocyanatomethyl-4-isocyanato- and l-n-propyl-4-i~ocyanatomethyl-2-i~ocyanato-cyclohexanee and more preferably l-methyl-2-i~ocyanatomethyl-4-isocyanato-, l-methyl-2-inocyanatomethyl-6-i~ocyanato-cyclohexanee as well a their ire mixture and l~methyl-4-isocyanatomethyl-2-i~ocyana~o-cyclohexa~e.
Demurrals corresponding to the dozes-notes cited above are used as the starting components for the preparation of the dli~ocyanate~ of the invention.
Here the following compound have proved to be particularly successful and are, therefore, preferably I
used: l-ethyl-2-a~inomethyl-4-amino-, 1-ethyl~4-amino-methyl-2~amino-cyclohexane, 1-n~propyl-2-aminomethyl-2-amino cyclohexane, l-n propyl-2-aminomethyl-4-amino- and 1-n-propyl-4 aminomethyl-2-amino-cyclohexane, and more preferably l-methyl-2-aminomethyl-4-amino-, 1-methyl-2-aminomethyl-6-amino-cyclohexane a well as their isomer mixer and l-methyl-4-aminomethyl-2-amino cyclohexane.
The dll~ocyanate3 and dominoes for these compound can be prevent in the form of isomer mixtures, mixtures of the tame immure but with different alkyd radical, or a mixture ox both types of mixture The preparation ox the novel dozes-antes can hollow the hollowing sequence, for example:
R R
: ON SHEEHAN
SIX) (Xj (XIj Pi ago I, C~2~H2 ICKY NH;2 (I) MY) Jo ..~
~3~5 The l-alkyl-2-cyanonitrobenzene~ (X) or the 1-alkyl-4-cyanonitrobenzene~ can Allah be prepared in even-tidally known procedures through the nitration of the corresponding l-~lkyl-2-cyanob2nzene~ (IX) or l-alkyl-4-cyanobenzenes, for example, in the manner described in thy (1~98), p. 2880 if. or in the Journal of American Chemical So 99 (1977), p. 6721 or suitable variant of these method.
Another method for the preparation of the alkyd-cyanonitrobenzenes cited a an example lie in the known process for exchanging the amino group in the alkyl-amino nitrobenzenes for a neural group, corresponding to Journal I (1979), p. 4003.
Thy l-alkyl-cyanonitrobenzene~ obtained in the nitration or their Homer mixtures can be reduced directly, i.e., without further purification, to l-alkyl-aminomethyl-aminobenzene~ or their isomer mixture. Similar, for example, to the process described for 2-cyanonitrotoluene in Formic peeve), Edit. Sat. 25 (1970), p. 163 (C. A. 72, ~21 101 d, 1970). The reduction of the vitro and the cyan group can be completed here in one or two ~equen',ial reaction Taipei. It it not always necessary to add ammonia.
The aromatic ring reduction of the alkali-aminomethyl-aminobenzenes I or the l-alkyl-4-aminomethyl-aminob~n Noah follows known prowesses, for example, those G
-or -I
cited in Hobnail, Methadone don organlsch~n Comma, Thea Ed., solo XI/l, (Stuttgart: Gorge Thyme Verlag, 1957~, p. 678 if., I Ferry Reaktionen don orqa~ en Saab (George Thyme V~rlag: Stuttgart, 19783, pp. 83, 90 of.;
A. E. ark doll et at, J. Amen Comma. Sock 75 (1953~, p. 1156, ye lo Lookers. (1982), pp. 603~606, Us S.
Patent 2,494,563 or German laid-open Application 21 32 547.
In order to prepare the l~alkyl-2-aminomethyl~
aminocyclohexane (~) or the l-alkyl-4-aminom~thyl amino-cyclohexane, one can alto tart directly with alkali-cyanonitrobenzenes (X).
The resulting l-alkyl aminomethyl-aminocyclo hexanes can be phosgenated in solvents either directly or as salts, preferably hydrogen chlorides. Suitable solvent are, for example: Tulane, zillion, chlorobenzene, or dichlorobenzene. A 301ution of the l-alXyl-aminomethyl-aminocyclohexane~ or a suspension of the corresponding salts is reacted accordingly at temperature of approximately 0C
to 100C, preferably from 10C to SKYE, with 1 to 6 moles pho~gene per NH2-HCl, preferably from 1 to 2.5 moles phosgene, and the intermediately formed carbamic chloride can by cleaved at temperature from 80C to 180C, prefer-ably from 120 to 160C in the l-alkyl-i30cyanato~eehyl-iRocyanatocyclohexane. The gaseous or liquid pho3g~ne is charged directly into the reaction mixture at such a rate it "
~23~
that the emerging gases primarily are composed of hydrogen chloride.
