CA2028040A1 - Ethylenically unsaturated, surface active urethane derivatives and process for their preparation - Google Patents
Ethylenically unsaturated, surface active urethane derivatives and process for their preparationInfo
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- CA2028040A1 CA2028040A1 CA002028040A CA2028040A CA2028040A1 CA 2028040 A1 CA2028040 A1 CA 2028040A1 CA 002028040 A CA002028040 A CA 002028040A CA 2028040 A CA2028040 A CA 2028040A CA 2028040 A1 CA2028040 A1 CA 2028040A1
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- Prior art keywords
- formula
- ethylenically unsaturated
- surface active
- urethane
- preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polyethers (AREA)
Abstract
Abstract of the disclosure Ethylenically unsaturated, surface active urethane derivatives and process for their preparation Ethylenically unsaturated surface active urethane deriva-tives prepared by reacting alkyl, aryl, aralkyl or cycloalkyl monoisocyanates with hydroxypolyoxyalkyleneoxycarbonylalkenes or with N-(hydroxypolyoxyalkylene)-alkenecarboxamides in the absence of water in bulk or in inert organic solvents or optionally also in reactive diluents, which are copoly-merizable ethylenically unsaturated monomeric compounds which are inert under the reaction conditions, such as, for example, vinyl esters, vinyl aromatics, and (meth)acrylic esters.
The urethane derivatives prepared according to the invention are surface active in their monomeric form and are in most cases solid or waxy or highly viscous pro-ducts. Their solubilities in water and in inert organic solvents or inert reactive diluents is highly dependent on the structure and size of the polyalkylene oxide radicals and also on the size of the hydrophobic radical at the nitrogen atom of the urethane group, so that, according to the invention, monomeric urethane deriva-tives which are readily soluble not only in water but also in inert organic solvents can be obtained. These are polymerizable or copolymerizable via their ethylenically unsaturated acyloxy or acylamido radicals and are versatile in use for the preparation of polymers or copolymers by free-radical initiated polymerization or copolymerization.
The urethane derivatives prepared according to the invention are surface active in their monomeric form and are in most cases solid or waxy or highly viscous pro-ducts. Their solubilities in water and in inert organic solvents or inert reactive diluents is highly dependent on the structure and size of the polyalkylene oxide radicals and also on the size of the hydrophobic radical at the nitrogen atom of the urethane group, so that, according to the invention, monomeric urethane deriva-tives which are readily soluble not only in water but also in inert organic solvents can be obtained. These are polymerizable or copolymerizable via their ethylenically unsaturated acyloxy or acylamido radicals and are versatile in use for the preparation of polymers or copolymers by free-radical initiated polymerization or copolymerization.
Description
~2',~
HOECHSl' AKTIENGESELLSCHAFT HOE 89/F 342 Dr.GM/bs Description Ethylenically unsaturated, surface active urethane deri~atives and proce~s for their preparation The invention relates to ethylenically unsaturated, surface active urethane derivatives, in particular urethane derivatives containing (meth)acrylic ester or (meth)acrylamide groups, these urethane derivatives sometimes having interesting and advantageous solu-bilities in water and/or organic solvents and being,among other methods, free-radical polymerizable or copolymerizable, and to processes for their preparation.
EP-A-197,635 discloses the preparation of ethylenically unsaturated surface active urethane derivatives contain-ing alkoxy(poly)alkylene glycol ether radicals, in whichurethane derivatives the urethane group is ~ubstituted at its carboxyl radical by an alkoxy(poly)alkyl~ne glycol ether alkoxy radical and at its nitrogen atom by an ethylenically unsaturated carboxylic ester alkyl radical, so that the urethane group is the joining member between the ethylenically unsaturated carboxylic ester alkyl radical and the alkoxy(poly)alkylene glycol ether radi-cal. The only use given for the surface active urethane derivatives described is as comonomers in proportions of 1 to 25% by weight of the total amount of monomers for the preparation of copolymer dispersions which, after neutralization of the copolymers which are anionic owing to their carboxyl group con~ent, can be effectively used in a great many, and if desired electrolyte-containin~, aqueous preparations at alkaline pH as thickeners.
