AU635077B2

AU635077B2 - Ethylenically unsaturated, surface active urethane derivatives and process for their preparation

Info

Publication number: AU635077B2
Application number: AU64780/90A
Authority: AU
Inventors: Hans-Ullrich Huth
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1989-10-21
Filing date: 1990-10-19
Publication date: 1993-03-11
Anticipated expiration: 2010-10-19
Also published as: DE3935138A1; JPH03140325A; EP0424750A2; EP0424750A3; AU6478090A; CA2028040A1

Description

AW

635077 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1352-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class In Form it. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art Name of Applicant Address of Applicant SActual Inventor Address for Service HOECHST AKTIENGESELLSCHAFT 50 Bruningstrasse, D-6230 Franfurt/Main 80, Federal Republic of Germany HANS-ULLRICH HUTH WATERMARK PATENT TRADEMARK ATTORNEYS.

LOCKED BAG NO. 5, HAWTHORN, VICTORIA 3122, AUSTRALIA Complete Specification for the invention entitled: ETHYLENICALLY UNSATURATED, SURFACE ACTIVE URETHANE DERIVATIVES AND PROCESS FOR THEIR PREPARATION The following statement is a full description of this invention, including the best method of performing it known to :us IOECHST AKTIENGESELLSCHAFT HOE 89/F 342 Dr.GM/bs Description Ethylenically unsaturated, surface active urethane derivatives and process 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 solubilities 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- 15 ing alkoxy(poly)alkylene glycol ether radicals, in which urethane derivatives the urethane group is substituted at its carboxyl radical by an alkoxy(poly)alkylene 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 radical. 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 content, can be effectively used •in a great many, and if desired electrolyte-containing, aqueous preparations at alkaline pH as thickeners.

Homopolymers of the abovementioned surface active urethane derivatives have not been disclosed and the monomeric 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 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 copolymerization dissolved in comonomer.

Surprisingly, urethane derivatives containing ethylenically 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 S. formula I

SR

1

H

.R

C C-C-Z-(CH2-CH 2 -0)x-(CH 2 -CH-0)y-(CH2-CH-)k-C-N-R R2 R 3 0 CH 3

C

2

H

5

(I)

in which the radicals R 1 to R 4 and Z and the numerical indices x, y and k have the following meaning: ,R ,R ,which may be identical or different, H, -CH 3 -COOH, -CH 2 -COOH, preferably H, -CH 3 Z oxygen or NH, preferably oxygen, x,y,k which may be identical or different, -ea=f- Z: .w represent a number from 0 to 100 with the proviso that x+y+k 2, preferably x+y 2 to 30 with k 0, or ?5 ii the case where Z oxygen, represent a number from 0 to 100 with the proviso that x+y+k t 3, preferably x+y+k 3 to 30 with k 1,

R

4 optionally substituted (C 1

-C

30 )-alkyl, preferably (Ci-C 1 e)-alkyl, optionally substituted

C

10 )-aryl, optionally substituted (C 7

-C

30 )-aralkyl, optionally substituted (C 5 -C )-cycloalkyl, an Soptionally substituted 5- to 7-membered hetero- R /cycle.

3 Moreover, particular preference is given to urethane derivatives in which, in the formula I, R 1

R

2 H, R 3 -CH3 or R 1

R

3 H, R 2 -CH3, Z oxygen and x+y+k 3 to with k 1.

The invention furthermore provides a process for the preparation of ethylenically unsaturated surface active urethane derivatives of the formula I,

R

1

H

C C-C-Z-(CH2-CH2-)CH2- -(CH2-CH-0)y-(CH-CH-0)-C-N-R 2 3 l 1 I R R O CH 3

C

2

H

5 0 S in which R 1 to R 4 Z, x, y and k are as defined above, by reacting isocyanates with hydroxypolyoxyalkyleneoxycarbonylalkenes or with N-(hydroxypolyoxyalkylene)-alkenecarboxamides, which comprises reacting isocyanates of the formula II