After completion of pho~genation and cleavage, the solvent it distilled off at reduced pressure, for example, from lo to lo mar. However, it may Allah be Advents to trip the hydrogen chloride or any excel phosgene which may be present Prom the doesn't solution with the aid of nitrogen or another inert gee before the solvent it distilled off.
The resulting crude l-alkyl-2- or 4-isocyanato-methyl-lsocyanatocyclohexane~ or isomer mixtures can by separated and purified by distillation at reduced prowar.
The disunites of the invention can also be Jo prepared through the thermal cleavage of the corresponding diurethane~ in the guy or liquid phase, if Nasser in the prank of c~ta.ly~t3, whereby the diurethane~ are obtained in an efficacious manner according to the process described in European Patent published application 18 583 (U. S. Patent 4, 278, 805) through the reaction of carbamate I with the l-alkyl-aminocyclohexane~ in the presence of alcohols and, if necessary, urea.
The l-alkyl-2- or 4-aminomethyl-aminocyclohexane~
and alkali- or 4-i~ocyanatomethyl-i30cyanatocylohexane~
are valuable intermediate and eed~tock~ for crop protect lion agent and plastic ~23~ 5 The dominoes are preferably converted into diisocyanat~s. Such diisocyanates are particularly well suited for the preparation of polyurethane foam, adhesives, paints, coatings, and sealants.
The following examples art intended to further explain the invention without necessarily limiting it scope.
' J
I
eye a) Preparation of an isomer mixture of l-methyl-2-cyano~4-nitrobsnzene and 1-methyl-2-cyano-6-nitrobenzene Twelve hundred part by weight concentrated sulfuric acid were cooled to -5C in a reaction flask equipped with an addition funnel, a stirrer, and a thermometer.
While stirring well, 200 weight part 2-cyanotoluene followed by 151 weight parts concentrated nitric acid between -5~C and ~5C were added drops within one hour. In order to complete the nitration, stirring continued for an additional 1.5 hour at 0C, whereupon the reaction mixture was poured onto 2000 weight part ice The precipitate way filtered off, the filtered solid was thoroughly washed with water and dried on clay.
Two hundred and eighty-two weight part of a crude isomer mixture of l-methyl-2-cyano-4- and 6-nitrobenzene were obtained at a weigh ratio of approximately 87:13 and having a melting point ox from glC to 92~C.
0 by Preparation of an isomer mixture of l-methyl-2-amino-methyl-4- and 6-aminobenzene JO
r-One hundred weigh parts of the isomer mixture of 1-methyl-2-cyano-4- and 6-nitroben~ene obtained it accordance with a) were dissolved in 800 weight part ethanol and hydrogenated at 50 bar and 80C after adding 25 weigh part Rangy nickel. Thy catalyst way filtered off after cooling to room temperature, the filtrate was concentrated at reduced pressure, and the residue way dwelled. One then obtained 76 weight parts of a mixture of l-methyl-2-aminomethyl-4- and 6-aminob~nzene in the form of an oil which qolidifiad quickly. This mixture distilled at 135C to 180C ~0.3 mar).
;
C8H12N2 (Molecular weight 136, ma spectrometer) c) Preparation of an isomer mixture of 1 methyl-2-a~ino-methyl-4- and 6-aminocyclohexane Fifty weight part of the l-methyl~2-aminomethyl-4- and 6-aminobenzene obtained in accordance with b) wore hydrogenated in 400 volume parts Dixon in thy presence of 1.5 weight parts ruthenium oxide hydrate (prepared in accordance with German Patent 2132547~ at 150C and 250 bar. After cooling to room temperature, the catalyst was filtered off, the filtrate way concentrated at a reduced prowar and the residue way detailed I, Jo Thirty two weight part of a mixture of l-methyl-2-aminome~hyl 4 and 6-aminocyclohexane were obtained.
This mixture distilled at 83C to 85C (0.4 mar).
Analy8iq: C8H18~2 (Molecular weight: 142, Miss spectrum try C El N
Calculated, % by wt. 67.55 12.75 19.69 Found, % by weight 67. 30 12 . 70 19. 60 d) Preparation of an isomer mixture of l-methyl-2-i~o-cyanatomethyl-4- and 6-isocyanatocyclohexane 301ution of 14.2 weight part of the isomer mixture of l-methyl~2-aminomethyl--4 and 6-aminocyclohexane obtained in accordance with c) in 100 weight part o-dichlorobenzQne were added drops while stirring to a mixture of 260 weight part o-dichlorobenzene and 80 weight parts phosgene cooled to 0C. Aster completion of the addition, the mixture way heated slowly to 130C
and phosgene way directed through the reaction mixture : a this temperature for 1.5 hour. Then the reaction mixture was cooled to room temperature and excess phosgene was removed by purging nitrogen into thy mixture. Then the solvent way first distilled off at 10 to 20 mar and thereupon the residue way distilled under high vacuum. Ten and one-half weight part ox a mixture of l-methyl-2-i3Oeyanatomethyl-4- and 6-i~ocyanatocyclo-hexane having a distillation range of 110C to 112C
(cay. 0.1 bar) were obtained.