Homopolymers of the abovementioned surface active ure-thane derivatives have not been disclosed and the mono-meric compounds do not appear to possess any significant solubility in water, since, in the examples of emulsion copolymerization, they are invariably used in aqueous dispersion as comonomers. Neither do the abovementioned 2 ~ 2 ~
urethane monomers appear to dissolve to any significant extent in the vinyl comonomers used, since in none of the examples are these urethane monomers used for copoly-merization dissolved in comonomer.
Surprisingly, urethane derivatives containing ethyleni-cally unsaturated carboxyl or carboxamide radicals have now been found which have moderate to good solubility in water and/or in organic solvents, which are polymerizable and copolymerizable and are advantageous and versatile in use, for example for the preparation of polymers or copolymers.
The present invention accordingly provides ethylenically unsaturated surface active urethane derivatives of the formula I
\C = C~c-z-~cH2-cH2-o)x-(cH2-cH-o)y-(cH2-cH )k C N
R2 R30 - - CH3 C~5 (I) in which the radicals R1 to R4 and Z and the numerical indices x, y and k have the following meaning:
Rl,RZ,R3,which may be identical or different, = H, -CH3, -COOH, -C~2-COOH, preferably H, -CH3, Z = oxygen or NH, preferably oxygen, x,y,k which may be identical or different, in the case where Z = NH represent a numbex from O to 100 with the proviso that x+y+k 2 2, preferably x+y = 2 to 30 with k = O, or in the case where Z = oxygen, represent a number from 1 to 100 with the proviso that x+y+k 2 3, preferably x+y+k = 3 to 30 with k = 1, R4 = optionally substituted (C1-C303-alkyl, prefer-ably (Cl-Cla)-alkyl, optionally substituted ~C6-ClO)-aryl, optionally substituted (C7-C30)-aralkyl, optionally ~ubstituted (C5-Ca)-cycloalkyl, an optionally substituted 5- to 7-membered hetero-cycle.
~2X ~
Moreover, particular preference i8 given to urethane derivatives in which, in the formula I, Rl, R2 _ H, R3 =
-CH3 or Rl, R3 = H, R2 = -CH3, Z = oxygen and x~y+k = 3 to 30 with k = 1.
The invention furthermore provides a process for the preparation of ethylenically unsaturated surface active urethane derivatives of the formula I, \C = C-C-Z-(CH~-CH2-0)X-(C~2-CH-O)y~(C~2_CH )k ~~
R2 R30 CH3 C2H5 (I) in which R1 to R4, Z, x, y and k are as defined above, by reacting isocyanates with hydroxypolyoxyalkyleneoxy-carbonylalkenes or with N-(hydroxypolyoxyalkylene~-alkene-carboxamides, w~ich comprises reacting isocyanates of the formula II
R4 - NC0 (Il) in which R4 is as defined in formula I, with equimolar amounts of hydroxyl compounds of the formula III
R \
C = C-c-æ- ~CH2-CH2^0)X- (CH2-~-o)y (CH2-CH o)k H
R2~ R30 CH3 C2H5~ (III) in which Rl, R2, R3~ Z/ x, y and k are as defined in formula I.
Preferred compounds of the formula III are polyalkylene glycol monoesters of ethylenisally unsaturated carboxylic acids, preferably of acrylic acid~ methacrylic acid or crotonic acid.
The process is preferably carried out according to the invention preferably by carrying out the reactions in bulk or in inert organic solvents or optionally in copolymerizable ethylenically unsaturated monomeræ which are inert under the re~ction conditions (reactive 2 ~
diluents) in the abæence of water, preferably at tempera-tures of between 0C and room temperature or at an elevated temperature, preferably up to 60C.
Suitable inert organic solvents are the inert solvents customarily used in organic synthe~es using isocyanates in anhydrous media, as long as they comply with, inter alia, the requirements regarding solvent action and boiling range.
Examples of preferred inert 601vents are toluene, tetra-hydrofuran (THF), ethyl acetate and hexane.
