CA1111063A - Process for the manufacture of carbamic acid esters of high-boiling alcohols - Google Patents
Process for the manufacture of carbamic acid esters of high-boiling alcoholsInfo
- Publication number
- CA1111063A CA1111063A CA292,686A CA292686A CA1111063A CA 1111063 A CA1111063 A CA 1111063A CA 292686 A CA292686 A CA 292686A CA 1111063 A CA1111063 A CA 1111063A
- Authority
- CA
- Canada
- Prior art keywords
- carbamic acid
- mole
- relatively high
- acid esters
- reaction
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
PROCESS FOR THE MANUFACURE OF CARBAMIC ACID ESTERS OF
HIGH-BOILING ALCOHOLS
Abstract of the disclosure:
An improved process for the manufacture of carbamid acid esters of high-boiling alcohols by trans-esterification of lower aliphatic carbamic acid esters with relatively high-boiling alcohols in the presence of an alkyl titanate as a catalyst.
HIGH-BOILING ALCOHOLS
Abstract of the disclosure:
An improved process for the manufacture of carbamid acid esters of high-boiling alcohols by trans-esterification of lower aliphatic carbamic acid esters with relatively high-boiling alcohols in the presence of an alkyl titanate as a catalyst.
Description
The conventional method ~or the manufacture of carbamic acid esters of relatively high molecular weight is to synthesize ~ - chlorocarbonic acid esters from the corresponding relatively - hig~ molecular weight alcohols by phosgenation followed by aminolysis of these esters.
This expensive method of manufacture can be replaced by . R reaction of lower aliphatic carbamic acid esters with rela~
tively high molecular weight alcohols. In U.S. Patent Specification 2,934,549, S. Beinfest et al. describe a process o~ this type, and propose the use of aluminum alcoholat~es as - catalysts.
- It has now been found? surprisingly, that low molecular weight alkyl titanates are substantially more active catalysts :. x than the- aluminum alcoholates for esterification reactions of this type. When using alkyl titanates it generally proves possible, under otherwise identical conditions, to shorten the reaction times to half, and in many cases to one-tenth, of the time required when using aluminum alcoholates.
Usin~ the new method according to the invention, it is also not necessary to employ an excess of lower aliphatic car-bamic acid esters, as is described in Examples 1 and 5 - 7 of U.S. Patent Specification 2,934,559. Thus, in the trans-esterification of ethyl carbamate with 1,5-pentanediol, des-cribed in Example 6 of U.S. Patent Specification 2,g~4,559, it proved possible~ when using the method according to the inven tion, to increase the yield from 68.5% to 91% in spite of reducing the amount of carbamic acid ester from 1.~ molesto one mole equivalent. The reaction time was reduced from 4 hours x the ' to 1~ hours.
In the case of the trans-esterification with relatively high molecular weight polyglycol ethers, -the method according to U.S. Patent Specification 2,934,559, using aluminum alcoholate as the catalyst, proves even more disadvantageous since, for example, when using a polyglycol of molecu:Lar weight 1,000 the reaction time must be increased by more than 20 hours in order to achieve 70% con-verslon.
Accordingly, the invention relates to a process for the manufacture of a carbamic acid ester of a relatively high boiling alcohol selected from alkanols and alkanediols, their oxalkylation products, and the oxalkylation products of trihydric or tetrahydric aliphatic alcohols, said relatively high boiling alcohol having a boiling point of above 190C, which comprises transesterifying one mole of C2-C5-alkyl carbamic acid ester with one mole of said relatively high boiling alcohol in the presence of a Cl-C4-alkyl titanate as a catalyst and distilling off from the reaction mixture the lower alcohol resulting from the carbamic acid ester.
By relatively high-boiling alcohols there are essentially to be understood alkanols or alkanediols, their oxyalkylation pro-ducts and the oxyalkylation products of trihydric or tetrahydric aliphatic alcohols which at normal conditions have a boiling point above 190 and above of the low molecular weight carbamic acid esters employed.
The reaction temperature, in the reaction according to the invention of low molecular weight carbamic acid esters with relatively high-boiling alcohols is in general set to from about 80 to 210C at pressures of from about 25 to 760 mm Hg.