Analog: Clue (Molecular weight: 194, Moe spectrometer ) Calculated, % by wt. 61.83 7.2614.42 16.47 Found, % by White 7.5014.40 16.00 Example 2 a) Preparation of l-methyl-4-cyano-2-nitrobenzene Two hundred and forty weight parts of concentrated sulfuric acid were cooled to -5C in a reaction flask equipped with an addition funnel, stirrer, and thermos-eater. While stirring well, 40 weight parts Sweeney-Tulane way added in portions and then 25 volume parts concentrated nitric acid between -5C and ~5~C was added drops. In order to complete the nitration, eke mixture was stirred for an additional two hours a 09C
I
and the reaction Myra way then poured onto 400 weight part ice. The precipitate way filtered off, the filtered material way thoroughly washed with water and air-dried.
The product (50.9 weight parts) way 1-methyl-4-cyano-2-nitrobenzene having a melting point ox from 105C to 106C.
Preparation of l-methyl 4-aminomethyl-2-aminobenzene Sixty weigh part of the l-methyl-4-cyano-2-~itro-Bunsen obtained in accordance with a) were dissolved in ~00 weigh part ethanol and, after adding 20 weight part Rangy nickel, hydrogenated at 10 bar and 60~C
until no further hydrogen way consumed After adding 8 volume parts 3 percent ammonia solution, the hydrogen lion way again undertaken at 10 bar and 60C. After cooling to room temperature, the catalyst was filtered off and the filtrate way concentrated at reduced`
pressure. The residue was distilled under a high vacuum. Thirty-two and one-tenth weight part l-methyl-4-aminom~thyl-2-aminobenzene wore obtained, having a distillation range of from 130C Jo 135C (0.3 mar).
, C H N
Calculated, % by we. OWE 8.88 20.57 Found, % by wt. 70.80 9..00 19.90 I Preparation of l-methyl-4~aminomethyl-2-aminocyclohexane Twenty weight part of the l-methyl-4-aminomethyl~2-aminobenzene obtained in accordance with b) were hydrogenated in 150 volume part Dixon in the presence of 0.5 weight part ruthenium oxide hydrate (prepared in accordance with German Patent 2132547~ at 150C and 250 bar. After cooling to room temperature, the catalyst way filtered off, the filtrate way concentrated at reduced prowar, and the rudely way distilled.
Fourteen and four-tenths weight part methyl aminomethyl-2-aminocyclohexane were obtained having a boiling point of from 60C to 63C (0~04 mar).
Annul C8H18N2 (molecular weight: 142~ mast Jo ~pec~rometry) .
C H
Jo Calculated, % by wt. 67.55 12.75 19.69 I-: 20 Found, % by White 12.60 lg~.90 I
d) Preparation of l-methyl-4-i~ocyanatomeehyl-2-isocyanato-eyclohexane A solution of 9.1 weight part of the 1-methyl-4-a~ino-methyl-~-aminocyclohexan0 obtained in accordance with c) in 75 weight parts o~dichlorobenzene were added drops while mixing to a mixture of 150 weight parts ode-chlorobenzene and 55 weight part pho~gene cooled to 0C. After completion ox this addition, the mixture way Wylie heated to 130C and phosgene way directed into Jo 10 the reaction mixture at this temperature for 15 hour.
I;
I: Then the reaction mixture way cooled to room tempera-lure, and the excel phosgene was separated by using nitrogen. Thereupon, the solvent way distilled off at from 10 to 20 mar and the residue way distilled under high vacuum. Two and four tenth weight parts l-methyl-4-isocyanatomethyl-2-i~ocyanatocyclohexane having a boiling point of 9BC Jo 102~C (0.4 mar) were obtained.
Analysis Clown molecular weight: 194~ maws Bp~c~ome~cry ) Jo ï . ~,~ Us Jo
Claims (7)
1. A diisocyanate selected from the group consisting of (I), (II), and a mixture thereof, in which R is an alkyl group having from 1 to 12 carbon atoms.
2. A diisocyanate of claim 1 selected from the specific isomers of the following formulas (III), (IV), and a mixture thereof, in which R is an alkyl group having from 1 to 12 carbon atoms.
3, A diisocyanate of claim 2 in which R is a methyl, ethyl, n-propyl, isopropyl or n-butyl group.
4. 1-Methyl-2-isocyanatomethyl-4-isocyanato-cyclohexane.