Furthermore, in some cases reactive diluents can beadvantageous as solvents, these reactive diluents being copolymerizable monomers which are inert under the synthesis conditions of the urethane group formation according to the invention but can subsequently be copolymerized under suitable polymerization conditions with the unsaturated urethane derivatives of the Formula I according to the invention. Examples of preferred inert reactive diluents are accordingly (meth)acrylic ester~, styrene and vinyl esters, these being used preferably with the reactants at below their saturation concentra-tion.
If desired, a catalyst is used during the isocyanate addition according to the invention so that, among other reasons, the reaction temperature can be kept as low as possible, which can be advantageous in particular when using reactive diluents. Preferred catalysts are organic tin compounds which are preferably used dissolved in an inert organic solvent.
Particular preference is given to the use of dibutyltin dilaurate, optionally in combination with tert.-butyl-catechol.
The isocyanates of the formula II used can, in par~icular, be the customary known alkyl, aryl, aralkyl and cycloalkyl monoisocyanates. Particular preference is given, for exEmple, to methyl isocyanate, ethyl isocya-nate, butyl isocyanate, nonyl isocyanate, octadecyl isocyanate, phenyl isocyanate, 3-chlorophenyl i~ocyanate, 3-toluyl isocyanate and cyclohexyl isocyanate.
The compounds of the formula I prepared according to the invention are in most cases obtained directly in solid or waxy or highly viscous form and can, if appropriate after elimination of solvents which have been used, generally be further used as intermediates without further purifi-cation and drying. In some cases, compounds of the formula I also occur in liquid-viscous form and can likewise be directly further used as intermediates.
Obviously, the crude reaction products which result from the synthesis according to the invention can also be purified by customary methods such as, for example, elution, recrystallization, reprecipitation and/or distillation off of volatile components, optionally under reduced pressure, and the compounds of the formula I can be obtained in chemically pure form.
Solubility experLments have demonstrated inter alia that the solubilities of compounds of the formula I are highly dependent on the magnitude of the total of (x+y+k), preferably of ~x+y), in particular of x. For instance, compounds for which x is small and (y+k) = O or for which x > (y+k) are usually soluble in water and the compounds are generally also soluble in inert orqanic solYents and in inert reactive diluents. As x decreases in magnitude, and (y+k) increases in magni~ude, the water solubility of the compounds dLminishes.
This variable solubility behaviour opens up interesting applications for the ethylenically unsaturated and surface active urethane derivatives of the formula I, in particular as comonomers in polymerization~. In this regard, it has surprisingly been found that copolymers which have preferably been prepared by free-radical-initiated emulsion or suspension polymerization and are based on ethylenically unsaturated monomers which contain at least 1~ by weight of monomer units of urethane S derivatives of the formula I of the present invention, have unexpectedly advantageous properties. These copoly-mers, their applicability, particularly in the form of their aqueous copolymer dispersions, as thickener poly-mers in agueous preparations and also their preparation using monomeric urethane derivatives of the formula I of the present invention as starting materials are the subject of Patent Application HQE 89/F 341 (File Number P 3935137.8) filed at the same date to which reference is hereby made.
The invention is explained in more de~ail by means of the examples which follow.
~amples 1 - lO
Preparation of urethane derivatives of the formula I by reacting equimolar amounts of starting components of the formulae II and III in bulk S A 0.25 l four-necked flask fitted with a stirrer, thermo-meter, dropping funnel and reflux condenser having a CaCl2 terminal tube is first charged, in each of Examples 1 - 8, with 0.2 mol of a polyalkylene glycol methacrylate having the degree of alkoxylation siven in Table 1 (= number of alkylene oxide equivalent units x or y or k), together with 0.1 g of dibutyltin dilaurate and 0.05 g of tert.-butylcatechol and then, in each case, 0.195 mol of a mono~socyanate of the composition given in Table 1 is added dropwise with stirring in the cour e of about 40 minutes at room temperature. Then the mixture is stirred at room temperature until the NCO band has disappeared from the IR spectrum of the reaction mixture (duration, about 20 hours). In Examples 9 and 10, meth-acrylic esters are replaced by crotonic esters having the degrees of alkoxylation [x, y, k) given in Table 1 and reacted with the monoisocyanates given in Table 1 in equimolar zmounts and by the identical procedure of Examples 1 - 8.
