United States Patent [i91 US005 166297A [iI] Patent Number: 5,166,297 O'Lenick, Jr. 1451 Date of Patent: Nov. 24, 1992 [54] SILICONE ESTER QUATERNARY cone copolyol halo ester intermediate which conforms COMPOUNDS to the following structure; [75] Inventor: Anthony J. O'Lenick, Jr., Lilburn, Ga. R"O-(CH2CH20),--(CH2CH(CH3)0)y-(CH2CH20),--(CH2)3 [73] Assignee: Siltech Inc., Norcross, Ga. [21] Appl. NO.: 822,752 0- Si [22] Filed: Jan. 21, 1992 CH3 Related U.S. Application Data [63] Continuation-in-part of Ser. No. 674,410, Mar. 25, 1991, Pat. No. 5,098,979. [5 11 Int. C1.5 .............................................C. 08G 77/06 U.S. C1. ........................................ 528/26; 528/15; 528/3 1; 525/474 Field of Search ....................... 528/26, 15, 31, 28; 427/387;424/70; 548/951 References Cited wherein R" is -C(O)-CH2-Cl; a is an integer from 0 to 200; b is an integer from 0 to 200; c is an integer from 1 to 200: U.S. PATENT DOCUMENTS R1 is selected from -(cH~),cH~ or phenyl; 4,185,087 1/1980 Morlino et al. ....................... 424/70 n is an integer from 0 to 10; 4,800,077 1/1989 O'Lenick, Jr. et al. .............. 424/70 R2 is -(CH2)3-(0CH2CH2)x-(0CH2CH(CH3- 5,070,168 12/1991 O'Lenick, Jr. ........................ 528/10 ))y-(OCH2CH2)z-OH; 5,073,619 12/1991 O'Lenick, Jr. ........................ 528/26 x, y and z are integers and are independently selected 5,098,979 3/1992 O'Lenick, Jr. ........................ 528/15 from 0 to 20, which is useful as an intermediate for Primary Examiner-John C. Bleutge reaction with amines to prepare silicone based qua- Assistant Examiner-M. W. Glass ternary compounds. The present invention is directed to a novel dimethi- 8 Claims, No Drawings SILICONE ESTER QUATERNARY COMPOUNDS RELATED APPLICATION This application is a continuation in part of copending 5 application Ser. No. 07/674,410, filed Mar. 25, 1991, now U.S. Pat. No. 5,098,979. BACKGROUND OF THE INVENTION (1) Field of Invention 10 The present invention relates to a series of novel cpaternHry silicone polymers, an intermediate useful in softening hair, and fiber and conditioning skin. Since the compounds of the present invention are high molecular weight silicone polymers, they have a high degree of oxidative stability, even at elevated temperatures. In addition, these compounds are non volatile and unlike many other traditional fatty quaternary compounds are non yellowing when applied to textile sub- 20 strates and are non irritating to eyes and skin. The compounds of the present invention are prepared by the reaction of chloracetic acid with a pendant hydroxyl group which is present on a silicone polymer, followed by the reaction of the halo-ester with a tertiary 25 amine to give a quaternary compound. In a preferred embodiment the hydroxy containing silicone polymer has been alkoxylated with ethylene oxide, propylene ,297 2 This is achieved by selection of the hydroxy silicone polymer used as a raw material. Application of the compounds of the invention can be from solvent, aqueous dispersion or solution, or applied neat in these process. It is anticipated that the effective conditioning concentration of the compound of this invention ranges from 0.1% to 25% by weight. The silicone polymers, suitable as raw materials, in a preferred embodiment, contain varying amounts of ethylene oxide, propylene oxide or mixtures thereof. The presence of the oxide in the silicone polymer results in compounds with an inverse cloud point. Inverse cloud point phenomenon are well known to those skilled in the art of nonionic surface active agents. The inverse cloud point is defined as a temperature above which the polymer has minimal solubility in water. If heat is applied to an aqueous solution of the nonionic at the inverse cloud point the material will become insoluble, and the solution will turn milky. It is at this point that the polymer has minimal water solubility. Since the product is no longer in solution at