R

4 NCO (II) in which R 4 is as defined in formula I, with equimolar amounts of hydroxyl compounds of the formula III

R

1 C C-C-Z-(CH2-CH2-0)x-(CH2-CH-0) -(CH2-CH-O)k-H

R

2

R

3 0 CH3 C2H5, (III) in which R 1

R

2

R

3 Z, x, y and k are as defined in formula I.

Preferred compounds of the formula III are polyalkylene glycol monoesters of ethylenically 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 monomers which are inert under the reaction conditions (reactive 4 diluents) in the absence of water, preferably at temperatures of between 0 C and room temperature or at an elevated temperature, preferably up to 60 0

C.

Suitable inert organic solvents are the inert solvents customarily used in organic syntheses 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 solvents are toluene, tetrahydrofuran (THF), ethyl acetate and hexane.

Furthermore, in some cases reactive diluents can be advantageous 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 esters, styrene and vinyl esters, these being used preferably with the reactants at below their saturation concentration.

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 0: using reactive diluents. Preferred catalysts am. 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.-butylcatechol.

The isocyanates of the formula II used can, in particular, be the customary known alkyl, aryl, aralkyl and cycloalkyl monoisocyanates. Particular preference is given, for example, to methyl isocyanate, ethyl isocyanate, butyl isocyanate, nonyl isocyanate, octadecyl isocyanate, phenyl isocyanate, 3-chlorophenyl isocyanate, 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 purification 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 experiments have demonstrated inter alia that the solubilities of compounds of the formula I are highly dependent on the magnitude of the total of 25 preferably of in particular of x. For instance, compounds for which x is small and 0 or for which x are usually soluble in water and the compounds are generally also soluble in inert organic solvents and in inert reactive diluents. As x decreases in magnitude, and increases in magnitude, the water solubility of the compounds diminishes.

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 polymerizations. In this regard, it has surprisingly been found that copolymers 6 which have preferably been prepared by free-radicalinitiated emulsion or suspension polymerization and are based on ethylerically unsaturated monomers which contain at least 1% by weight of monomer units of urethane derivatives of the formula I of the present invention, have unexpectedly advantageous properties. These copolymers, their applicability, particularly in the form of their aqueous copolymer dispersions, as thickener polymers in aqueous preparations and also their preparation using monomeric urethane derivatives of the formula I of the present invention as starting materials are, the Cetrr o?FVcdCa:,'n cV3) (Ijo, subject of Patent Application HOE 89/F 341 (1Y-«NtmnbzE= P 3935137.8) filed at the same date to which reference is hereby made.

The invention is explained in more detail by means of the examples which follow.

7 Examples 1 Preparation of urethane derivatives of the formula I by reacting equimolar amounts of starting components of the formulae II and III in bulk A 0.25 1 four-necked flask fitted with a stirrer, thermometer, dropping funnel and reflux condenser having a CaC1 2 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 given in Table 1 number of alkylene oxide equivalent units x or y k3), together with 0.1 g of dibutyltin dilaurate and 0.05 g of tert.-butyloatechol and then, in each case, 0.195 mol of a monoisocyanate of the composition given in Table 1 is added dropwise with stirring in the course 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, methacrylic esters are replaced by crotonic esters having the degrees of alkoxylation y, A) given in Table 1 and reacted with the monoisocyanates given in Table 1 in equimolar amounts and by the identical procedure of Examples 1 8.

The urethane derivatives according to the invention of 5 Examples 1 10 are obtained in virtually quantitative yield and are in the form of light-coloured waxy products.

Table 1 gives a summary of the starting components of the formulae II and III and the solubilities of the resulting ?0 urethane derivatives of the formula I according to the invention, moderately soluble, readily soluble, very readily soluble).