The urethane derivatives according to the invention of Examples 1 - 10 are obtained in virtually quantitative yield and are in the form of light-coloured waxy pro-ducts.
Table 1 gives a summary of the starting components of the formulae II and III and the solubilities of the resulting urethane derivatives of the formula I according to the invention, ~(+) = moderately soluble, + = readily soluble, +~ = very readily soluble).
~ ~ 2 ~
~ . . , " , _ _ , , .C~'I
0~ + + + + + + + + + +
~ H
R ~ ~
~00~ + +++$ +$++$
o~ 8z - z Z _ , _ Z , _ Z
tn ~ I O ~ o I -- ~ o111 H O --I U P`~ t 0 ~1 U --H ~) _ z ~ u I a~ z a) z ~ Z~ o,~ Z~ ~;' æ~ o ' ~ o_1 o ~
~ o ~ 08 ~ 8 ~ u P~ ~ 00 H O ~ ~ -- C ) -- U -- ~.) -- C.) -- V -- U `-- U --. _ _ _ .
~_ ~¢ ~ U~ O ~0 0 ~ C~ ~ O d' _~
H X
H O .
__ _l O l,.
O N C)--U ~
~ ~ H U ~ _ _I ~I H O O ~ =O
O U~ O O = U ~ O =1.1 ~
_~ Pl 5~ ~ U C_~
_~ _ . ~ .
. ~ X O O
E ~ 1~ :Z --i N ~9 ~ 1~') 10 t` CX:I ~ _I
_ ~
HOECHSl' AKTIENGESELLSCHAFT HOE 89/F 342 Dr.GM/bs Description Ethylenically unsaturated, surface active urethane deri~atives and proce~s for their preparation The invention relates to ethylenically unsaturated, surface active urethane derivatives, in particular urethane derivatives containing (meth)acrylic ester or (meth)acrylamide groups, these urethane derivatives sometimes having interesting and advantageous solu-bilities in water and/or organic solvents and being,among other methods, free-radical polymerizable or copolymerizable, and to processes for their preparation.
EP-A-197,635 discloses the preparation of ethylenically unsaturated surface active urethane derivatives contain-ing alkoxy(poly)alkylene glycol ether radicals, in whichurethane derivatives the urethane group is ~ubstituted at its carboxyl radical by an alkoxy(poly)alkyl~ne glycol ether alkoxy radical and at its nitrogen atom by an ethylenically unsaturated carboxylic ester alkyl radical, so that the urethane group is the joining member between the ethylenically unsaturated carboxylic ester alkyl radical and the alkoxy(poly)alkylene glycol ether radi-cal. The only use given for the surface active urethane derivatives described is as comonomers in proportions of 1 to 25% by weight of the total amount of monomers for the preparation of copolymer dispersions which, after neutralization of the copolymers which are anionic owing to their carboxyl group con~ent, can be effectively used in a great many, and if desired electrolyte-containin~, aqueous preparations at alkaline pH as thickeners.
Homopolymers of the abovementioned surface active ure-thane derivatives have not been disclosed and the mono-meric compounds do not appear to possess any significant solubility in water, since, in the examples of emulsion copolymerization, they are invariably used in aqueous dispersion as comonomers. Neither do the abovementioned 2 ~ 2 ~
urethane monomers appear to dissolve to any significant extent in the vinyl comonomers used, since in none of the examples are these urethane monomers used for copoly-merization dissolved in comonomer.
Surprisingly, urethane derivatives containing ethyleni-cally unsaturated carboxyl or carboxamide radicals have now been found which have moderate to good solubility in water and/or in organic solvents, which are polymerizable and copolymerizable and are advantageous and versatile in use, for example for the preparation of polymers or copolymers.
