CA2123149A1 - Process for the production of compounds containing aliphatically bound amide or urethane groups - Google Patents
Process for the production of compounds containing aliphatically bound amide or urethane groupsInfo
- Publication number
- CA2123149A1 CA2123149A1 CA 2123149 CA2123149A CA2123149A1 CA 2123149 A1 CA2123149 A1 CA 2123149A1 CA 2123149 CA2123149 CA 2123149 CA 2123149 A CA2123149 A CA 2123149A CA 2123149 A1 CA2123149 A1 CA 2123149A1
- Authority
- CA
- Canada
- Prior art keywords
- formate
- aliphatically bound
- groups
- compound
- 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.)
- Abandoned
Links
Classifications
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4623—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing primary or secondary terminal aminogroups
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A PROCESS FOR THE PRODUCTION OF COMPOUNDS CONTAINING
ALIPHATICALLY BOUND AMIDE OR URETHANE GROUPS
ABSTRACT OF THE DISCLOSURE
Compounds containing aliphatically bound amide groups or ure-thane groups are produced by reacting at least one compound containing an aliphatically bound ester or carbonate group with at least one compound containing at least one aliphatically bound amine group. This reaction is carried out in the presence of a catalytically active quantity of at least one alkali metal alkylate and at least one alkyl formate. These compounds are particularly useful as chain extending agents in the polyisocyanate addition process.
ALIPHATICALLY BOUND AMIDE OR URETHANE GROUPS
ABSTRACT OF THE DISCLOSURE
Compounds containing aliphatically bound amide groups or ure-thane groups are produced by reacting at least one compound containing an aliphatically bound ester or carbonate group with at least one compound containing at least one aliphatically bound amine group. This reaction is carried out in the presence of a catalytically active quantity of at least one alkali metal alkylate and at least one alkyl formate. These compounds are particularly useful as chain extending agents in the polyisocyanate addition process.
Description
` 2~231~9 Mo4059 LeA 29,717 A PROCESS FOR THE PRODUCTION OF COMPOUNDS CONTAINING
ALIPHATICALLY BOUND AMIDE OR URETHANE GROUPS
The present invention relates to a process for the production of compounds containing aliphatically bound amide or urethane groups.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel process for the production of compounds containing aliphatically bound amide or urethane groups.
It is another object of the present invention to provide a catalyst ~ ~ ~
system useful in the production of compounds containing aliphatically :
-bound amide or urethane groups.
It is a further objec~ of the present invention to provide a process for the prsduction of polyol mixtures terminated by ffee amino groups which are useful in the polyisocyanate polyaddition process for the production of polyurethanes.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting (1) a compound containing an aliphatically bound ester or carbonate group with (2) a compound containing at least one aliphatically bound amine group in the presence of (3) a catalytically effective amount of a catalyst component which is made up of (a) an alkali metal alkylate and (b) an alkyl formate. -DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention relates to a process for the production of compounds containing aliphatically bound amide or urethane groups from compounds containing aliphatically bound ester or carbonate groups. In this process, (1) at least one compound containing an aliphatically bound ester or carbonat~ group is reacted with (2) a compound containing at least one aliphatically bound amine group in the presence of (3) a specific combination of catalytically active quantities of at least one aLkali metal alkylate and at least one alkyl formate.
LeA29717-U.S
:~ . , . . . :: , ;.:: '' ' : . "' ' ' ' .. ' : : ' ' '' ,:,: . , . '' ' , : : ' :
I" . ' ':' , ' ` : ' " ' ' .,' :: . ' .
~ 21231~9 For compounds containing carbonate groups, the reaction which occurs in the process of the present invention may be represented by the following reaction scheme:
X--R' O--C O--R2 X' + H2N--R3--Y
10Cat. ¦¦
c y R3 N C O R2_X' ~ X-- R1--OH
H
inwhich ~ :
15 X and X' (which may be the same or different) each represents -H, OH
or -OR, Y represents-H,-OH,-NH2,-OR, R represents an alkyl, cycloalkyl or aralkyl group, ;
R ' and R 2 (which may be the same or different) each represents an organic radical which may optionally contain additional carbonate groups, and R3 represents an aliphatic or cycloaliphatic radical.
The reaction scheme for oompounds containing aliphatically bound ester groups is analogous to the above-given reaction scheme.
The process of the present invention may be carried out by first mixing the compound containing at least one ester or carbonate group and the compound containing at least one amine group and then adding the catalysts thereafter. It is also possible to incorporate the catalysts in one of the reactive compounds (either the compound cont~ining the ester ,.. :.,.. , - . -" - , . , ............. . , , , i, ~ ", : , "
; : .. , i . ~ ,, ~ .
2~231~9 or carbonate group or the compound containing an amine group) before that compound is mixed with the other reactive compound.
At least one of the reactants should be liquid at room temperature or at a slightly elevated temperature. It is preferred that the other 5 reactant also be liquid at room temperature or slightly elevated temperature or be soluble in the other reactant which is liquid.
A key feature of the process of the present invention is the simultaneous use of catalytic quantities of alkali metal alkylate and alkyl formate. Preferred alkali metal alkyiates include the methylates and/or 10 ethylates of lithium, sodium or potassium. Sodium methylate is particu-larly preferred. Methyl formate and/or ethyl formate are preferably used as the alkyl formates. Methyl formate is particularly preferred.
The two catalyst substances are preferably used in a molar ratio of alkylate to formate of from about 1:3 to about 3:1.