5. 1-Methyl-2-isocyanatomethyl-6-isocyanato-cyclohexane.
6. 1-Methyl-4-isocyanatomethyl-2-isocyanato-cyclohexane.
7. A process for the preparation of a diiso-cyanate of claim 1 wherein a diamine of formulae:
(V) (VI) or mixtures thereof, is phosgenated in a solvent at a temperature of about 0 to 100°C and the resulting carbamic chloride is thermally cleaved at a temperature of from about 80 to 180°C.
(V) (VI) or mixtures thereof, is phosgenated in a solvent at a temperature of about 0 to 100°C and the resulting carbamic chloride is thermally cleaved at a temperature of from about 80 to 180°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000529628A CA1248552A (en) | 1983-05-17 | 1987-02-12 | 1-alkyl-2-aminomethyl-aminocyclohexane and/or 1-alkyl- 4-aminomethyl-aminocyclohexane |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3317875A DE3317875A1 (en) | 1983-05-17 | 1983-05-17 | 1-ALKYL-2-ISOCYANATOMETHYL-ISOCYANATO-CYCLOHEXANE AND / OR 1-ALKYL-4-ISOCYANATOMETHYL-ISOCYANATO-CYCLOHEXANE, AND THE CORRESPONDING DIAMINES, METHOD AND PRODUCTION THEREOF |
| DEP3317875.5 | 1983-05-17 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000529628A Division CA1248552A (en) | 1983-05-17 | 1987-02-12 | 1-alkyl-2-aminomethyl-aminocyclohexane and/or 1-alkyl- 4-aminomethyl-aminocyclohexane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1239415A true CA1239415A (en) | 1988-07-19 |
Family
ID=6199161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000454484A Expired CA1239415A (en) | 1983-05-17 | 1984-05-16 | Amino-aminomethylcyclohexanes, useful for the preparation of their corresponding diisocyanates |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0128382B1 (en) |
| CA (1) | CA1239415A (en) |
| DE (2) | DE3317875A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5786438A (en) * | 1996-04-11 | 1998-07-28 | Bayer Aktiengesellschaft | Mixtures of cycloaliphatic diisocyanates, a process for their preparation and their use for the production of polyisocyanate addition products |
| US5837796A (en) * | 1996-07-10 | 1998-11-17 | Bayer Aktiengesellschaft | Polyisocyanates containing isocyanurate groups and prepared by trimerizing alkyl-substituted cycloaliphatic diisocyanates |
| US8586794B2 (en) | 2008-07-25 | 2013-11-19 | Basf Se | 5-isopropyl-3-aminomethyl-2-methyl-1-amino-cyclohexane (carvone diamine), and method for the production thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4879410A (en) * | 1986-11-03 | 1989-11-07 | American Cyanamid Company | Preparation of primary aralkyl urethanes and ureas and isocyanates derived therefrom |
| EP0976723A3 (en) * | 1998-07-31 | 2001-02-07 | Daicel Chemical Industries, Ltd. | A cycloaliphatic polyisocyanate compound, a process for the preparation thereof, a polyurethane therefrom, and an adhesive composition |
| WO2010009994A2 (en) * | 2008-07-25 | 2010-01-28 | Basf Se | 3-aminomethyl-1-cyclohexylamine, and method for the production thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2692275A (en) * | 1953-01-23 | 1954-10-19 | Rohm & Haas | Preparation of 1, 8-diisocyanato-p-menthane |
| CH572460A5 (en) * | 1972-07-28 | 1976-02-13 | Ciba Geigy Ag |
-
1983
- 1983-05-17 DE DE3317875A patent/DE3317875A1/en not_active Withdrawn
-
1984
- 1984-05-14 DE DE8484105472T patent/DE3479886D1/en not_active Expired
- 1984-05-14 EP EP84105472A patent/EP0128382B1/en not_active Expired
- 1984-05-16 CA CA000454484A patent/CA1239415A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5786438A (en) * | 1996-04-11 | 1998-07-28 | Bayer Aktiengesellschaft | Mixtures of cycloaliphatic diisocyanates, a process for their preparation and their use for the production of polyisocyanate addition products |
| US5837796A (en) * | 1996-07-10 | 1998-11-17 | Bayer Aktiengesellschaft | Polyisocyanates containing isocyanurate groups and prepared by trimerizing alkyl-substituted cycloaliphatic diisocyanates |
| US8586794B2 (en) | 2008-07-25 | 2013-11-19 | Basf Se | 5-isopropyl-3-aminomethyl-2-methyl-1-amino-cyclohexane (carvone diamine), and method for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0128382B1 (en) | 1989-09-27 |
| EP0128382A1 (en) | 1984-12-19 |
| DE3317875A1 (en) | 1984-11-22 |
| DE3479886D1 (en) | 1989-11-02 |
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