The present invention accordingly provides ethylenically unsaturated surface active urethane derivatives of the formula I
\C = C~c-z-~cH2-cH2-o)x-(cH2-cH-o)y-(cH2-cH )k C N
R2 R30 - - CH3 C~5 (I) in which the radicals R1 to R4 and Z and the numerical indices x, y and k have the following meaning:
Rl,RZ,R3,which may be identical or different, = H, -CH3, -COOH, -C~2-COOH, preferably H, -CH3, Z = oxygen or NH, preferably oxygen, x,y,k which may be identical or different, in the case where Z = NH represent a numbex from O to 100 with the proviso that x+y+k 2 2, preferably x+y = 2 to 30 with k = O, or in the case where Z = oxygen, represent a number from 1 to 100 with the proviso that x+y+k 2 3, preferably x+y+k = 3 to 30 with k = 1, R4 = optionally substituted (C1-C303-alkyl, prefer-ably (Cl-Cla)-alkyl, optionally substituted ~C6-ClO)-aryl, optionally substituted (C7-C30)-aralkyl, optionally ~ubstituted (C5-Ca)-cycloalkyl, an optionally substituted 5- to 7-membered hetero-cycle.
~2X ~
Moreover, particular preference i8 given to urethane derivatives in which, in the formula I, Rl, R2 _ H, R3 =
-CH3 or Rl, R3 = H, R2 = -CH3, Z = oxygen and x~y+k = 3 to 30 with k = 1.
The invention furthermore provides a process for the preparation of ethylenically unsaturated surface active urethane derivatives of the formula I, \C = C-C-Z-(CH~-CH2-0)X-(C~2-CH-O)y~(C~2_CH )k ~~
R2 R30 CH3 C2H5 (I) in which R1 to R4, Z, x, y and k are as defined above, by reacting isocyanates with hydroxypolyoxyalkyleneoxy-carbonylalkenes or with N-(hydroxypolyoxyalkylene~-alkene-carboxamides, w~ich comprises reacting isocyanates of the formula II
R4 - NC0 (Il) in which R4 is as defined in formula I, with equimolar amounts of hydroxyl compounds of the formula III
R \
C = C-c-æ- ~CH2-CH2^0)X- (CH2-~-o)y (CH2-CH o)k H
R2~ R30 CH3 C2H5~ (III) in which Rl, R2, R3~ Z/ x, y and k are as defined in formula I.
Preferred compounds of the formula III are polyalkylene glycol monoesters of ethylenisally unsaturated carboxylic acids, preferably of acrylic acid~ methacrylic acid or crotonic acid.
The process is preferably carried out according to the invention preferably by carrying out the reactions in bulk or in inert organic solvents or optionally in copolymerizable ethylenically unsaturated monomeræ which are inert under the re~ction conditions (reactive 2 ~
diluents) in the abæence of water, preferably at tempera-tures of between 0C and room temperature or at an elevated temperature, preferably up to 60C.
Suitable inert organic solvents are the inert solvents customarily used in organic synthe~es using isocyanates in anhydrous media, as long as they comply with, inter alia, the requirements regarding solvent action and boiling range.
Examples of preferred inert 601vents are toluene, tetra-hydrofuran (THF), ethyl acetate and hexane.
Furthermore, in some cases reactive diluents can beadvantageous as solvents, these reactive diluents being copolymerizable monomers which are inert under the synthesis conditions of the urethane group formation according to the invention but can subsequently be copolymerized under suitable polymerization conditions with the unsaturated urethane derivatives of the Formula I according to the invention. Examples of preferred inert reactive diluents are accordingly (meth)acrylic ester~, styrene and vinyl esters, these being used preferably with the reactants at below their saturation concentra-tion.
If desired, a catalyst is used during the isocyanate addition according to the invention so that, among other reasons, the reaction temperature can be kept as low as possible, which can be advantageous in particular when using reactive diluents. Preferred catalysts are organic tin compounds which are preferably used dissolved in an inert organic solvent.
Particular preference is given to the use of dibutyltin dilaurate, optionally in combination with tert.-butyl-catechol.
The isocyanates of the formula II used can, in par~icular, be the customary known alkyl, aryl, aralkyl and cycloalkyl monoisocyanates. Particular preference is given, for exEmple, to methyl isocyanate, ethyl isocya-nate, butyl isocyanate, nonyl isocyanate, octadecyl isocyanate, phenyl isocyanate, 3-chlorophenyl i~ocyanate, 3-toluyl isocyanate and cyclohexyl isocyanate.