above this temperature, it is within this temperature range that the product has maximum substantivity to a fiber. The ability to use temperature to deposit a lubricant, antistat onto a fiber offers a great advantage in cost effectiveness of fiber treatment, and results in less product usage. (3) DESCRIPTION OF THE - - - ARTS AND oxide, or mixtuies thereof. ~he-abilityto regulate both PRACTICES the type of alk~leneo xide and amount of alk~leneo xide 30 Silicone oils (dimethylpolysiloxane) have been present in the silicone polymer results in a series of lcnown to be active at the surface of plastic, cellulosic products ranging in water/oil solubility. The technol- ,d synthetic fibers as well as paper. it^ the fact Ogy used produce the the present that they are lubricants that are stable to oxidation, their invention is very flexible and allows us to prepare per- high cost and lack of durability has made them cost formance tailored molecules for specific applications. 35 prohibitive in most application areas. silicone oils need (2) Object of the Invention to be emulsified prior to application. This requires high pressure equipment, surface active agents and generally It is the object of the present invention to provide a in a milky emulsion, ~ ~have expe~rienct.d l ~ i series of novel quaternary silicone polymers, which are stability problems both in terns of freeze thaw instabilsubstantive to skin and hair. This substantivity results in 4 ity and upon heating. This has resulted in minimal acsuperior softening, conditioning and antistatic proper- ceptance of them in commercial products. ties. The compounds of the present invention contain a The low eficiency of silicone oils is due to the fact fatty portion which is derived from a fatty amine. Incor- that the oil is very water insoluble. Emulsions are generporation of this type of group into the silicone molecule ally which contain silicone dispersed in miresults in increased solubility in many organic solvents. 45 celles. While this method of application is easier for This ability to marry fatty chemistry with silicone processing, much of the oil stays in the surfactant michemistry results in unexpected solubilities and surface celle and never gets deposited on the fiber. That which active properties. The compounds also contain varying does deposit on the fiber surface remains there by hy- - amounts of ethylene oxide and propylene oxide in the drophobic binding, not ionic bonding. Since the polydimolecule. This results in the ability to vary water soh- 50 methylsiloxane is not ionically bonded the effect is very bility and introduce an inverse cloud point into the transient. The product is removed with one washing. molecule. Inverse cloud point is well known to those Fatty quaternary compounds have been known as skilled in the surfactant art. It is generally found in softerners for many years. They have a much lower nonionic surface active agents. It is not found in quater- molecular weight than the silicone based compounds of nary compounds. The inverse cloud point is that tem- 55 the present invention. For this reason, they are much perature at which a soluble compound looses it's solu- more irritating to skin and eyes than those materials bility in water. Inverse cloud point, also called high based upon silicone polymers. cloud point, is thought to be associated with the ability Standard fatty quaternary compounds are prepared of the alkyleneoxide chain to hydrogen bond with the by quaternization of a tertiary amine with such agents as water. 60 benzyl chloride or di-methyl sulfate or di-ethyl sulfate It is another objective of the current invention to or methyl cloride. These materials are relatively inexprovide quaternary silicone polymers which have very pensive but offer several key disadvantages. These inlow irritation values when applied to skin and eyes. clude yellowing of fabrics, a tendency to build-up upon Irritation is a major problem with traditional fatty cati- repeated treatment, and variability in hand (i.e. softness onic materials. 