This expensive method of manufacture can be replaced by . R reaction of lower aliphatic carbamic acid esters with rela~
tively high molecular weight alcohols. In U.S. Patent Specification 2,934,549, S. Beinfest et al. describe a process o~ this type, and propose the use of aluminum alcoholat~es as - catalysts.
- It has now been found? surprisingly, that low molecular weight alkyl titanates are substantially more active catalysts :. x than the- aluminum alcoholates for esterification reactions of this type. When using alkyl titanates it generally proves possible, under otherwise identical conditions, to shorten the reaction times to half, and in many cases to one-tenth, of the time required when using aluminum alcoholates.
Usin~ the new method according to the invention, it is also not necessary to employ an excess of lower aliphatic car-bamic acid esters, as is described in Examples 1 and 5 - 7 of U.S. Patent Specification 2,934,559. Thus, in the trans-esterification of ethyl carbamate with 1,5-pentanediol, des-cribed in Example 6 of U.S. Patent Specification 2,g~4,559, it proved possible~ when using the method according to the inven tion, to increase the yield from 68.5% to 91% in spite of reducing the amount of carbamic acid ester from 1.~ molesto one mole equivalent. The reaction time was reduced from 4 hours x the ' to 1~ hours.
In the case of the trans-esterification with relatively high molecular weight polyglycol ethers, -the method according to U.S. Patent Specification 2,934,559, using aluminum alcoholate as the catalyst, proves even more disadvantageous since, for example, when using a polyglycol of molecu:Lar weight 1,000 the reaction time must be increased by more than 20 hours in order to achieve 70% con-verslon.
Accordingly, the invention relates to a process for the manufacture of a carbamic acid ester of a relatively high boiling alcohol selected from alkanols and alkanediols, their oxalkylation products, and the oxalkylation products of trihydric or tetrahydric aliphatic alcohols, said relatively high boiling alcohol having a boiling point of above 190C, which comprises transesterifying one mole of C2-C5-alkyl carbamic acid ester with one mole of said relatively high boiling alcohol in the presence of a Cl-C4-alkyl titanate as a catalyst and distilling off from the reaction mixture the lower alcohol resulting from the carbamic acid ester.
By relatively high-boiling alcohols there are essentially to be understood alkanols or alkanediols, their oxyalkylation pro-ducts and the oxyalkylation products of trihydric or tetrahydric aliphatic alcohols which at normal conditions have a boiling point above 190 and above of the low molecular weight carbamic acid esters employed.
The reaction temperature, in the reaction according to the invention of low molecular weight carbamic acid esters with relatively high-boiling alcohols is in general set to from about 80 to 210C at pressures of from about 25 to 760 mm Hg.
- 2 -' :
' ' ' . ~ ' ' ': -~ ~;
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3~-3 i The reaction temperature depends on the boiling point of the ; alcohol liberated and on the structure of the relatively high-~`:
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:
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'''"`
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~, ~,.
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boiling alcohol. Whilst, for example, polyethylene glycols of molecular weigh-t up to about 300 undergo trans-esterification even at atmospheric pressure and temperatures of from about 160 to about 180C, it is necessary, when employing relatively high molecular weight polyethylene glycols, to use reduced pressure of, for example, 100 to 300 mm Hg. Lower pressures are alsv o~ advantage if the reaction can be carried out at low reaction temperatures. In the trans-esterification reaction according to Ihe invention, the reaction temperatures and pressures to be used are limited by the boiling point of the low molecular weight carbamic acid esters employed. When using carbamic acid ethyl ester, for eæample, these limits are 180C at a pressure of 760 mm Hg or, for example, 140C at a pressure of 240 mm Hg. Preferably3 the reaction is carried out at ~emperatures of about 140 - 160 and pressures of 100 to 240 mm Hg, provided the reactants permit this.