The compounds of the formula I prepared according to the invention are in most cases obtained directly in solid or waxy or highly viscous form and can, if appropriate after elimination of solvents which have been used, generally be further used as intermediates without further purifi-cation and drying. In some cases, compounds of the formula I also occur in liquid-viscous form and can likewise be directly further used as intermediates.
Obviously, the crude reaction products which result from the synthesis according to the invention can also be purified by customary methods such as, for example, elution, recrystallization, reprecipitation and/or distillation off of volatile components, optionally under reduced pressure, and the compounds of the formula I can be obtained in chemically pure form.
Solubility experLments have demonstrated inter alia that the solubilities of compounds of the formula I are highly dependent on the magnitude of the total of (x+y+k), preferably of ~x+y), in particular of x. For instance, compounds for which x is small and (y+k) = O or for which x > (y+k) are usually soluble in water and the compounds are generally also soluble in inert orqanic solYents and in inert reactive diluents. As x decreases in magnitude, and (y+k) increases in magni~ude, the water solubility of the compounds dLminishes.
This variable solubility behaviour opens up interesting applications for the ethylenically unsaturated and surface active urethane derivatives of the formula I, in particular as comonomers in polymerization~. In this regard, it has surprisingly been found that copolymers which have preferably been prepared by free-radical-initiated emulsion or suspension polymerization and are based on ethylenically unsaturated monomers which contain at least 1~ by weight of monomer units of urethane S derivatives of the formula I of the present invention, have unexpectedly advantageous properties. These copoly-mers, their applicability, particularly in the form of their aqueous copolymer dispersions, as thickener poly-mers in agueous preparations and also their preparation using monomeric urethane derivatives of the formula I of the present invention as starting materials are the subject of Patent Application HQE 89/F 341 (File Number P 3935137.8) filed at the same date to which reference is hereby made.
The invention is explained in more de~ail by means of the examples which follow.
~amples 1 - lO
Preparation of urethane derivatives of the formula I by reacting equimolar amounts of starting components of the formulae II and III in bulk S A 0.25 l four-necked flask fitted with a stirrer, thermo-meter, dropping funnel and reflux condenser having a CaCl2 terminal tube is first charged, in each of Examples 1 - 8, with 0.2 mol of a polyalkylene glycol methacrylate having the degree of alkoxylation siven in Table 1 (= number of alkylene oxide equivalent units x or y or k), together with 0.1 g of dibutyltin dilaurate and 0.05 g of tert.-butylcatechol and then, in each case, 0.195 mol of a mono~socyanate of the composition given in Table 1 is added dropwise with stirring in the cour e of about 40 minutes at room temperature. Then the mixture is stirred at room temperature until the NCO band has disappeared from the IR spectrum of the reaction mixture (duration, about 20 hours). In Examples 9 and 10, meth-acrylic esters are replaced by crotonic esters having the degrees of alkoxylation [x, y, k) given in Table 1 and reacted with the monoisocyanates given in Table 1 in equimolar zmounts and by the identical procedure of Examples 1 - 8.
The urethane derivatives according to the invention of Examples 1 - 10 are obtained in virtually quantitative yield and are in the form of light-coloured waxy pro-ducts.
Table 1 gives a summary of the starting components of the formulae II and III and the solubilities of the resulting urethane derivatives of the formula I according to the invention, ~(+) = moderately soluble, + = readily soluble, +~ = very readily soluble).
~ ~ 2 ~
~ . . , " , _ _ , , .C~'I
0~ + + + + + + + + + +
~ H
R ~ ~
~00~ + +++$ +$++$
o~ 8z - z Z _ , _ Z , _ Z
tn ~ I O ~ o I -- ~ o111 H O --I U P`~ t 0 ~1 U --H ~) _ z ~ u I a~ z a) z ~ Z~ o,~ Z~ ~;' æ~ o ' ~ o_1 o ~
~ o ~ 08 ~ 8 ~ u P~ ~ 00 H O ~ ~ -- C ) -- U -- ~.) -- C.) -- V -- U `-- U --. _ _ _ .
~_ ~¢ ~ U~ O ~0 0 ~ C~ ~ O d' _~
H X
H O .