65 and feel). Standard softeners used are selected from the Still another object of the present invention is to following classes: provide a series of quaternary silicone polymers which Class #I. Alkyl Imidazoline Quaternary Compounds have differing solubilities in water and organic solvents. made from the quaternization of an imidazoline made 5,166: 3 by reacting diethylenetriamine, and a high molecular weight fatty acid such as stearic acid. The standard quaternizating agents are di-ethyl sulfate, or methyl chloride, or di-methyl sulfate, or methyl chloride or benzyl chloride. 5 Class #2. Alkyl or dialkyl tertiary amines quaternized with benzyl chloride or di-ethyl sulfate or methyl chloride or di-methyl sulfate. Class #3. Quaternary compounds of ethoxylated, propoxylated or nonalkoxylated amido amines derived 10 from the reaction of a high molecular weight fatty acid like stearic acid and a polyamine like diethylene triamine. The standard quaternizating agents are di-ethyl sulfate or di-methyl sulfate or methyl chloride or benzyl THE INVENTION 1) Summary of the Invention The present invention relates to a series of novel quaternary silicone polymers. These polymers have a pendant quaternary nitrogen functional group present. The polymers by virtue of the pendent group deposit on hair, skin and fiber surfaces forming effective nonvolatile nonirritating, surface modifying finishes. The compounds of the present invention are excellent conditioners, antistats and non-yellowing, softeners. The compounds of this invention are represented by the following formula; chloride. l5 R-0-C(0)--CHI-R' Class #4. Amido amine salts derived from partially acid neutralized amines. wherein It is known that under certain catalytic conditions, R is epichlorohydrin reacts with certain alcohols to give an intermediate which can be used to react with tertiary amines to quaternary compounds. U.S. Pat. No. 30 3,445,440 to Susi (May 1969) and U.S. Pat. No. 3,517,045 to Susi (June 1970) teaches the use of chlorohydroxypropyl ether to alkylate specific tertiary amines which are the reaction product of a primary fatty amine and ethylene or propylene oxide. The com- 35 pounds are used as antistatic agents in polymeric compositions such as polyolefin. The antistatic properties of these compounds are achieved by the minimization of static charges on the polymer surface. These anti-static materials are incorporated into the polymer melt and 40 are effective by virtue of their insolubility in the molten polymer. The quaternary compounds migrate to the polymer surface and are effective antistatic agents. U.S. Pat. No. 4,144,122 to Emanuelsson issued Mar. 13, 1979 teaches that tallow alcohol and certain other 45 higher molecular weight non-guerbet alcohols and their alkoxylates can be reacted with epichlorohydrin, then subsequently with tertiary amines to give compounds suitable for paper debonding. U.S. Pat. No. 4,215,064 to Lindemann et a1 issued Jul. 50 29, 1980 teaches that phosphobetaines can be prepared by the reaction of a phosphate or phosphite salt with epichlorohydrin under aqueous conditions. U.S. Pat. No. 4,283,541 to O'Lenick, et al, issued Aug. 11, 1981 teaches the process for the preparation of the phos- 55 phobetaines described in Lindemann (U.S. Pat. No. 4,215,064). None of these patents teach the compounds of the present invention. U.S. Pat. No. 4.800.077 issued Jan. 1989 to O'Lenick , , teaches guerbet alcohol quaternary compounds can be 60 prepared by reacting epichlorohydrin with guerbet alcohols then subsequently reacting the intermediate with arnines. None of the above incorporate silicone into the quaternary compound. Consequently, the unique softening 65 and substantivity properties achieved using the compounds of the present invention are not realized with the above technologies. a is an integer from 0 to 200; b is an integer from 0 to 200; c is an integer from 1 to 200; Rl is selected from -(CH2),CH3 or phenyl; n is an integer from 0 to 10; R2 is -(CH~)~-(OCH~CH~)X-(OCH~CH(CH~- ))y-(OCH2CH2)z-OH; x, y and z are integers and are independently selected from 0 to 20; R' is selected from R3, R4, and R5 are each independently alkyl having from 1 to 20 carbon atoms; R6 is alkyl having from 6 to 20 carbon atoms; R7 and R8 are independently selected from methyl and ethyl; or wherein R9 is alkyl having from 6 to 20 carbon atoms; v is an integer from 1 to 5. The products of the present invention are prepared by reaction of a hydroxyl containing silicone polymer with a halo acid, most commonly chloracetic acid resulting in a halo ester which in a subsequent step is reacted with an amine to give the desired quaternary compounds which can be used to make the products of compounds. this invention. CH2=CH-CH2-O-(CH2-CH24)~-(CH2-~~(~~3)-0)Y-(~~2-~~2-0)z-~ Molecular Designation x Y z Weight DIMETHICONE COPOLYOL HALO-ESTER PREPARATION OF INTERMEDIATES INTERMEDIATE Silicone intermediates of the type used to make the The intermediate silicone copolyol halo-ester is an compounds of this invention are well known to those additional aspect of the present invention. It is useful as skilled in the art. International Publication (Silicone an intermediate in the preparation of the compounds of 20 Alkylene Oxide Copolymers As Foam Control Agents) the present invention. WO 86/0541 by Paul Austin Sep. 25, 1986) p. 16 (exam- R"O-(CH~CH~O)~-(CH~CH(CH~)O)~-(CH~CH~O)X-(CH~)~ CH3 H20 and C H 3C-I H~3 O - ~ O - [ ~ O ! 7 T O - ~ i - C HC3H 3 C1 H3 wherein R" is -C(O)-CH2-Cl; a is an integer from 0 to 200: ples 1 to 6) is one of many references which teaches how to make the following intermediates. b is an integer from 0 to 200'; c is an integer from 1 to 200; 40 HYDROSILATION OF INTERMEDIATES R' is selected from -(CH2),CH3 or phenyl; Silanic Hydrogen Containing Compounds n is an integer from 0 to 10; R2 is -(CH2)3-(OCH2CH2)x-(OCHzCH(CH3- ))y-(OCH2CH2)z-OH; CH3 CH3 CH3 CH3 45 I I I I x, y and z are integers and are independently selected CH~-si-0-si-0-si-0-si-CH~ from 0 to 20. CI H3 CI H3 H1 CIH 3 The compounds of the related invention of which this is a continuation in part are based upon the reaction of M I D I D * I M epichlorohydrin with a dimethicone copolyol. We have unecxpectantly found that the esterification reaction of Group Desimations the dimethicone copolyol is easier and results in im- Average Equivalent Austin Group Molecular Molecular proved purity. The ester linkage also results in some- ~~~~~l~ ~~~~~l~ ~ ~ Weiight ~Weight ~ ~ ~ what improved solubility of the quat in polar solvents. 1 1 MD20 D'3.2 M 1,850 551 DIMETHICONE COPOLYOL REACTANTS 55 : 4 MDlmD'5 M 24,158 4,831 6 MD20 D.10 M 2,258 225 One method of ~.r e.~ a r-i tnhge reactive hvdroxvl containing silicone polymer is to react silanic hydrogen containing polymer with ally1 alcohol or ally1 alcohol HYDROSILATION COMPOUNDS alkoxylate monomer. Procedures this reaction are well 60 The hydrosilation reaction used to make the known those '' the art. Pat. No. pounds of this invention are well known to those skilled 4,083,856 describe suitable processes. in the art. Reference; International Publication (Silicone EXAMPLES Vinvl Intermediate Com~ounds Alkylene Oxide CopoIymers As Foam Control- ~ ~ e n t s ) WO 86/0541 by Paul Austin (Sep. 25, 1986) p.19. LC 0 J Compounds of this class are prepared by alkoxylation EXAMPLE 4 of allyl alcohol using methods well known to those To a 22 liter three necked round bottom flask fitted skilled in the art. The following are some of the many with a mechanical agitator, thermometer with a Thermo- watch temperature regulator, nitrogen sparge tube vented reflux condenser and heating mantle is added 189.0 grams of Vinyl Intermediate Example #A. Next add 225 grams of Silanic Hydrogen Containing Compound Example #3 and 3,000 grams of toluene. Heat to 5 115 C. to remove azeotropically remove any water and 200 ml of toluene. The temperature is reduced to 85 C. and 3.5 ml of 3% H2PtC16 in ethanol is added. Light to then excluded from the flask by covering it with a black cloth. An exotherm is noted to about 95 C., while the lo contents are stirred for about 2 hours. During this time Grams of Grams of Calalyst Dimethicone Copolyol Chloroacetic Stannous Example Example # Grams Acid SnO Oxylate 1 1 4 740.0 94.0 4 0 12 5 7009.0 94.0 2 2 13 6 943.0 94.0 0 4 14 7 608.0 94.0 4 0 I5 8 7771.0 94.0 2 2 16 9 1105.0 94.0 0 4 silanic hydrogen concentration drops to nil. cool to 65 17 10 202 I .o 94.0 4 o C. and slowlv add 60 a of sodium bicarbonate. allow to mix overnight and filter through a 4 micron pad. Distill off any toluene at 100 C. and 1 torr. l5 QUATERNARY REACTION SEQUENCE EXAMPLE 5-10 All amine reactants are commercially available from Tomah Products Division of Exxon Chemicals Milton The above procedure is repeated, only this time replacing both the silanic hydrogen compound #3 with 20 Wi. the specified number of grams of the specified silanic hydrogen compound and the vinyl intermediate exam- ple A with the specified number of grams of the speci- /R3 R ~ O C ( 0 ) C H 2 ~ C I + N-R4 + tied vinyl intermediate. 25 'R5 Silanic CRR~ Vinyl Intermediate Hydrogen Compound Examole Examole Grams Examole Grams PREPARATION OF THE SILICONE HYDROXYPROPYLETHER HALIDE Reaction Sequence R-OH + HO-C(0)-CH2CI R contains the silicone portion of the molecule The following examples further illustrate the objects and advantages of this invention, though it should be understood that the various reactants and amounts thereof, reaction conditions, and other details are merely illustrative and should not be construed to unduly limit this invention. AMINE REACTANT GROUP 1 The reactants are tertiary amines conforming to the following structure; R contains the silicone portion of the molecule. Example Number R3 R4 R S 50 The following examples further illustrate the objects 18 C10H21 CH3 CH3 19 and advantages of this invention, though it should be C1zH2s CH3 CH3 20 Ci4Hz9 CH3 CH3 understood that the various reactants and amounts 2 I c1c.H~ CH3 CH3 thereof. reaction conditions. and other details are 22 CIRHJ~ CH3 CH1 merely illustrative and should not be construed to un- 55 duly limit this invention. General Procedure 26 C14H29 CZOQI CH3 27 C16H33 c10Hz1 CH3 Place the indicated amount of the dimethicone copo- 28 C18H37 CIZH~S CH3 lyol produced by the example shown in a suitable ves- 60 29 C2&1 Ci4Hz9 CH3 sel. Add the desired amount of catalyst as shown under 30 W I ~ W I ~ -13 good agitation and a nitrogen sparge. The specified 3 I C2H5 CH3 C2Hs amount of monochloracetic acid is added. A molar 32 c1oH21 c10H21 c10Hz1 excess of 0.1 to 0.5 of chloracetic acid is added. The temperature is held between 160-200 degrees C. for two 65 to six hours. Reaction progress is monitored by acid AMINE REACTANT GROUP 2 value analysis and at the end of the reaction reaches The reactants are amido tertiary amines conforming theoretical for the mole ratio used. to the following structure; R7 Amine Reactants Silicone Reactants Water 6 I Example Example Grams Example Grams Grams R-c(o)N(H)-(CH~)~-N-R~ 5 63 21 253.0 14 702.0 955.0 Example Number R6 R7 R8 64 22 279.0 15 7,865.0 8,144.0 65 23 305.0 16 1,119.0 1,424.0 AMINE REACTANT GROUP 3 87 45 4,928.0 17 3,155.0 8,083.0 25 88 46 300.0 11 834.0 1,134.0 The reactants are imidazoline compounds conform- 89 47 328.0 12 7,103.0 7,431.0 90 48 1,782.0 13 ing to the following structure; 9 I 49 1,370.0 1143 1,700327..00 22,,801792..00 92 50 1,103.0 15 7,865.0 8,968.0 93 51 1,131.0 16 1,119.0 2,250.0 (CH212 - N 30 94 52 184.0 17 3,155.0 3,339.0 I 11 95 53 212.0 11 834.0 1,046.0 N--c-R9 96 54 240.0 12 7,103.0 7,343.0 I 97 55 268.0 13 1,037.0 1,305.0 CHzCHzOH 98 56 296.0 14 702.0 998.0 99 57 324.0 15 7,865.0 8,189.0 Example Number R9 58 352.0 16 1,119.0 1,471.0 35 :: 52 CsHl I 59 380.0 17 3,155.0 3,535.0 53 C7His 54 C9H19 55 CllH23 56 C13H27 APPLICATIONS EVALUATION 57 CISH~I 40 Applications of the Compounds of The Invention 58 C17H35 59 C19H39 Compounds of this invention were compared to standard compounds commercially available using AATCC Test Method 117-1979. The color fastness heat test uses GENERAL REACTION PROCEDURE a 400 F. (205 F.) hot iron which is applied for 60 and 180 The products of the present invention are generally 45 seconds.~hec olor is rated on a 1 5b asis for yellow- ~. r e. ~ a r eind aaueous solution or dis~ersion.T he Dre- ness, (5 being the most yellow). ferred concentration is about 50% solids. Additionally, alcohols such as methanol, ethanol, isopropanol, glycols such as ethylene glycol, propylene glycol, polypropyl- 50 ene glycol, polyethylenegylcol, hexylene glycol, and cyclomethicone can be added to improve clarity if desired. To a suitable flask, equipped with a thermometer and agitator is added the specified amount of water. Next 55 add the specified amount of the type of silicone reactant. Heat to 50 C. Next add the specified amount of the specified amine under good agitation. THe reaction mass is heated to 85-95 C. and held from between 5 and Compound CAS Number

Yellowness Stearyl Imidazoline Quat 68122-86-1 4 (Alkaquat ST) Distearyl Quat 61789-81-9 4 Tallow Amido Quat 65098-88-6 5 (Alkaquat DAET-90) Stearyl Amido Propyl Salt 68308-45-2 4 Example 63 1 Examole 92 2 WET COMB OUT TEST l5 hours. The progress is monitored % 60 A laboratory test is conducted to screen the wet inorganic chloride, which approaches 98% of theoreti- comb Droverties of a member of the famcal. ily of novel compounds. Hair swatches are purchased from a supply of human hair from the same head. Each Reactants silicone R~~~~~~~ water test swatch contains 7 grams of hair and is 11 inches in ~~~~~l~ ~~~~~l~ G~~~~ ~~~~~l~ G~~~~ G~~~~ 65 length. The hair is tied tightly 1 inch from one end with 60 18 185.0 11 834.0 1,019,0 string. THe swatch is pre-cleaned with a 3% solution of 61 19 201.0 12 7,103.0 ammonium lauryl sulfate. Subsequently, the swatch is 62 20 227.0 13 1,037.0 1,264.0 washed under running tap water. The hair is then squeezed out and while still damp dipped into a 200 ml R"O-(CHzCH20);-(CH2CH(CH3)O),--(CH2CH2O),--(CH2)3 solution of 0.29% active auaternarv. Another rinse is - -. ,- ,- 1 - made, then the swatch is blotted dry. The swatch is then treated by holdiqg the hair swatch, combing the hair as rapidly as possible while alternating the side of the - L J o L J b L CH3 swatch combed. The time needed to get one smooth 10 free stroke without tangling is recorded. Typical results for the standard quaternary compounds used in hair conditioning (stearyldimethylbenzyl ammonium chlo- wherein; 15 R" is -C(O)-CH2-CI; ride) range frop 12-14 seconds. a is an integer from 0 to 200; b is an integer from 0 to 200, c is an integer from 1 to 200, Xinse Conditioner (Wet Comb Out Test) R1 is -(cH~),cH~ or phenyl; 20 n is an integer from 0 to 10; PrMuct Time in Seconds R2 is -(CH2)3-(OCH2CH2)x-(OCH2CH(CH3- ))y-(OCH2CH2)z-OH; Product Example 60 11 x, y and z are integers which independently range Product Example 92 13 from 0 to 20. Stearyldimethylbenryl 12 25 2. A compound of claim 1 wherein x is 3, y is 0, and z is 0. ammonium chloride 3. A compound of claim 1 wherein x is 9, y is 27, and z is 3. 4. A compound of claim 1 wherein x is 11, y is 3, and As can be seen, the compounds of the invention give 30 is 0. significant conditioning properties to hair, and coupled 5. A wherein is O, y is 0* and z is 0. with their mild nature with regard to skin and eyes, 6. A compound of claim 1 wherein x is 20, y is 20, and makes it a prime candidate for cosmetic applications. is 20. 35 7. A compound of claim 1 wherein x is 20, y is 0, and I claim: z is 0. 1. A dimethicone copolyol halo ester intermediate 8. A compound of claim 1 wherein x is 10, y is 10, and z is 10. which conforms to the following strupure; 40