Relatively high boiling alcohols which can be used for the trans-esterification reaction according to the invention are, above all, aliphati~, saturated monohydric or polyhydric alcohols or ether-alcohols which have a boiling point, under the reaction conditions, above that of the low molecular weight carbamic acid ester employed. The boiling point of the relatively high-boiling alcohols should be above 190C &nd preferably above 210C. Relatively high-boiling aîcohols which may be used in particular are alcohols, above all so-called fatty alcohols with about 8 to 20 carbon atoms~ for example cctyl alcohol, dodecyl alcohol 7 stea~yl alcohol or c~tjl alcohol, and their reaction products with about 1 to 5C moles .
.. ';
of ethylene oxide~ or of ethylene oxide and propylene oxide, ~- for example pentaethoxy-dodecanol and tetrapropoxy-heptaethoxy-- octadecanol, as well as alkanediols with 2 to 5 carbon atoms in ~ . .
the reaction products of these alkanediols or of trihydric and ., tetrahydric alcohols, such as pentaerythritol or glycerol, with about l to 200 moles of ethylene oxide, or of ethylene oxide and propylene oxide. Preferred examples of such relatively high-boiling alcohols which may be mentioned are ethylene glycol~
diethylene glycol, polyethylene glycols wi-1;h molecular weights of 150 to about lO,000, and also propylene glycol, butylene glycol,pentane-1,5-glycol,..
In view of the possible use of the reaction products according to the invention as plasticizers for cellulose art icles, polyethylene glycols with molecular weights of from about 200 to 5,000 are preIerentially employed for the trans-esterification reaction.
Low molecular weight carbamic acid esters which can be .
used are the alkyl carbamates containing 2 to 5 carbon atoms, such as carbamic acid methyl ester, ethyl ester, propyl ester, isopropyl ester and butyl ester, or mixtures of the said car-bamates.
Suitable alkyl titanates are above all those with 1 to carbon atoms. For example, methyl titanate, ethyl titan-ate or isopropyl titanate can be employed. m e concentra-tion o~ the alkyl titanates to be used in the trans-esterification process according to the invention can va~y within wide limits5 i-t should be optimized in each particular case. Preferably, O.OOl to about O.l mole of the alkyl tit~na-te is employed per mole of the relatively high-boiling alcohol.
- To carry out the trans-esteri~cation according to the invention, the two components, namely the carb~mic acid ester and the relatively high-boiling alcohol are advantageously employed in about the equivalent ratio. The reaction time for the trans-esterification according to the invention depends above all on the nature of the relatively high-boiling alcohol used and on the reaction conditions employed. In most cases, ~ a reaction time of about 1 - 2 hours suffices; however, in order to achie~e as far-reaching a trans-ecterification as poss-ible, this will in general be followed by a post-reaction period of about 2 - 4 hours.
- The carbamic acid esters of relatively high-boiling alcohols obtained according to the invention can be used as plasticizers for fibers and films of natural and regenerated cellulose and as agents for rendering synthetic fibers hydro-philic. Reaction of the carbamic acid esters according to ~he invention ~ith formaldehyde gives products which possess groups which are reactive towards cellulose and can be used as reactive plasticizers for cellulose fibers and films.
Example 1:
200 g (1 mole) of a polyethylene glycol of molecular weight 200, together with 178 g (2 moles) of carbamic acid ethyl ester and 2 g of ethyl titanate are heated to 160 - 180C
in a four-necked flask equipped with a distillation a-t-tachmen~
thermometer, stirrer and heater. Hereupon, 82 g of ethanol (1.78 moles) distil off in the course of 2 hours. Poly-ethylene glycol(200) bis-carbamic acid ester is obtained ~n a .
-. :
.
yield of 258 g (89~' of theory).
Example 2 500 g (0.5 mole) of a polyethylene glycol of molecularweight 1,000 together with 89 g (1 mole) of carbamic acid ethyl ester and 2 g of isopropyl titanate are heated under a pressure of 200 mm Hg to 140 - 150C whilst stirring and the ethanol ~ormed is collected in a cold trap. A~t;er as little as 90 minutes' reaction time, 41.5 g (90% of theory)'of the alcohol ha~e distilled over.'In the course of a further 40 minutes'period of heating, a further 45 g of ethanol are obtained. 530 g of polyethylene glycol(l,OOQ) bis-carbamic acid ester are obtained, corresponding to a conversion of 97.7%.
Example 3 135 g (0.5 mole) of octadecyl alcohol together with 51.5 g (0.5 mole) of carbamic acid isopropyl ester and 1 g of iso-propyl titanate are heated under a pressure of 300 ~m Hg to 150 - 155C, whilst stirring. Hereupon, 29 g of isopropanol distil off in the course of 75 minutes. Carbamic acid octa-, -decyl ester is obtained in a yield of 136 g (99% of theory) and with a melting point of 93 - 94C (after recrystallization from ethanol).
Exam~le 4 31 g (0.5 mole) of ethylene glycol and 89 g (1 mole) of carbamic acid ethyl ester are heated together with 2 g of iso-propyl titanate. Using an external temperature of 180 -195C, 41 g of ethanol hereupon distil off in the couuse o~ 6 hours t~Lrough a descending condenser.
After'recrystallization from eth~-lol) 55 g o~ ethylene , glycol bis-carbamic acid ester are obtained, corresponding to a yield of 74%.
Example 5 1,000 g (0.2 mole) of a polyether-alcohol of molecular weight 5,000, obtained by reacting 1 mole of pentaerythri-tol with 20 moles of propylene oxide and 80 moles of ethylene oxide, are heaied together with 35.6 g (0.4 mole) of carbamic acid ethyl ester and 2 g of isopropyl titanate to 150C under a pres-sure of 300 mm Hg. m e 18.2 g of eth~nol which hereupon distil off in the course of 6 hours and are collected in a cold trap correspond to a conversion of 98% based on the carbamic acid ethyl ester employed.
Example 6 ` 500 g (0.5 mole) of a polyethylene glycol cf molecular weight 1,000, 117 g (1.0 mole) of carbamic acid butyl ester and 1.3 g (0.05 mole) of ethyl titanate are heated under a pressure 140 mm Hg to 150 - 160C, whilst stirring- Hereupon~ 65g of~uta-ncl distil off, in the courseof3hours,anda~ collected, ~ a adescending condenser, in an ice-coo'ed receiver. This corresponds to . ~
a conversion of 88~.
Polyethylene glycol(l,000) bis-carbamic acid ester is ` obtained in a yield of 548 g.
:' . ~ , 338 g (0.4 mole) of a reaction product of 1 mole of dodecyl alcohol with 15 moles of ethylene oxide are heated together with 47 g (0.4 mole) of butylurethane ~nd 2 g o~ iso-propyl titanate ~nder a pressure of 140 mm Hg to 150 160C, whilst stirring. After 2 hours, the pressure is reduced to .:
' '. ' .
' ~
60 mm Hg. Hereupon, 31.7 g of alcohol distil over, in which 26 g (82% of theory) of butanol were found by gas chromatography. m is corresponds to a conversion of ~8%.
- The yield of carbamic acid ester of ethoxylated dodecyl alcohol is 320 g (90% of theory).
;~.' ' ` , ' .
. - . .
, . . .
, .
: ~ .
. ~
;,.
~ . .
:
':' ',.:
'''"`
'' :;
~, ~,.
` - 2a -, ~, .
boiling alcohol. Whilst, for example, polyethylene glycols of molecular weigh-t up to about 300 undergo trans-esterification even at atmospheric pressure and temperatures of from about 160 to about 180C, it is necessary, when employing relatively high molecular weight polyethylene glycols, to use reduced pressure of, for example, 100 to 300 mm Hg. Lower pressures are alsv o~ advantage if the reaction can be carried out at low reaction temperatures. In the trans-esterification reaction according to Ihe invention, the reaction temperatures and pressures to be used are limited by the boiling point of the low molecular weight carbamic acid esters employed. When using carbamic acid ethyl ester, for eæample, these limits are 180C at a pressure of 760 mm Hg or, for example, 140C at a pressure of 240 mm Hg. Preferably3 the reaction is carried out at ~emperatures of about 140 - 160 and pressures of 100 to 240 mm Hg, provided the reactants permit this.
Relatively high boiling alcohols which can be used for the trans-esterification reaction according to the invention are, above all, aliphati~, saturated monohydric or polyhydric alcohols or ether-alcohols which have a boiling point, under the reaction conditions, above that of the low molecular weight carbamic acid ester employed. The boiling point of the relatively high-boiling alcohols should be above 190C &nd preferably above 210C. Relatively high-boiling aîcohols which may be used in particular are alcohols, above all so-called fatty alcohols with about 8 to 20 carbon atoms~ for example cctyl alcohol, dodecyl alcohol 7 stea~yl alcohol or c~tjl alcohol, and their reaction products with about 1 to 5C moles .
.. ';
of ethylene oxide~ or of ethylene oxide and propylene oxide, ~- for example pentaethoxy-dodecanol and tetrapropoxy-heptaethoxy-- octadecanol, as well as alkanediols with 2 to 5 carbon atoms in ~ . .
the reaction products of these alkanediols or of trihydric and ., tetrahydric alcohols, such as pentaerythritol or glycerol, with about l to 200 moles of ethylene oxide, or of ethylene oxide and propylene oxide. Preferred examples of such relatively high-boiling alcohols which may be mentioned are ethylene glycol~
diethylene glycol, polyethylene glycols wi-1;h molecular weights of 150 to about lO,000, and also propylene glycol, butylene glycol,pentane-1,5-glycol,..
In view of the possible use of the reaction products according to the invention as plasticizers for cellulose art icles, polyethylene glycols with molecular weights of from about 200 to 5,000 are preIerentially employed for the trans-esterification reaction.
Low molecular weight carbamic acid esters which can be .
used are the alkyl carbamates containing 2 to 5 carbon atoms, such as carbamic acid methyl ester, ethyl ester, propyl ester, isopropyl ester and butyl ester, or mixtures of the said car-bamates.
Suitable alkyl titanates are above all those with 1 to carbon atoms. For example, methyl titanate, ethyl titan-ate or isopropyl titanate can be employed. m e concentra-tion o~ the alkyl titanates to be used in the trans-esterification process according to the invention can va~y within wide limits5 i-t should be optimized in each particular case. Preferably, O.OOl to about O.l mole of the alkyl tit~na-te is employed per mole of the relatively high-boiling alcohol.
- To carry out the trans-esteri~cation according to the invention, the two components, namely the carb~mic acid ester and the relatively high-boiling alcohol are advantageously employed in about the equivalent ratio. The reaction time for the trans-esterification according to the invention depends above all on the nature of the relatively high-boiling alcohol used and on the reaction conditions employed. In most cases, ~ a reaction time of about 1 - 2 hours suffices; however, in order to achie~e as far-reaching a trans-ecterification as poss-ible, this will in general be followed by a post-reaction period of about 2 - 4 hours.
- The carbamic acid esters of relatively high-boiling alcohols obtained according to the invention can be used as plasticizers for fibers and films of natural and regenerated cellulose and as agents for rendering synthetic fibers hydro-philic. Reaction of the carbamic acid esters according to ~he invention ~ith formaldehyde gives products which possess groups which are reactive towards cellulose and can be used as reactive plasticizers for cellulose fibers and films.
Example 1:
200 g (1 mole) of a polyethylene glycol of molecular weight 200, together with 178 g (2 moles) of carbamic acid ethyl ester and 2 g of ethyl titanate are heated to 160 - 180C
in a four-necked flask equipped with a distillation a-t-tachmen~
thermometer, stirrer and heater. Hereupon, 82 g of ethanol (1.78 moles) distil off in the course of 2 hours. Poly-ethylene glycol(200) bis-carbamic acid ester is obtained ~n a .
-. :
.
yield of 258 g (89~' of theory).
Example 2 500 g (0.5 mole) of a polyethylene glycol of molecularweight 1,000 together with 89 g (1 mole) of carbamic acid ethyl ester and 2 g of isopropyl titanate are heated under a pressure of 200 mm Hg to 140 - 150C whilst stirring and the ethanol ~ormed is collected in a cold trap. A~t;er as little as 90 minutes' reaction time, 41.5 g (90% of theory)'of the alcohol ha~e distilled over.'In the course of a further 40 minutes'period of heating, a further 45 g of ethanol are obtained. 530 g of polyethylene glycol(l,OOQ) bis-carbamic acid ester are obtained, corresponding to a conversion of 97.7%.
Example 3 135 g (0.5 mole) of octadecyl alcohol together with 51.5 g (0.5 mole) of carbamic acid isopropyl ester and 1 g of iso-propyl titanate are heated under a pressure of 300 ~m Hg to 150 - 155C, whilst stirring. Hereupon, 29 g of isopropanol distil off in the course of 75 minutes. Carbamic acid octa-, -decyl ester is obtained in a yield of 136 g (99% of theory) and with a melting point of 93 - 94C (after recrystallization from ethanol).
Exam~le 4 31 g (0.5 mole) of ethylene glycol and 89 g (1 mole) of carbamic acid ethyl ester are heated together with 2 g of iso-propyl titanate. Using an external temperature of 180 -195C, 41 g of ethanol hereupon distil off in the couuse o~ 6 hours t~Lrough a descending condenser.
After'recrystallization from eth~-lol) 55 g o~ ethylene , glycol bis-carbamic acid ester are obtained, corresponding to a yield of 74%.
Example 5 1,000 g (0.2 mole) of a polyether-alcohol of molecular weight 5,000, obtained by reacting 1 mole of pentaerythri-tol with 20 moles of propylene oxide and 80 moles of ethylene oxide, are heaied together with 35.6 g (0.4 mole) of carbamic acid ethyl ester and 2 g of isopropyl titanate to 150C under a pres-sure of 300 mm Hg. m e 18.2 g of eth~nol which hereupon distil off in the course of 6 hours and are collected in a cold trap correspond to a conversion of 98% based on the carbamic acid ethyl ester employed.
Example 6 ` 500 g (0.5 mole) of a polyethylene glycol cf molecular weight 1,000, 117 g (1.0 mole) of carbamic acid butyl ester and 1.3 g (0.05 mole) of ethyl titanate are heated under a pressure 140 mm Hg to 150 - 160C, whilst stirring- Hereupon~ 65g of~uta-ncl distil off, in the courseof3hours,anda~ collected, ~ a adescending condenser, in an ice-coo'ed receiver. This corresponds to . ~
a conversion of 88~.
Polyethylene glycol(l,000) bis-carbamic acid ester is ` obtained in a yield of 548 g.
:' . ~ , 338 g (0.4 mole) of a reaction product of 1 mole of dodecyl alcohol with 15 moles of ethylene oxide are heated together with 47 g (0.4 mole) of butylurethane ~nd 2 g o~ iso-propyl titanate ~nder a pressure of 140 mm Hg to 150 160C, whilst stirring. After 2 hours, the pressure is reduced to .:
' '. ' .
' ~
60 mm Hg. Hereupon, 31.7 g of alcohol distil over, in which 26 g (82% of theory) of butanol were found by gas chromatography. m is corresponds to a conversion of ~8%.
- The yield of carbamic acid ester of ethoxylated dodecyl alcohol is 320 g (90% of theory).
;~.' ' ` , ' .
. - . .
, . . .
, .
: ~ .
. ~
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the manufacture of a carbamic acid ester of a relatively high boiling alcohol selected from alkanols and alkanediols, their oxalkylation products, and the oxalkylation products of trihydric or tetrahydric aliphatic alcohols, said relatively high boiling alcohol having a boiling point of above 190°C, which comprises transesterifying one mole of C2-C5-alkyl carbamic acid ester with one mole of said relatively high boiling alcohol in the presence of a C1-C4-alkyl titanate as a catalyst and distilling off from the reaction mixture the lower alcohol resulting from the carbamic acid ester.
2. A process as claimed in Claim 1, wherein the reaction is carried out at a pressure of 25 to 760 mm Hg and at a temperature of 80 - 210°C.
3. A process as claimed in Claim 1 or 2, wherein the alkyl titanate is employed in an amount of 0.001 to 0.1 mole per mole of the relatively high-boiling alcohol used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762655741 DE2655741A1 (en) | 1976-12-09 | 1976-12-09 | METHOD FOR PRODUCING CARBAMID ACID ESTERS OF HIGH-BOILING ALCOHOLS |
| DEP2655741.5 | 1976-12-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1111063A true CA1111063A (en) | 1981-10-20 |
Family
ID=5995046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,686A Expired CA1111063A (en) | 1976-12-09 | 1977-12-08 | Process for the manufacture of carbamic acid esters of high-boiling alcohols |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5373520A (en) |
| AR (1) | AR220690A1 (en) |
| AT (1) | AT359516B (en) |
| AU (1) | AU514123B2 (en) |
| BE (1) | BE861700A (en) |
| BR (1) | BR7708161A (en) |
| CA (1) | CA1111063A (en) |
| CH (1) | CH630343A5 (en) |
| DE (1) | DE2655741A1 (en) |
| ES (1) | ES464677A1 (en) |
| FR (1) | FR2373520A1 (en) |
| GB (1) | GB1592463A (en) |
| IT (1) | IT1089317B (en) |
| NL (1) | NL7713388A (en) |
| ZA (1) | ZA777334B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3529531A1 (en) * | 1985-08-17 | 1987-02-26 | Basf Ag | METHOD FOR PRODUCING CARBAMID ACID ESTERS |
| US6228953B1 (en) * | 1999-08-20 | 2001-05-08 | Ppg Industries,Ohio, Inc. | Process for the preparation of carbamate functional polymers |
| US9334234B2 (en) * | 2014-05-08 | 2016-05-10 | Basf Coatings Gmbh | Method using titanium catalyst for producing carbamate-functional materials |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2184545B1 (en) * | 1972-05-17 | 1980-03-14 | Rhone Poulenc Ind |
-
1976
- 1976-12-09 DE DE19762655741 patent/DE2655741A1/en not_active Withdrawn
-
1977
- 1977-12-02 ES ES464677A patent/ES464677A1/en not_active Expired
- 1977-12-02 NL NL7713388A patent/NL7713388A/en not_active Application Discontinuation
- 1977-12-06 AT AT872277A patent/AT359516B/en not_active IP Right Cessation
- 1977-12-06 CH CH1490277A patent/CH630343A5/en not_active IP Right Cessation
- 1977-12-07 IT IT30515/77A patent/IT1089317B/en active
- 1977-12-07 AR AR270276A patent/AR220690A1/en active
- 1977-12-08 ZA ZA00777334A patent/ZA777334B/en unknown
- 1977-12-08 JP JP14666577A patent/JPS5373520A/en active Pending
- 1977-12-08 AU AU31361/77A patent/AU514123B2/en not_active Expired
- 1977-12-08 BR BR7708161A patent/BR7708161A/en unknown
- 1977-12-08 CA CA292,686A patent/CA1111063A/en not_active Expired
- 1977-12-08 GB GB51149/77A patent/GB1592463A/en not_active Expired
- 1977-12-08 FR FR7736985A patent/FR2373520A1/en not_active Withdrawn
- 1977-12-09 BE BE183330A patent/BE861700A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA777334B (en) | 1978-10-25 |
| DE2655741A1 (en) | 1978-06-15 |
| AU3136177A (en) | 1979-06-14 |
| NL7713388A (en) | 1978-06-13 |
| IT1089317B (en) | 1985-06-18 |
| AT359516B (en) | 1980-11-10 |
| ES464677A1 (en) | 1978-09-01 |
| FR2373520A1 (en) | 1978-07-07 |
| AR220690A1 (en) | 1980-11-28 |
| BR7708161A (en) | 1978-08-15 |
| AU514123B2 (en) | 1981-01-29 |
| GB1592463A (en) | 1981-07-08 |
| CH630343A5 (en) | 1982-06-15 |
| JPS5373520A (en) | 1978-06-30 |
| ATA872277A (en) | 1980-04-15 |
| BE861700A (en) | 1978-06-09 |
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