S

at S t a.

at a a at. 9 a a a S a a a ta a a a at ta a ta a att a a. a a a a tat S a a a a at at S. t a a Sat.

a a. a a 5 Table 1 Ex. JPolyalkylens glycol x or y in formula Isocyanates I Solubility of the resulting No. esters of the III (1401 Al~aylene Iof the formula I compounds in: formula III oxide units) formula II J Water, Ethyl acrylate 0 11 CHn 2

CHZ-CH

2 -O x-H

LI''

0 CH.t 2

(CH

2 -CH-O -H I I

CH

3

LCH

3

CH

3 -CH=CH-C-O- (CH 2

-CH

2 0).-H

CAHNCO

(Butyl-NCO)

C

18

-H

37

NCO

(Octadecyl-NCO)

CH

3

NCO

(Me thyl-NCO)

CAH

1

NCO

(Cyclohexyl-NCO)

CAHNCO

(Phenyl-NCO)

C

18

H

37

NCO

(Octadecyl-NCO)

CAHNCO

(Butyl-NCO)

CAH

1

NCO

(Cyclohexyl-NCQ)

CAHNCO

(Phenyl-NCO)

CIBH

37

NCO

(Octadecyl-NCO) S S

Claims

1. An ethylenically unsaturated, surface active urethane derivative of the formula I H RI I C C-C-Z-(CH 2 -CH 2 -O)x-(CH 2 -CH-O)y- (CH 2 -CH-O)k- C-N-R 4 R2II I I II R 3 0 CH 3 C 2 H 5 O (I) in which the radicals R1 to R 4 and Z and the numerical indices x, y and k have the following meanings: Ri, R2,R3, which may be identical or different, SH, -CH 3 -COOH, -CH 2 -COOH with the proviso that Ri and R2 are different if one of R1 or R2 is H, Z oxygen or NH, x,y,k which may be identical or different, represent a number from 0 to 100 with the proviso that x+y+k 2, or in the case where Z oxygen, -represent-a-number-f r t- 4-- x+y+k 3, R 4 optionally substituted (Ci-Cso)-alkyl, optionally substituted (C 6 -Clo)-aryl, optionally substituted (C 7 -C 3 0 )-aralkyl, optionally substituted (Cs-C8)-cycloalkyl, an optionally S: substituted 5- to 7-membered heterocycle.

2. A urethane derivative as claimed in claim 1 wherein R1, R2, R3 are H or CH 3

3. A urethane derivative as claimed in claim 1 or 2 wherein Z oxygen.

4. A urethane derivative as claimed in any one of claims 1-3 wherein x+y=2 to with k=0. A urethane derivative as claimed in any one of claims 1-3 wherein x+y+k=3 to with k=l.

6. A urethane derivative as claimed in any one of claimc" 1-5 wherein R4 (C 1 -C18)-alkyl.

7. A urethane derivative as claimed in any one of claims 1-6, wherein, in formula I, 1R--Rz t -RI, R3 H, R2 -CH 3 Z oxygen and x+y+k 3 to with k 1.

8. A process for the preparation of ethylenically unsaturated surface active urethane derivatives of the formula I as claimed in any one of claims 1-7, H R1 1 C C-C-Z-(CH 2 -CH 2 -O)x-(CH 2 -CH-O)y-(CH 2 -CH- O)k-C-N-R 4 R2II I I II R 3 0 CH 3 C 2 H 5 O (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 R 4 is as defined in formula I, with equimolar amounts of hydroxyl compounds of the formula III R1 *C C-C-Z-(CH 2 -CH 2 O)x- (CH 2 -CH-O)y-(CH 2 CH-O)k-H R 2 I II I I R 3 0 CHi C 2 H 5 (II) in which R1, R2, R3, Z, x, y and k are as defined in formula I.

9. The process as claimed in claim 8, wherein the reaction is carried out in bulk or in inert organic solvents or in copolymerizable ethylenically unsaturated 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. The process as claimed in claim 8 or 9, wherein the compounds of the formula III used are polyalkylene glycol monoesters of ethylenically unsaturated carboxylic acids, preferably of acrylic acid, methacrylic acid or crotonic acid. DATED this 24th day of August, 1992. HOECHST AKTIENGESELSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRAUA DBM/KJS/ML DOC 020 AU6478090.WPC