__ _l O l,.
O N C)--U ~
~ ~ H U ~ _ _I ~I H O O ~ =O
O U~ O O = U ~ O =1.1 ~
_~ Pl 5~ ~ U C_~
_~ _ . ~ .
. ~ X O O
E ~ 1~ :Z --i N ~9 ~ 1~') 10 t` CX:I ~ _I
_ ~
Claims (5)
1. An ethylenically unsaturated, surface active urethane derivative of the formula I
(I) in which the radicals R1 to R4 and Z and the numerical indices x, y and k have the following meanings:
R1,R2,R3,which may be identical or different, = H, -CH3, -COOH, -CH2-COOH, preferably H, -CH3, Z = oxygen or NH, preferably oxygen, x,y,k which may be identical or different, in the case where Z = NH represent a number from 0 to 100 with the proviso that x+y+k > 2, prefer-ably x+y = 2 to 30 with k = 0, or in the case where Z = oxygen, represent a number from 1 to 100 with the proviso that x+y+k > 3, preferably x+y+k = 3 to 30 with k = 1, R4 = optionally substituted (C1-C30)-alkyl, preferably (C1-C1a)-alkyl, optionally sub-stituted (C1-C10)-aryl, optionally substituted (C7-C30)-aralkyl, optionally substituted (C5-C8)-cycloalkyl, an optionally substituted 5-to 7-membered heterocycle.
(I) in which the radicals R1 to R4 and Z and the numerical indices x, y and k have the following meanings:
R1,R2,R3,which may be identical or different, = H, -CH3, -COOH, -CH2-COOH, preferably H, -CH3, Z = oxygen or NH, preferably oxygen, x,y,k which may be identical or different, in the case where Z = NH represent a number from 0 to 100 with the proviso that x+y+k > 2, prefer-ably x+y = 2 to 30 with k = 0, or in the case where Z = oxygen, represent a number from 1 to 100 with the proviso that x+y+k > 3, preferably x+y+k = 3 to 30 with k = 1, R4 = optionally substituted (C1-C30)-alkyl, preferably (C1-C1a)-alkyl, optionally sub-stituted (C1-C10)-aryl, optionally substituted (C7-C30)-aralkyl, optionally substituted (C5-C8)-cycloalkyl, an optionally substituted 5-to 7-membered heterocycle.
2. A urethane derivative as claimed in claim 1, wherein, in formula I, R1, R2 = H, R3 = -CH3 or R1, R3 = H, R2 =
-CH3, Z = oxygen and x+y+k = 3 to 30 with k = 1.
-CH3, Z = oxygen and x+y+k = 3 to 30 with k = 1.
3. A process for the preparation of ethylenically un-saturated surface active urethane derivatives of the formula I as claimed in claim 1 and/or 2, (I) in which R1 to R4, Z, x, y and k are as defined for formula I in claim 1 and/or 2, by reacting isocyanates with hydroxypolyoxyalkyleneoxycarbonylalkenes or with N-(hydroxypolyoxyalkylene)-alkenecarboxamides, which comprises reacting isocyanates of the formula II
R4 - NCO (II) in which R4 is as defined in formula 1, with equimolar amounts of hydroxyl compounds of the formula III
(III) in which R1, R2, R3, Z, x, y and k are as defined in formula I.
R4 - NCO (II) in which R4 is as defined in formula 1, with equimolar amounts of hydroxyl compounds of the formula III
(III) in which R1, R2, R3, Z, x, y and k are as defined in formula I.
4. The process as claimed in claim 3, wherein the reac-tion is carried out in bulk or in inert organic solvents or in copolymerizable ethylenically un-saturated monomers which are inert under the reaction conditions, in the absence of water, preferably at temperatures of between 0°C and room temperature or at an elevated temperature.