A catalytically active quantity of a formate (e.g., methyl formate) is generally from about ~.01 to 0.08 mole (preferabiy from about 0.01 to 0.05 mole) per mole of amino groups in the compound containing an ~ ;
aliphaticamino group.
A catalytically active quantity of an alkylate (e.g., sodium methyl-20 ate) is generally from about 0.01 to about 0.1 mole (preferably fromabout 0.01 to about 0.08 mole) per mole of amino groups in the compound containing an aliphatically bound amino group.
The reaction according to the invention is generally carried out at normal pressure and at temperatures of from about 20 to about 120C, 25 preferably at temperatures of from about 30 to about 80C.
The present invention also relates to the catalyst system used in the process of the present invention to promote the reaction of aliphatically bound ester or carbonate groups with aliphatically bound amine groups to form amide or urethane groups. This catalyst system is ",,..., ....... ~ ., . . . . ~ ..
,:,~ , . .. . ~
~ , . . . ~ ;
.,, .. , .. , ~ - . .
, ~. ~ .,. . ~ ;
, ~ - . , . ~ , .;; , , . ~ . , .: . : ,, : . . ~
2~231~9 made up of at least one alkali metal alkylate and at least one alkyl formate.
The catalyst system of the present invention is particularly useful for the production of a polyol or polyol mixture in which the polyol or 5 polyols are terminated by free amino groups. These amine terminated polyols are produced by reacting a hydroxyfunctional aliphatic polycarbonate or polyester (preferably a polycarbonate) with an aliphatic polyamine.
The following reaction scheme illustrates the production of an 10 amine terminated polyol from a polycarbonate using the catalyst system of the present invention:
HOR, O C O R2OH + H2N R3 NH2 O - ..
.
H
Cat.
H2N--R3--N-- I O R2 OH + H~R' ~H
b in which R' and R2 each represent recurring units of the polycarbonate containing carbonate groups and 25 R3 represents an aliphatic or cycloaliphatic radical.
The reaction of the polyamine with the polycarbonate or the polyester may be terminated by the addition of an acid. A polyol or mix-ture of polyols terminated by free amino groups is obtained when the reaction is terminated after at least one amino group of the polyamine 2~231~9 has been reacted to form the amide or urethane group.
Inorganic or organic acids having a pKa value below 3 are prefera-bly used to terminate the reaction. Specific examples of suitable acids include methanesulfonic acid, sulfuric acid and phosphoric acid. The 5 acid is preferably used in an amount which is equivalent to the quantity of alkali metal catalyst.
The progress of the reaction and the time at which it is terminated may readily be determined: (1) by infrared (IR) analysis of the reduction in intensity of a band at 1,590 cm ' which is assigned to the free 10 (psly)amine in the mixture; (2) by the increase in refractive index; or (3) by determination of the reduction in the "base N", i.e. the percentage reduction in the nitrogen content of the free amino groups.
Examples of polycarbonates useful as starting materials in the process ol' the present invention include the aliphatic hydroxyfunctionai polycarbonates of the type used as diol component for the synthesis of .
polyurethane plastics such as those described in the Encyclopedia of Polymer Science and Engineering, Vol. 11, pages 648 to 650, New York 1988). Examples of hydroxyfunctional polyesters useful as starting materials in the process of the present invention include those disclosed, 20 for example, in Kunststoff-Handbuch, "Polyurethane", Vol. 7, edited by G.
Oertel, pages 54-62, Munich 1983. Any of the known (poly)amines con- -taining at least two aliphatically bound primary amino groups may be used in the process of the present invention.
The polyols terminated by free amino groups produced in accor-25 dance with the present invention prel'erably have OH values of fromabout 100 to about 140 for an amine nitrogen content (expressed as N, atomic weight 14) of 0.4 to 1.0% by weight.
Polyols terminated by free amino groups are valuable starting materials for the production of polyurethanes by the polyisocyanate . : . , , .. " ... . " ~ - . - . . ......................... .
., ~: . . . . . .
2~3149 polyaddition process. These polyols are useful as chain-extending agents.
Having thus described our invention, the fo!lowing Examples are given as being illustrative thereof. All parts and percentages given in 5 these Examples are parts by weight and percentages by weight, unless otherwise indicated.
ExamPles A) Preparation of the polyol mixtures according to the invention The following materials were used in the Examples 1 through 10:
10 POLYCARBONATE 1: Polycarbonate based on 1,6-hexanediol/
caprolactone (molar ratio 1:1), diphenyl carbonate having an OH value of 57,6 and a molecular weight of 2 000.
POLYCARBONATE 2: Polycarbonate based on 1,6-hexanediol, diphenyl carbonate having an OH value of 56 and a molecular weight of 2,000.
15 POLYESTER 1: Polyester based on adipic acid/1,6-hexanediol/neopentyl glycol (molar ratio 1:0.73:0.49) hav~ng an OH value of 66 and a moleclllar weight of 170û.
AMINE 1: 2-Methylpentam~thylene-1,5-diamine which is commercially available under the name DYTEK-A from DuPont.
AMINE 2: The triamine obtained by amination of the terminal OH groups 20 of a polyether based on trimethylol propane/propylene oxide having a molecular weight of 440 and base N content of 9.5% which is commercially available under the name Jeffamine T403 from Texaco.
AMINE 3: 5-Amino-1-aminomethyl-1 ,3,3-trimethyl cyclohexane.
AMINE 4: 1 ,6-diaminohexane.
25 ExamPle 1 1,200 9 of dehydrated POLYCARBONATE 1 were mixed with 69.7 9 (0.6 mole) of AMINE 1 at 40C. 3 g of methyl formate were added to the mixture. 2.2 9 of a 30% sodium methylate solution (in methanol~ were then added to the polycarbonate/amine mixture dropwise ,,~, :. , . , . , , , -:
with stirring at 40~C. After stirring for 4 hours at 40C, the reaction was terminated by addition of 1.2 9 of methanesulfonic acid. The reaction mixture was degassed in vacuo. A clear polyol having the following characteristics was obtained:
5 OH value: 112 Viscosity (23C): 5,000 mPas Base N: 0~7% nD23C 1.470~
During the reaction, the IR band at ~1,590 cm-' (amine band) decreased and a band at ~1,510 cm ' (urethane band) increased.
Example 2 (Comparative) Example 1 was repeated with the exception that no methyl formate was added to the reaction mixture. No reaction between the polycarbonate and the amine took place. The s~arting values for "base N" and "refractive index" remained unchanged. The IR band at ~1,590 cm ' remained uniform in intensity. Even brief subsequent heating to 15 100C did not produce any changes.
Exam~le 3 (Comparative) Example I was repeated without using msthyl ~orrnate and sodium methyl-ate. The reaction of polycarbonate with amine did not take place. The mixture remained unchanged.
20 Exam~le 4 1,200 g of dehydrated POLYCARBONATE 1 were mixecl with 176 9 (0.4 mole) of AMINE 2 at 50C. 3 9 of methyl formate were added to the mixture. 3.9 g of a 30% sodium methylate solution were then added dropwise to the polycarbonate/amine mixture with stirring. After stirring 25 for 3 hours at 60~C, another 1.0 g of 30% sodium methylate solution was added dropwise. After stirring for a total of 7 hours at 60C, the reaction was terminated by the addition of 2.7 9 of methanesulfonic acid.
The reaction mixture was degassed in vacuo. A clear polyol having the following characteristics was obtained:
.
~',' ~':' ' , ': ' , . ' ' ' ~ ' . . ..
~.~ , ': , -- 21231 ~9 ; -8 -OH value: 106 Viscosity (23C): 6,500 mPa s Base N: 0.8% nD23C: 1.4692 Example 5 Example 1 was repeated with the exception that AMINE 1 was re-placed by 69.7 9 (0.6 mole) of AMINE 4 and a total of 4 9 of the sodium methylate solution was used. The polyol obtained had the following properties:
OH value: 114 Viscosity (23C): 4,500 mPa s Base N: 0.63% nD23c 1.4706 Example 6 12,000 g of dehydrated POLYCARBONATE 1 were mixed with 102 9 (0.6 mole) of AMINE 3 at 40C. 3 9 of methyl formate were added to the mixture. A total of 4 9 of sodium methylate solution in portions was subsequently added dropwise with stirring. After siirring for 4.5 hours at 40C, the reaction was terminated by the addition of 2.1 9 of methanesulfonic acid. The reaction mixture was degassed in vacuo. A
clear polyol having the following characteristics was obtained:
OH value: 112 Viscosity (23C): 7,000 mPa-s Base N: 0.66% nD23c 1.4730 Example 7 400 9 of dehydrated POLYCARBONATE 2 were mixed with 58.7 9 (0.13 mole) of AMINE 2 at 60C. 2 9 of methyl formate were then added to the mixture. A total of 3 g of sodium methylate solution (30% in methanol) was then added dropwise with stirring. After stirring for 6 hours at 60C, the reaction was terminated by the addition of 1.6 9 of methanesulfonic acid. The reaction mixture was degassed in vacuo.
The polyol obtained solidifled on cooling to form a wax-like substance ~: . ' ~ , , :
~3149 , g and had the following characteristics:
OH value: 104 Base N: 0.8%
ExamPle 8 1,200 g of dehydrated POLYCARBONATE 2 were mixed with 93 g (0.8 mole) of AMINE 1 at 60C. 3 g of methyl formate were added to the mixture. A total of 6 9 of sodium methylate solution (30% in methanol) was then added dropwise with stirring. After stirring for 7 hours at 60C, the reaction was terminated by the addition of 3.3 9 of phosphoric acid.
The reaction mixture was degassed in vacuo. The polyol obtained solidified on cooling to form a wax-like substance and had the following characteristics:
OH value: 125 Base N: 0.9%
FxamDle 9 1,050 g of dehydrated POLYESTER 1 were mixed with 70 9 (0.6 mole) of AMINE 1 at 60C. 3 9 of methyl formate were added. 14 9 of a 30% sodium methylate solution (in methanol) were added dropwise with stirring. After stirring for 24 h at 80C, the reaction was terminated by the addition of 7.5 9 of methanesulfonic acid. The reaction mixture was then degassed in vacuo. The polyol became wax-like at roorn tempera-ture but remained fluid and had the following characteristics:
OH value: 137 Base N: 0.7%
Example 10 1,050 9 of dehydrated POLYESTER 1 were stirred at 80C with a mixture of 102 y (0.6 mole) of AMINE 3 and 5 9 of methyl formate. 16 g of a 30% sodium methylate solution (in methanol) were then added dropwise with stirring. After stirring for 20 hours at 120C, the reaction ., , , . . ~ , .
,., . : :
s , , . .; , , .
i' ~,.~ , . ~ ! ' , , ' ' ' , ! ' , ~ . ' ' , .
1~ , ~," ~ ' ' ' ~-" 21231~
was terminated by the addition of 8.5 g of methanesulfonic acid. The reaction mixture was then degassed in vacuo. A fluid wax-like polyol having the following characteristics was obtained:
OH value: 132 5 Base N: 0.7%
B) Production of polyurethane plastics from the polyols of the present invention.
Example 11 100 g of the polyol mixture of Example 1 were mixed with 26.2 9 10 of finely ground 1,5-diisocyanatonaphthalene (NDI, Mp. 127C, parlicle size 20 to 40 ,l~m). The resulting mixture was stable in storage at room temperature (i.e., the isooyanate did not react with the reactive OH
groups). After brief degassing in a water jet vacuum, the liquid mixture was poured into a mold which was then heated to 1~0 to 140C. The 15 liquid quickly solidified to form a ~ransparent polyurethane plastic having high elasticity and a Shore A hardness (DIN 53 505) of 90.
ExamPle 12 100 g of the polyol mixture of Example 1 were mixed with 50.9 g of 4,4'-dimethyl-3,3'-diaminodiphenyl urea (prepared from 2 moles of 2,4-20 diisocyanatotoluene and 1 mole of water in acetone). This mixture wasstable in storage at room temperature and solidified within a few minutes when heated to 120-140C. After brief degassing in a water jet vacuum, the liquid mixture was poured into a mold which was then heated to 120 to 140C. A microporous opaque polyurethane material having a Shore 25 A hardness of 80 to 85 was obtained.
Example 13 100 g of the polyol mixture of Example 1 were mixed with 30.7 g :~
9f solid 4,4'-diisocyanatodiphenyl methane (MDI, prepared by running an MDI melt into cleaner's naphtha).
"'~, . ~ ,." ~ ' ' ' : ' . , .. :~' : : ' t~ " .'. : " '.', ,~ : ' ~' ' ,'~ ' ' . ' ~ :
,': ,.. , ' , ' :
,,,: ' , , :
21'23149 The resulting mixture was not stable in storage and underwent a drastic increase in viscosity after oniy a few minutes (pot iife: 5 to 7 minutes at room temperature).
The test specimen was then heated for 1 hour at 120C. A trans-5 parent flexible polyurethane material having a Shore A hardness of 65 to 70 was obtained.
_ample 14 100 9 of the polyol mixture of Example 4 were mixed at roorntemperature with 24.8 9 of the NDI used in Example 11. The resulting 10 mixture was viscosity-stable up to a temperature range of 60 to 80CC.
After brief degassing in a water jet vacuum, the mixture was poured into a mold which was then heated to 1~0 to 140C. The mixture quickly solidified to form a polyurethane plastic having the following properties:
Shore A hardness: 85 15 Impact resilience: 40% (DIN 53 512).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein :
by those skilled in the art without departing from the spirit and scope of 20 the invention except as it may be limited by the claims.
. .\
i,,. ~ ": : , . . .
,~ "., . , . , . ,, ,, ., . ~. , : .
ALIPHATICALLY BOUND AMIDE OR URETHANE GROUPS
The present invention relates to a process for the production of compounds containing aliphatically bound amide or urethane groups.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel process for the production of compounds containing aliphatically bound amide or urethane groups.
It is another object of the present invention to provide a catalyst ~ ~ ~
system useful in the production of compounds containing aliphatically :
-bound amide or urethane groups.
It is a further objec~ of the present invention to provide a process for the prsduction of polyol mixtures terminated by ffee amino groups which are useful in the polyisocyanate polyaddition process for the production of polyurethanes.
These and other objects which will be apparent to those skilled in the art are accomplished by reacting (1) a compound containing an aliphatically bound ester or carbonate group with (2) a compound containing at least one aliphatically bound amine group in the presence of (3) a catalytically effective amount of a catalyst component which is made up of (a) an alkali metal alkylate and (b) an alkyl formate. -DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention relates to a process for the production of compounds containing aliphatically bound amide or urethane groups from compounds containing aliphatically bound ester or carbonate groups. In this process, (1) at least one compound containing an aliphatically bound ester or carbonat~ group is reacted with (2) a compound containing at least one aliphatically bound amine group in the presence of (3) a specific combination of catalytically active quantities of at least one aLkali metal alkylate and at least one alkyl formate.
LeA29717-U.S
:~ . , . . . :: , ;.:: '' ' : . "' ' ' ' .. ' : : ' ' '' ,:,: . , . '' ' , : : ' :
I" . ' ':' , ' ` : ' " ' ' .,' :: . ' .
~ 21231~9 For compounds containing carbonate groups, the reaction which occurs in the process of the present invention may be represented by the following reaction scheme:
X--R' O--C O--R2 X' + H2N--R3--Y
10Cat. ¦¦
c y R3 N C O R2_X' ~ X-- R1--OH
H
inwhich ~ :
15 X and X' (which may be the same or different) each represents -H, OH
or -OR, Y represents-H,-OH,-NH2,-OR, R represents an alkyl, cycloalkyl or aralkyl group, ;
R ' and R 2 (which may be the same or different) each represents an organic radical which may optionally contain additional carbonate groups, and R3 represents an aliphatic or cycloaliphatic radical.
The reaction scheme for oompounds containing aliphatically bound ester groups is analogous to the above-given reaction scheme.
The process of the present invention may be carried out by first mixing the compound containing at least one ester or carbonate group and the compound containing at least one amine group and then adding the catalysts thereafter. It is also possible to incorporate the catalysts in one of the reactive compounds (either the compound cont~ining the ester ,.. :.,.. , - . -" - , . , ............. . , , , i, ~ ", : , "
; : .. , i . ~ ,, ~ .
2~231~9 or carbonate group or the compound containing an amine group) before that compound is mixed with the other reactive compound.
At least one of the reactants should be liquid at room temperature or at a slightly elevated temperature. It is preferred that the other 5 reactant also be liquid at room temperature or slightly elevated temperature or be soluble in the other reactant which is liquid.
A key feature of the process of the present invention is the simultaneous use of catalytic quantities of alkali metal alkylate and alkyl formate. Preferred alkali metal alkyiates include the methylates and/or 10 ethylates of lithium, sodium or potassium. Sodium methylate is particu-larly preferred. Methyl formate and/or ethyl formate are preferably used as the alkyl formates. Methyl formate is particularly preferred.
The two catalyst substances are preferably used in a molar ratio of alkylate to formate of from about 1:3 to about 3:1.
A catalytically active quantity of a formate (e.g., methyl formate) is generally from about ~.01 to 0.08 mole (preferabiy from about 0.01 to 0.05 mole) per mole of amino groups in the compound containing an ~ ;
aliphaticamino group.
A catalytically active quantity of an alkylate (e.g., sodium methyl-20 ate) is generally from about 0.01 to about 0.1 mole (preferably fromabout 0.01 to about 0.08 mole) per mole of amino groups in the compound containing an aliphatically bound amino group.
The reaction according to the invention is generally carried out at normal pressure and at temperatures of from about 20 to about 120C, 25 preferably at temperatures of from about 30 to about 80C.
The present invention also relates to the catalyst system used in the process of the present invention to promote the reaction of aliphatically bound ester or carbonate groups with aliphatically bound amine groups to form amide or urethane groups. This catalyst system is ",,..., ....... ~ ., . . . . ~ ..
,:,~ , . .. . ~
~ , . . . ~ ;
.,, .. , .. , ~ - . .
, ~. ~ .,. . ~ ;
, ~ - . , . ~ , .;; , , . ~ . , .: . : ,, : . . ~
2~231~9 made up of at least one alkali metal alkylate and at least one alkyl formate.
The catalyst system of the present invention is particularly useful for the production of a polyol or polyol mixture in which the polyol or 5 polyols are terminated by free amino groups. These amine terminated polyols are produced by reacting a hydroxyfunctional aliphatic polycarbonate or polyester (preferably a polycarbonate) with an aliphatic polyamine.
The following reaction scheme illustrates the production of an 10 amine terminated polyol from a polycarbonate using the catalyst system of the present invention:
HOR, O C O R2OH + H2N R3 NH2 O - ..
.
H
Cat.
H2N--R3--N-- I O R2 OH + H~R' ~H
b in which R' and R2 each represent recurring units of the polycarbonate containing carbonate groups and 25 R3 represents an aliphatic or cycloaliphatic radical.
The reaction of the polyamine with the polycarbonate or the polyester may be terminated by the addition of an acid. A polyol or mix-ture of polyols terminated by free amino groups is obtained when the reaction is terminated after at least one amino group of the polyamine 2~231~9 has been reacted to form the amide or urethane group.
Inorganic or organic acids having a pKa value below 3 are prefera-bly used to terminate the reaction. Specific examples of suitable acids include methanesulfonic acid, sulfuric acid and phosphoric acid. The 5 acid is preferably used in an amount which is equivalent to the quantity of alkali metal catalyst.
The progress of the reaction and the time at which it is terminated may readily be determined: (1) by infrared (IR) analysis of the reduction in intensity of a band at 1,590 cm ' which is assigned to the free 10 (psly)amine in the mixture; (2) by the increase in refractive index; or (3) by determination of the reduction in the "base N", i.e. the percentage reduction in the nitrogen content of the free amino groups.
Examples of polycarbonates useful as starting materials in the process ol' the present invention include the aliphatic hydroxyfunctionai polycarbonates of the type used as diol component for the synthesis of .
polyurethane plastics such as those described in the Encyclopedia of Polymer Science and Engineering, Vol. 11, pages 648 to 650, New York 1988). Examples of hydroxyfunctional polyesters useful as starting materials in the process of the present invention include those disclosed, 20 for example, in Kunststoff-Handbuch, "Polyurethane", Vol. 7, edited by G.
Oertel, pages 54-62, Munich 1983. Any of the known (poly)amines con- -taining at least two aliphatically bound primary amino groups may be used in the process of the present invention.
The polyols terminated by free amino groups produced in accor-25 dance with the present invention prel'erably have OH values of fromabout 100 to about 140 for an amine nitrogen content (expressed as N, atomic weight 14) of 0.4 to 1.0% by weight.
Polyols terminated by free amino groups are valuable starting materials for the production of polyurethanes by the polyisocyanate . : . , , .. " ... . " ~ - . - . . ......................... .
., ~: . . . . . .
2~3149 polyaddition process. These polyols are useful as chain-extending agents.
Having thus described our invention, the fo!lowing Examples are given as being illustrative thereof. All parts and percentages given in 5 these Examples are parts by weight and percentages by weight, unless otherwise indicated.
ExamPles A) Preparation of the polyol mixtures according to the invention The following materials were used in the Examples 1 through 10:
10 POLYCARBONATE 1: Polycarbonate based on 1,6-hexanediol/
caprolactone (molar ratio 1:1), diphenyl carbonate having an OH value of 57,6 and a molecular weight of 2 000.
POLYCARBONATE 2: Polycarbonate based on 1,6-hexanediol, diphenyl carbonate having an OH value of 56 and a molecular weight of 2,000.
15 POLYESTER 1: Polyester based on adipic acid/1,6-hexanediol/neopentyl glycol (molar ratio 1:0.73:0.49) hav~ng an OH value of 66 and a moleclllar weight of 170û.
AMINE 1: 2-Methylpentam~thylene-1,5-diamine which is commercially available under the name DYTEK-A from DuPont.
AMINE 2: The triamine obtained by amination of the terminal OH groups 20 of a polyether based on trimethylol propane/propylene oxide having a molecular weight of 440 and base N content of 9.5% which is commercially available under the name Jeffamine T403 from Texaco.
AMINE 3: 5-Amino-1-aminomethyl-1 ,3,3-trimethyl cyclohexane.
AMINE 4: 1 ,6-diaminohexane.
25 ExamPle 1 1,200 9 of dehydrated POLYCARBONATE 1 were mixed with 69.7 9 (0.6 mole) of AMINE 1 at 40C. 3 g of methyl formate were added to the mixture. 2.2 9 of a 30% sodium methylate solution (in methanol~ were then added to the polycarbonate/amine mixture dropwise ,,~, :. , . , . , , , -:
with stirring at 40~C. After stirring for 4 hours at 40C, the reaction was terminated by addition of 1.2 9 of methanesulfonic acid. The reaction mixture was degassed in vacuo. A clear polyol having the following characteristics was obtained:
5 OH value: 112 Viscosity (23C): 5,000 mPas Base N: 0~7% nD23C 1.470~
During the reaction, the IR band at ~1,590 cm-' (amine band) decreased and a band at ~1,510 cm ' (urethane band) increased.
Example 2 (Comparative) Example 1 was repeated with the exception that no methyl formate was added to the reaction mixture. No reaction between the polycarbonate and the amine took place. The s~arting values for "base N" and "refractive index" remained unchanged. The IR band at ~1,590 cm ' remained uniform in intensity. Even brief subsequent heating to 15 100C did not produce any changes.
Exam~le 3 (Comparative) Example I was repeated without using msthyl ~orrnate and sodium methyl-ate. The reaction of polycarbonate with amine did not take place. The mixture remained unchanged.
20 Exam~le 4 1,200 g of dehydrated POLYCARBONATE 1 were mixecl with 176 9 (0.4 mole) of AMINE 2 at 50C. 3 9 of methyl formate were added to the mixture. 3.9 g of a 30% sodium methylate solution were then added dropwise to the polycarbonate/amine mixture with stirring. After stirring 25 for 3 hours at 60~C, another 1.0 g of 30% sodium methylate solution was added dropwise. After stirring for a total of 7 hours at 60C, the reaction was terminated by the addition of 2.7 9 of methanesulfonic acid.
The reaction mixture was degassed in vacuo. A clear polyol having the following characteristics was obtained:
.
~',' ~':' ' , ': ' , . ' ' ' ~ ' . . ..
~.~ , ': , -- 21231 ~9 ; -8 -OH value: 106 Viscosity (23C): 6,500 mPa s Base N: 0.8% nD23C: 1.4692 Example 5 Example 1 was repeated with the exception that AMINE 1 was re-placed by 69.7 9 (0.6 mole) of AMINE 4 and a total of 4 9 of the sodium methylate solution was used. The polyol obtained had the following properties:
OH value: 114 Viscosity (23C): 4,500 mPa s Base N: 0.63% nD23c 1.4706 Example 6 12,000 g of dehydrated POLYCARBONATE 1 were mixed with 102 9 (0.6 mole) of AMINE 3 at 40C. 3 9 of methyl formate were added to the mixture. A total of 4 9 of sodium methylate solution in portions was subsequently added dropwise with stirring. After siirring for 4.5 hours at 40C, the reaction was terminated by the addition of 2.1 9 of methanesulfonic acid. The reaction mixture was degassed in vacuo. A
clear polyol having the following characteristics was obtained:
OH value: 112 Viscosity (23C): 7,000 mPa-s Base N: 0.66% nD23c 1.4730 Example 7 400 9 of dehydrated POLYCARBONATE 2 were mixed with 58.7 9 (0.13 mole) of AMINE 2 at 60C. 2 9 of methyl formate were then added to the mixture. A total of 3 g of sodium methylate solution (30% in methanol) was then added dropwise with stirring. After stirring for 6 hours at 60C, the reaction was terminated by the addition of 1.6 9 of methanesulfonic acid. The reaction mixture was degassed in vacuo.
The polyol obtained solidifled on cooling to form a wax-like substance ~: . ' ~ , , :
~3149 , g and had the following characteristics:
OH value: 104 Base N: 0.8%
ExamPle 8 1,200 g of dehydrated POLYCARBONATE 2 were mixed with 93 g (0.8 mole) of AMINE 1 at 60C. 3 g of methyl formate were added to the mixture. A total of 6 9 of sodium methylate solution (30% in methanol) was then added dropwise with stirring. After stirring for 7 hours at 60C, the reaction was terminated by the addition of 3.3 9 of phosphoric acid.
The reaction mixture was degassed in vacuo. The polyol obtained solidified on cooling to form a wax-like substance and had the following characteristics:
OH value: 125 Base N: 0.9%
FxamDle 9 1,050 g of dehydrated POLYESTER 1 were mixed with 70 9 (0.6 mole) of AMINE 1 at 60C. 3 9 of methyl formate were added. 14 9 of a 30% sodium methylate solution (in methanol) were added dropwise with stirring. After stirring for 24 h at 80C, the reaction was terminated by the addition of 7.5 9 of methanesulfonic acid. The reaction mixture was then degassed in vacuo. The polyol became wax-like at roorn tempera-ture but remained fluid and had the following characteristics:
OH value: 137 Base N: 0.7%
Example 10 1,050 9 of dehydrated POLYESTER 1 were stirred at 80C with a mixture of 102 y (0.6 mole) of AMINE 3 and 5 9 of methyl formate. 16 g of a 30% sodium methylate solution (in methanol) were then added dropwise with stirring. After stirring for 20 hours at 120C, the reaction ., , , . . ~ , .
,., . : :
s , , . .; , , .
i' ~,.~ , . ~ ! ' , , ' ' ' , ! ' , ~ . ' ' , .
1~ , ~," ~ ' ' ' ~-" 21231~
was terminated by the addition of 8.5 g of methanesulfonic acid. The reaction mixture was then degassed in vacuo. A fluid wax-like polyol having the following characteristics was obtained:
OH value: 132 5 Base N: 0.7%
B) Production of polyurethane plastics from the polyols of the present invention.
Example 11 100 g of the polyol mixture of Example 1 were mixed with 26.2 9 10 of finely ground 1,5-diisocyanatonaphthalene (NDI, Mp. 127C, parlicle size 20 to 40 ,l~m). The resulting mixture was stable in storage at room temperature (i.e., the isooyanate did not react with the reactive OH
groups). After brief degassing in a water jet vacuum, the liquid mixture was poured into a mold which was then heated to 1~0 to 140C. The 15 liquid quickly solidified to form a ~ransparent polyurethane plastic having high elasticity and a Shore A hardness (DIN 53 505) of 90.
ExamPle 12 100 g of the polyol mixture of Example 1 were mixed with 50.9 g of 4,4'-dimethyl-3,3'-diaminodiphenyl urea (prepared from 2 moles of 2,4-20 diisocyanatotoluene and 1 mole of water in acetone). This mixture wasstable in storage at room temperature and solidified within a few minutes when heated to 120-140C. After brief degassing in a water jet vacuum, the liquid mixture was poured into a mold which was then heated to 120 to 140C. A microporous opaque polyurethane material having a Shore 25 A hardness of 80 to 85 was obtained.
Example 13 100 g of the polyol mixture of Example 1 were mixed with 30.7 g :~
9f solid 4,4'-diisocyanatodiphenyl methane (MDI, prepared by running an MDI melt into cleaner's naphtha).
"'~, . ~ ,." ~ ' ' ' : ' . , .. :~' : : ' t~ " .'. : " '.', ,~ : ' ~' ' ,'~ ' ' . ' ~ :
,': ,.. , ' , ' :
,,,: ' , , :
21'23149 The resulting mixture was not stable in storage and underwent a drastic increase in viscosity after oniy a few minutes (pot iife: 5 to 7 minutes at room temperature).
The test specimen was then heated for 1 hour at 120C. A trans-5 parent flexible polyurethane material having a Shore A hardness of 65 to 70 was obtained.
_ample 14 100 9 of the polyol mixture of Example 4 were mixed at roorntemperature with 24.8 9 of the NDI used in Example 11. The resulting 10 mixture was viscosity-stable up to a temperature range of 60 to 80CC.
After brief degassing in a water jet vacuum, the mixture was poured into a mold which was then heated to 1~0 to 140C. The mixture quickly solidified to form a polyurethane plastic having the following properties:
Shore A hardness: 85 15 Impact resilience: 40% (DIN 53 512).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein :
by those skilled in the art without departing from the spirit and scope of 20 the invention except as it may be limited by the claims.
. .\
i,,. ~ ": : , . . .
,~ "., . , . , . ,, ,, ., . ~. , : .
Claims (17)
1. A process for the production of compounds containing aliphatically bound amide or urethane groups comprising reacting a) a compound containing aliphatically bound ester or carbonate groups with b) a compound containing at least one aliphatically bound amine group in the presence of c) a catalytically active quantity of (1) an alkali metal alkylate and (2) an alkyl formate.
2. The process of Claim 1 in which the alkali metal alkylate c)(1) is selected from methylates of lithium, methylates of sodium, methylates of potassium, ethylates of lithium, ethylates of sodium, ethylates of potassium and mixtures thereof.
3. The process of Claim 2 in which the alkyl formate c)(2) is selected from methyl formate, ethyl formate and mixtures thereof.
4. The process of Claim 2 in which the compound a) contains aliphatically bound carbonate groups.
5. The process of Claim 1 in which the alkali metal alkylate c)(1) is sodium methylate.
6. The process of Claim 5 in which the alkyl formate c)(2) is selected from methyl formate, ethyl formate and mixtures thereof.
7. The process of Claim 1 in which the alkyl formate c)(2) is selected from methyl formate, ethyl formate and mixtures thereof.
8. The process of Claim 1 in which methyl formate is used as the alkyl formate c)(2).
9. The process of Claim 1 in which an aliphatic hydroxyfunctional polycarbonate is used as compound a).
10. The process of Claim 1 in which an aliphatic hydroxy-functional polyester is used as compound a).
11. The process of Claim 1 in which an aliphatic polyamine is used as compound b).
12. The process of Claim 1 in which the reaction is terminated by addition of an acid when the desired degree of amide or urethane group formation has been achieved.
13. The process of Claim 1 in which an inorganic or organic acid having a pKa value below 3 is used to terminate the reaction.
14. A process for the production of a polyol terminated by free amino groups comprising:
1) reacting a) a polyamine terminated by at least two aliphatically bound amino groups with b) an aliphatic hydroxyfunctional polycarbonate or an aliphatic hydroxyfunctional polyester terminated by at least two hydroxyl groups in the presence of c) a catalytically active quantity of (1) an alkali metal alkylate and (2) an alkyl formate and 2) terminating the reaction when at least one equivalent of the amino groups (per molecule) has been reacted to form the corresponding urethane group or the amide group.
1) reacting a) a polyamine terminated by at least two aliphatically bound amino groups with b) an aliphatic hydroxyfunctional polycarbonate or an aliphatic hydroxyfunctional polyester terminated by at least two hydroxyl groups in the presence of c) a catalytically active quantity of (1) an alkali metal alkylate and (2) an alkyl formate and 2) terminating the reaction when at least one equivalent of the amino groups (per molecule) has been reacted to form the corresponding urethane group or the amide group.
15. A process for the production of a polyurethane plastic comprising reacting a polyisocyanate with an isocyanate-reactive compound in the presence of a chain extending agent in which the chain extending agent is a product of the process of Claim 14.
16. A product of the process of Claim 1.
17. A product of the process of Claim 14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934315662 DE4315662A1 (en) | 1993-05-11 | 1993-05-11 | Process for converting ester or carbonate groups to amide or urethane groups |
| DEP4315662.2 | 1993-05-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2123149A1 true CA2123149A1 (en) | 1994-11-12 |
Family
ID=6487787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2123149 Abandoned CA2123149A1 (en) | 1993-05-11 | 1994-05-09 | Process for the production of compounds containing aliphatically bound amide or urethane groups |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0624614A1 (en) |
| CA (1) | CA2123149A1 (en) |
| DE (1) | DE4315662A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6534620B1 (en) | 1996-05-13 | 2003-03-18 | Bayer Aktiengesellschaft | Hydroxy-functional polyurethane carbonates, a process for their preparation and their use as binders |
| CN115003723A (en) * | 2020-01-07 | 2022-09-02 | 诠达化学股份有限公司 | Thermoplastic polyurethane with high tensile strength, preparation formula and manufacturing method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100700122B1 (en) * | 2001-09-20 | 2007-03-28 | 바이오콘 리미티드 | Modified alumina catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT390947B (en) * | 1988-09-29 | 1990-07-25 | Chemie Linz Gmbh | METHOD FOR PRODUCING DIPHENYL ACETE DIMETHYLAMIDE |
| JP2929730B2 (en) * | 1991-01-17 | 1999-08-03 | 三菱瓦斯化学株式会社 | Method for producing urethane compound |
-
1993
- 1993-05-11 DE DE19934315662 patent/DE4315662A1/en not_active Withdrawn
-
1994
- 1994-04-28 EP EP94106666A patent/EP0624614A1/en not_active Withdrawn
- 1994-05-09 CA CA 2123149 patent/CA2123149A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6534620B1 (en) | 1996-05-13 | 2003-03-18 | Bayer Aktiengesellschaft | Hydroxy-functional polyurethane carbonates, a process for their preparation and their use as binders |
| CN115003723A (en) * | 2020-01-07 | 2022-09-02 | 诠达化学股份有限公司 | Thermoplastic polyurethane with high tensile strength, preparation formula and manufacturing method thereof |
| CN115003723B (en) * | 2020-01-07 | 2023-12-05 | 诠达化学股份有限公司 | Thermoplastic polyurethane with high tensile strength, preparation formula and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0624614A1 (en) | 1994-11-17 |
| DE4315662A1 (en) | 1994-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101939350B (en) | Foamed, colour-fast polyurethane moulded parts | |
| US4605729A (en) | Process for the production of polyetherester polyols and the products and use thereof | |
| US3666726A (en) | Polymers which contain polyamide, urea and/or urethane groups and process for preparing same | |
| JPS63273623A (en) | Composition for manufacture of reaction injection formed elastomer | |
| US4191706A (en) | Aromatic amine-amides and use as chain-extenders | |
| GB2082608A (en) | Rim elastomer with improved heat distortion and tear properties | |
| US3954825A (en) | Biuret polyisocyanates | |
| US4468483A (en) | Aromatic polyester polycarbonates from polyols derived from recycled polyethylene terephthalate | |
| US4751255A (en) | Polymeric polyamines | |
| US4482690A (en) | Process for the production of polyurethane urea elastomers | |
| US4159369A (en) | Process for the production of poly (urethane silicate) cellular solid/solid products | |
| EP1013693A1 (en) | Polymeric acid funtional polyols, polyurethanes and method for making same | |
| EP0398304B1 (en) | Flexible polyurethane foams and process for preparing them | |
| JPS6356558A (en) | Manufacture of optionally foamed formed product having fine surface skin by reaction of reaction mixture in airtight mold | |
| US4618667A (en) | Nucleation of urethane compositions | |
| US3689443A (en) | Thermoplastically processable polyurethane elastomers | |
| CA2123149A1 (en) | Process for the production of compounds containing aliphatically bound amide or urethane groups | |
| US4897430A (en) | One Component polyurea | |
| US4386032A (en) | Liquid polyisocyanate compositions | |
| JP3459091B2 (en) | One-component composition for polyurethane elastomer and molding method thereof | |
| JPS60190413A (en) | Manufacture of urethane-reformed polyisocyanate composition | |
| JPH0347647B2 (en) | ||
| JPS63150347A (en) | Blend of alpha, omega-alkylene glycol and polyether polyol made compatible and production thereof | |
| US2987504A (en) | Polyurethane rubber via storable intermediates | |
| JPH01110522A (en) | Production of room temperature curable polyurethane urea elastomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |