WO1996006834A1

WO1996006834A1 - Silicone containing imidazoline compositions

Info

Publication number: WO1996006834A1
Application number: PCT/US1995/010993
Authority: WO
Inventors: Dennis L. Fost; Abe Berger
Original assignee: Mona Industries, Inc.
Priority date: 1994-08-31
Filing date: 1995-08-29
Publication date: 1996-03-07
Also published as: EP0778830A4; EP0778830A1

Abstract

There are provided silicone containing imidazoline compositions represented by formula (I) wherein: R is an aliphatic radical containing from 4 to 40 carbon atoms; R1 and R2, which may be the same or different is selected from hydrogen and lower alkyl; R3 is an organosilicone chain represented by formula (II) wherein: R5 may be R6, -R4- and mixutres thereof, wherein R4 is alkylene, branched alkylene and alkylene with heteroatoms, with the proviso that at least one of R5 is a -R4- group. R6 can be selected from alkyl, aryl and olefin; R7 and R8, which can be the same or different, are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl; a can be an integer of 0 to 50,000; b can be an integer of 0 to 5,000; c can be an integer of 0 to 100.

Description

SILT.CONE CONTAINING IMIDAZOLINE COMPOSITIONS

Field of the Invention

The present invention relates to novel imidazoline compositions and, more particularly, to silicone containing imidazoline compositions and to methods for preparing the same.

Background of the Invention

The production and marketing of imidazolines and various derivatives thereof has been carried on for a number of years. Such compositions have been widely used as surface active agents, metal treating compounds and a variety of other applications. Imidazolines are commonly prepared by condensing, under conditions of heating and stirring, a long chain aliphatic monocarboxylic or fatty acid or a source thereof such as amides (or esters of such acids) with an alkyl, hydroxyalkyl and/or aminoalkyl ethylene diamine derivative, such as hydroxyethyl ethylene diamine. Organosiloxane compositions including compositions having amine and diamine functional groups as well as many polysiloxane compositions which exhibit excellent properties as surface active agents, lubricants and the like are well known and have been used commercially over the years. While a variety of imidazoline and polysiloxane compositions and derivatives thereof are known, to the best of our knowledge there has been no disclosure of the novel silicone-containing and/or silicone derivatives of imidazolines herein described as well as the methods for preparing the same. Such compositions are widely useful as surfactants and a variety of applications. Summary of the Invention

It is accordingly an object of the present invention to provide highly useful novel silicone containing imidazoline compositions and the acid salts thereof.

It is a further object of the present invention to provide a method for directly and readily preparing silicone containing imidazoline compositions and the acid salts thereof.

In accordance with the present invention there are provided novel silicone containing imidazoline compositions that may be represented by the formula:

H,

K.

H-

wherein: R is an aliphatic radical containing from 4 to 40, preferably 8 to 22, carbon atoms; R_x and R₂, which may be the same or different is of the group consisting of hydrogen and lower alkyl (Cj-C₆); R₃ is a organosilicone backbone chain which may be represented by the formula:

wherein:

R₅, which can be the same or different, may be selected from Re,-R₄- and mixtures thereof, wherein R_e is as herein defined, R₄ is alkylene, branched alkylene and alkylene with heteroatoms, with the proviso that at least one of R₅ is a -R₄- group. R₆ can be the same or different and can be selected from alkyl, aryl and olefin (vinyl); R₇ and R_β, which can be the same or different, are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl (vinyl); a can be an integer of 0 to 50,000; b can be an integer of 0 to 5,000; c can be an integer of 0 to 100.

The present invention is also concerned with acid salts of silicone-containing imidazoline compositions formed with organic and mineral acids having anionic groups with valences from 1 to 3.

In another aspect of the present invention, there is also provided a method for readily preparing silicone- containing imidazoline compositions having effective surface active, substantivity and lubrication properties which comprises reacting an organosilicone fluid or composition having at least one terminal, lateral or combination of terminal and lateral aminoethyl aminoalkyl functional group with up to about a stoichiometric amount of a long chain monocarboxylic acid or amide or ester derivative thereof having from 4 to 40, preferably 8 to 22, carbon atoms, at an elevated temperature, preferably at least about 140°C, for a time necessary to substantially react the moncarboxylic acid and provide for the cyclization of the reaction product.

Description of the Preferred Embodiments

The present invention is concerned with novel and highly useful silicone-containing imidazoline compositions that can be represented by the formula:

wherein:

R is an aliphatic radical containing from 4 to

40, preferably 8 to 22, carbon atoms; R_x and R₂, which may be the same or different, is of the group consisting of hydrogen and lower alkyl(Ci-Cs) ; R₃ is an organosilicone chain which may be represented by the formula:

R₅, which can be the same or different, may be selected from Re,-R₄- and mixtures thereof, wherein Re is as herein defined, R₄ is alkylene, branched alkylene and alkylene with heteroatoms, with the proviso that at least one of R₅ is a -R₄- group.

Re can be the same or different and can be selected from alkyl, aryl and olefinic (vinyl);

R₇ and R_β, which can be the same or different, are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl (vinyl); a can be an integer of 0 to 50,000; b can be an integer of 0 to 5,000; and c can be an integer of 0 to 100. The novel imidazoline compositions of the present invention can be prepared by condensing, under conditions of heating and stirring either neat or in a solvent, a long chain aliphatic monocarboxylic or fatty acid (or a source thereof such as amides or esters of the acids) with a silicone composition having at least one aminoethyl aminoalkyl functional group as is described in greater detail hereinafter. The mole ratio of the acid to the amine functional silicone composition is variable but generally falls within the range of 1 mole of silicone composition having an amine functional group with up to a stoichiometric amount of the acid, and the temperature at which the condensation reaction is carried out is generally in excess of 100°C, preferably in excess of 140°C. The reaction time is several hours, usually within the range of about 4 to 12 hours, depending upon the particular reactants employed and the particular condensation temperature employed; or, where the reaction is carried out under less than atmospheric pressure, the reaction temperature may be somewhat reduced. Usually, the condensation temperature or temperature of heating and the duration of the heating are so correlated as to cause splitting out of water in excess of 2 moles for each mole of free acid and in excess of 1 mole of combined acid involved per diamine reactant.

The long chain aliphatic monocarboxylic or fatty acids useful in producing the imidazoline compositions of the invention include saturated as well as ethylenically unsaturated naturally occurring and synthetic acids containing from 4 to 40, particularly 8 to 22, carbon atoms and preferably acids that are not volatile or will decompose at a temperature of at least 140°C. Encompassed by such acids are lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid and commercial mixtures of various of such acid as are derived from animal, fish and vegetable oils and fats such as coconut oil, cottonseed oil, corn oil, tallow, soya oil, castor oil and also such monocarboxylic acid mixtures as are present in tall oil or refined tall oil and the like. In place of the free acids, the amides or ester thereof can be employed, including the glyceride esters such as the foregoing oils and fats, as well as the monohydric alcohol esters such as the methyl esters of the foregoing acids.

The silicone fluids or compositions, notably polysiloxane compositions having terminal, lateral and/or combinations of terminal and lateral aminoethylaminoalkyl functional groups, which are used to prepare the imidazoline compositions of the present invention, can be selected from a variety of aminoethylaminoalkyl functional silicone compositions including aminoethylaminopropyl functional silicone fluids commercially available from General Electric as SF1718-D1 and Shin-Etsu as KF393 and aminoethyl aminoisobutyl functional silicone fluid available from Dow Corning as DCX28200. While the molecular weight of the diamine functional polysiloxane compositions which may be employed is not critical, and suitable diamine functional compositions may have molecular weights of 12000, or even higher, silicone compositions having molecular weights from about 500 to 12000 are, in general, preferred.

The novel acid salts of the present invention which are produced from the aforementioned silicone- containing imidazolines may be represented by the following formula:

wherein:

R is as hereinabove defined;

R_x and R₂ are as hereinabove defined; R₃ is as hereinabove defined;

X is an anion group having a 1 to 3 valence; j is an integer from 1 to 3; and k is an integer from 1 to 3; with the proviso that (k-j) must be 0 or a positive interger.

The acid salts of the aforementioned silicone- containing imidazoline compositions of the present invention are readily prepared by simply admixing the imidazoline composition and an organic or mineral acid as illustrated below at temperatures between about room temperature and about 100° C, and preferably at ambient temperatures in from the range of about 20-30° C. The imidazoline and acid are desirably combined in approximately stoichiometric proportions, sufficient acid being added to substantially neutralize the amine groups present in the imidazoline composition.

Illustrative of such suitable mineral and organic acids are phosphoric acid, phosphorus acid, sulfuric acid, sulfurous acid, hydrochloric acid, acetic acid, carbonic acid, formic acid, hypochlorous acid, nitric acid.

The imidazoline compositions of the present invention and acid salts thereof lend themselves to a wide variety of practical applications. Such materials can be employed for example, as emulsifier and dispersing agents, wetting agents and as additives to surface active compositions. They are also useful to provide improved substantively to a variety of surfaces, as anaesthetic agents, foam stabilizers, as useful additives for metal cleaning and treating compositions and can be used to improve the lubricating properties for metal treating compositions and in a variety of personal treating and cosmetic compositions.

Various other materials can be added to the novel silicone-containing imidazoline composition of the preset invention and the acid salts thereof. For example, such additives include various surface active agents; alkaline builder salts and agents such as sodium carbonate, sodium bicarbonate, sodium sulfate and the like, as well as special purpose additives such as dyes, bleaches, brighteners and the like.

The invention is further illustrated by the following examples which are not to be considered as limitative of its scope.

Example 1

A Bis (Trimethyl capped) aminoethyl aminoisobutyl methyl siloxy co-Dimethyl Siloxy containing fluid obtained from Dow-Corning Corp. under the designation X2-8200 is used in this example. The silicone fluid has an amino content of 1.9 percent which corresponds to an equivalent weight of 1684.

168.4 grams of the silicone fluid is mixed with 28.3 grams of oleic acid in a reaction vessel. The fluids are incompatible when mixed and 95ml of xylene is added to the mixture which forms a compatible reaction mixture. The reaction mixture is heated to boiling for 4 hours while a total of 3.5ml of water is separated (theoretical 3.6ml).

The xylene is removed from the reaction mixture under reduced pressure of about 60mm following which the reaction mixture is heated to 200°C at 3mm vacuum for 3 hours.

The reaction mixture is cooled and a viscous yellow fluid is obtained having a characteristic absorption of 6.25 microns in the infra red. The alkali number of the reaction product is 32 (required is 29). Example 2

The silicone fluid of example 1 is used in this example.

168.2 grams of the silicone fluid is combined with 28.4 grams of stearic acid in a reaction vessel and then 95 grams of xylene is added to the mixture.

The reaction mixture is heated to boiling for 4 hours during which time 3.5 grams of water is collected.

After the xylene is removed from the reaction mixture, the temperature of the reaction mixture is raised to 200°C under a vacuum of 3mm and maintained at that temperature for -3 hours.

After cooling, the reaction product has an alkali number of 29.9 (theoretical 29) and an absorption of 6.25 micron in the infra red. The cooled reaction product forms a tan solid upon standing.

Example 3

A Bis (Trimethylsiloxy capped) aminoethyl aminoisobutyl methyl siloxy co-dimethylsiloxy containing fluid obtained from Dow Corning Corp. under the designation X2-8107 is used in this example. The silicone fluid has an amine content of 0.25 percent which corresponds to an equivalent weight of 12,800.

128 grams of the silicone fluid is combined with 2.83 grams of oleic acid and 75ml of xylene in a reaction vessel. The reaction mixture is heated to boiling under reflux for 4 hours while about 0.4ml of water is collected

(theoretical 0.36ml) .

The solvent is removed from the reaction mixture under vacuum followed by heating to 200°C at 3mm vacuum for 2 hours.

After cooling the reaction mixture, is a yellow liquid having an alkali number of 4.7 (theoretical 4.3). Example 4

The silicone fluid of example 3 is used in this example.

192 grams of the silicone fluid is mixed with 4.26 grams of stearic acid and 95ml of xylene in a reaction vessel using the reaction procedure of example 3 a light hazy yellow fluid is obtained having an alkali number of

5.47 (required 4.3).

Example 5

An aminoethyl aminopropyl trimethyl silyl capped silicone fluid having an amine equivalent weight of 745.2 obtained from Shin-Etsu under the designation KF-393 is used in this example.

A mixture of 276.3 grams (0.37 equivalent weight) of silicone fluid, 104.9 grams of oleic acid and 75ml of xylene is changed to a reaction vessel is heated to about 175°C-180°C under reflux for 6 hours. Water of condensation is azeotropicallly removed from the reaction vessel as it is formed. A total of 13.3ml of water (theoretical 13.3ml) is collected.

The reaction mixture is cooled to 80°C and a vacuum of 3mm is applied to the reaction vessel while slowly increasing the reaction mixture to a temperature of 185°C-190°C. The reaction mixture is maintained at that temperature and vacuum for 3 additional hours.

Upon cooling, the reaction product is a yellow fluid having an alkali number of 60 is obtained, (theory 56.5).

200 grams of the above reaction product (0.21 equivalent weight) is added to a reaction vessel and diluted with 200ml of isopropanol. 12.3 grams (0.1 mol) of 85% phosphoric acid is added with agitation to the diluted reaction product and a clear yellow solution is obtained.

Claims

11WHAT IS CLAIMED IS:

1. Silicone containing imidazoline compositions represented by the formula:

wherein:

R is an aliphatic radical containing from 4 to

40 carbon atoms; Ri and R₂, which may be the same or different is of the group consisting of hydrogen and lower alkyl; R₃ is a organosilicone backbone chain which is represented by the formula:

wherein:

R₅, which can be the same or different, is selected from R₆,-R₄- and mixtures thereof, wherein R₆ is as herein defined, R₄ is alkylene, branched alkylene and alkylene with heteroatoms, with the proviso that at least one of R₅ is a -R₄- group. R₆ can be the same or different and is selected from alkyl, aryl and olefin;

R₇ and R_β, which can be the same or different, are selected from alkyl, aryl, capped or uncapped polyoxyalkylene, alkaryl, aralkylene and alkenyl; a is an integer from 0 to 50,000; b is an integer from 0 to 5,000; c is an integer from 0 to 100.

2. Acid salts of silicone-containing imidazolines represented by the following formula:

liffc-l

I wherein:

R is an aliphatic radical containing from 4 to

ll_g-

wherein:

R₅, which can be the same or different, is selected from Re,-R₄- and mixtures thereof, wherein R_e is as herein defined, R₄ is alkylene, branched alkylene and alkylene with heteroatoms, with the proviso that at least one of R₅ is a -R₄- group. R₆ can be the same or different and is selected from alkyl, aryl and olefin;

X is an anion group having a 1 to 3 valence; j is an integer from 1 to 3; and k is an integer from 1 to 3; with priviso that (k-j) must be zero or a positive interger.

3. A method for readily preparing silicone- containing imidazoline compositions having effective surface active, substantivity and lubrication properties which comprises reacting an organosilicone fluid or composition having at least one terminal, lateral or combination of terminal and lateral aminoethyl aminoalkyl functional group with up to about a stoichiometric amount of a long chain monocarboxylic acid or amide or ester derivative thereof having from 4 to 40 carbon atoms, at an elevated temperature for a time necessary to substantially react the moncarboxylic acid and provide for the cyclization of the reaction product.

4. The method for preparing silicone-containing imidazoline compositions as claimed in Claim 3, wherein about a stoichiometric amount of monocarboxylic acid is reacted with said silicone composition based on the amine functional groups on the silicone composition.

5. The silicone containing imidazoline compositions as claimed in Claim 1, wherein R is an aliphatic radical containing from about 8 to 22 carbon atoms.

6. The silicone containing imidazoline compositions as claimed in Claim 1, wherein R₄ is alkylene.

7. The silicone containing imidazoline compositions as claimed in Claim 1, wherein R₄ is branched alkylene.

8. The silicone containing imidazoline compositions as claimed in Claim 4, wherein R₄ is alkylene.

9. The silicone containing imidazoline compositions as claimed in Claim 4, wherein R₄ is branched alkylene.

10. The acid salts of silicone-containing imidazolines as claimed in Claim 2, wherein R is an aliphatic radical containing from about 8 to 22 carbon atoms.

11. The acid salts of silicone-containing imidazolines as claimed in Claim 2, wherein R₄ is alkylene.

12. The acid salts of silicone-containing imidazolines as claimed in Claim 2, wherein R₄ is branched alkylene.