5. The process as claimed in claims 3 and/or 4, wherein the compounds of the formula III used are polyalkylene glycol monoesters of ethylenically unsaturated car-boxylic acids, preferably of acrylic acid, methacrylic acid or crotonic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3935138A DE3935138A1 (en) | 1989-10-21 | 1989-10-21 | ETHYLENICALLY UNSATURATED, INTERFACE-ACTIVE URETHAN DERIVATIVES AND METHOD FOR THEIR PRODUCTION |
| DEP3935138.6 | 1989-10-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2028040A1 true CA2028040A1 (en) | 1991-04-22 |
Family
ID=6391943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002028040A Abandoned CA2028040A1 (en) | 1989-10-21 | 1990-10-19 | Ethylenically unsaturated, surface active urethane derivatives and process for their preparation |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0424750A3 (en) |
| JP (1) | JPH03140325A (en) |
| AU (1) | AU635077B2 (en) |
| CA (1) | CA2028040A1 (en) |
| DE (1) | DE3935138A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412142A (en) * | 1993-06-30 | 1995-05-02 | National Starch And Chemical Investment Holding Corporation | Associative monomers |
| CN105008326A (en) * | 2013-02-25 | 2015-10-28 | 株式会社自动网络技术研究所 | Highly sensitive (meth)acrylate and radically curable material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6001935A (en) | 1997-11-10 | 1999-12-14 | Stephan Company | Durable hydrophilic polymer coatings |
| ES2179381T3 (en) * | 1996-12-18 | 2003-01-16 | Stepan Co | DURABLE HYDROPHYL POLYMER COATINGS. |
| DE19835860C1 (en) * | 1998-08-07 | 2000-04-20 | Siemens Ag | Circuit for device used for material investigation using eddy current |
| DE502008002161D1 (en) * | 2008-08-08 | 2011-02-10 | Bayer Materialscience Ag | Phenylisocyanate-based high refractive index urethane acrylates |
| JP4628489B1 (en) * | 2010-05-27 | 2011-02-09 | 和代 今野 | Binder with file for storing documents |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3734725A (en) * | 1969-05-28 | 1973-05-22 | Grace & Co | Silverless photographic printing paper |
| US3627819A (en) * | 1969-07-16 | 1971-12-14 | Dow Chemical Co | Adducts of alkenyl isocyanates with polyglycols |
| CA1196009A (en) * | 1981-12-10 | 1985-10-29 | Albert C. Chen | Acryloyl and alkylacryloyl polyalkoxy carbamates, compositions thereof and their use in radiation curable coatings |
| EP0295031A3 (en) * | 1987-06-12 | 1991-05-08 | SMITH & NEPHEW plc | Orthopaedic splinting material |
| JPH01170611A (en) * | 1987-12-26 | 1989-07-05 | Sanyo Chem Ind Ltd | Production of polyurethane |
-
1989
- 1989-10-21 DE DE3935138A patent/DE3935138A1/en not_active Withdrawn
-
1990
- 1990-10-12 EP EP19900119570 patent/EP0424750A3/en not_active Withdrawn
- 1990-10-19 CA CA002028040A patent/CA2028040A1/en not_active Abandoned
- 1990-10-19 JP JP2279472A patent/JPH03140325A/en active Pending
- 1990-10-19 AU AU64780/90A patent/AU635077B2/en not_active Ceased
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5412142A (en) * | 1993-06-30 | 1995-05-02 | National Starch And Chemical Investment Holding Corporation | Associative monomers |
| US5442091A (en) * | 1993-06-30 | 1995-08-15 | National Starch And Chemical Investment Holding Corporation | Associative monomers |
| US5478881A (en) * | 1993-06-30 | 1995-12-26 | National Starch And Chemical Investment Holding Corporation | Solutions, latexes and carpet coating compositions containing novel associative monomers and polymers |
| US5532036A (en) * | 1993-06-30 | 1996-07-02 | National Starch And Chemical Investment Holding Corporation | Methods for reducing volatile organic chemical contents of carpets |
| CN105008326A (en) * | 2013-02-25 | 2015-10-28 | 株式会社自动网络技术研究所 | Highly sensitive (meth)acrylate and radically curable material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0424750A3 (en) | 1991-11-13 |
| EP0424750A2 (en) | 1991-05-02 |
| DE3935138A1 (en) | 1991-04-25 |
| JPH03140325A (en) | 1991-06-14 |
| AU6478090A (en) | 1991-04-26 |
| AU635077B2 (en) | 1993-03-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |