FR2549843A1 - Catalyst based on substituted piperazine for the production of polyurethanes - Google Patents

Abstract

Catalytic composition comprising a substance which has the general formula: where R1 is an alkyl group containing 1 to 3 carbon atoms and R2 is a group chosen from -H, -CH3 and -CH2CH3. The catalytic composition is odourless and excellent in the reaction forming urethanes for the production of polyurethanes.

Description

 The subject of the present invention is new copolymers of acrylic or siethacrylic acid, of an alkyl acrylate or methacrylate and of an allylic derivative, and their use in cosmetics, in particular in compositions for the hair and the skin.

 These new polymers make it possible to provide properties which are particularly sought after in cosmetics.

 In the compositions for the hair, they make it possible to impart more volume and hold without the occurrence of non-cosmetic phenomena such as dusting, sticking or the shiny appearance of the hair.

 They also facilitate the disentangling of the hair and increase their shine.

 When these polymers are present in compositions for the skin, they give it a smoother and softer to the touch appearance while improving the texture of the compositions.

dans lesquelles:
R1 et R2 représentent un atome dthydrogene ou un radical méthyle,
R3 représente un radical alkyle, linéaire ou ramifié, ayant de 1 à 10 atomes de carbone,
R4 représente -OH, -NHCONH2, ou -OCOR5, R5 représentant un radical alkyle, linéaire ou ramifié, ayant de 1 à 5 atomes de carbone,
x représentant de 40 à 90% en poids,
y représentant de 8 à 50% en poids et,
z représentant de 2 à 25% en poids.The subject of the present invention is, as a new industrial product, copolymers of acrylic or methacrylic acid, of an alkyl acrylate or methacrylate and of an allylic derivative, these copolymers essentially consisting of repeating units of formulas following:

in which:
R1 and R2 represent a hydrogen atom or a methyl radical,
R3 represents an alkyl radical, linear or branched, having from 1 to 10 carbon atoms,
R4 represents -OH, -NHCONH2, or -OCOR5, R5 representing an alkyl radical, linear or branched, having from 1 to 5 carbon atoms,
x representing from 40 to 90% by weight,
representing from 8 to 50% by weight and,
z representing from 2 to 25% by weight.

 The copolymers according to the invention as defined above have a molecular weight of between 5,000 and 200,000 by weight and preferably between 10,000 and 50,000 measured by the light scattering method.

 The repeating units of formula (la) are derived from acrylic or methacrylic acid.

 The repeating units of formula (lob) are derived from at least one lower alkyl acrylate or methacrylate, in particular from methyl, ethyl, propyl, isopropyl, butyl, hexyl acrylate or methacrylate, 2-ethyl hexyl or octyl.

 The repeating units of formula (1c) are derived from allyl alcohol, allyl acetate, allyl propionate or allyl urea.

According to a preferred embodiment, the copolymers according to the invention are those in which:
- the repeating units of formula (la) represent from 50 to 85%
in weight,
- the repeating units of formula (lb) represent from 10 to 35%
in weight,
- the repeating units of formula (Ic) represent from 5 to 15%
in weight.

Among the polymers according to the invention, mention may be made of those comprising derived repeating units:
- acrylic acid, methyl acrylate and allyl alcohol,
- methacrylic acid, methyl methacrylate and alcohol
allylic,
- acrylic acid, ethyl acrylate and allyl alcohol,
- methacrylic acid, ethyl methacrylate and alcohol
allylic,
- acrylic acid, isopropyl acrylate and allyl alcohol,
- methacrylic acid, ethyl methacrylate and acetate
allyl,
- acrylic acid, ethyl acrylate and allyl-urea.

 The free acid functions of the copolymers according to the invention can, depending on their use, be totally or partially neutralized using an inorganic or organic base in order to improve their solubility.

 Among the organic bases, mention may be made of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, morpholine and also certain amino alcohols such as 2-amino-2-methyl-propanol-1 and 2-amino-methyl- 2 propanediol-1,3.

 According to the present invention, the copolymers can advantageously be neutralized with one of these bases in an amount equal to approximately 10 to 150% and preferably from 50 to 120% of the amount corresponding to the stoichiometric neutralization.

 The copolymers according to the invention can be obtained according to conventional methods of polymerization, that is to say either in solution in a solvent, in mass or optionally in emulsion.

 The solution polymerization process is generally carried out in an inert solvent such as, for example, ethyl acetate.

 The polymerization initiators which can be used in this polymerization process are preferably azobisisobutyronitrile, peresters, percarbonates or redox systems. The polymerization initiator can be used either alone or as a mixture.

 The amount of the polymerization initiator is generally between 0.1 and 6% by weight relative to the total weight of the monomers to be copolymerized.

 The polymerization reaction is preferably carried out at a temperature between 45 and 1000C and more particularly at the reflux temperature of the reaction mixture.

 The reaction time is preferably between 2 and 24 hours.

 Another particularly advantageous process can be used when it is desired to obtain polymers in which the radicals R1 and R2 are identical, that is to say represent either a hydrogen atom or a methyl radical.

 In fact, in this particular case, the polymerization reaction can be carried out in solution in an alcohol capable of partially esterifying the carboxylic acid functions of the starting acrylic or methacrylic acid.

 This process is very particularly preferred when the radical R3 of the repeating units of formula (lb) represents a lower alkyl having from 1 to 3 carbon atoms.

 According to this method, the polymerization reaction is carried out starting from acrylic or methacrylic acid and at least one monomer capable of leading to repeating units of formula (Ic).

 During the polymerization reaction, a partial esterification of the acid functions of acrylic or methacrylic acid takes place with lower aliphatic alcohol used as solvent.

 According to this process, it is thus possible to esterify up to about 20% of the acid functions of the starting acrylic or methacrylic acid.

In this process, the polymerization initiators are those commonly used such as organic compounds of the peroxide, perester or percarbonate type, but preferably azobisisobutyronitrile or systems
Redax.

 By playing on certain parameters of the operating conditions it is possible to adjust the molecular weights of the copolymers which it is desired to obtain.

 Generally, these parameters are firstly the amount of the polymerization initiator and secondly the concentration of the monomers in the reaction solvent.

 According to a preferred embodiment when it is desired to obtain polymers of molecular weight between 10,000 and 50,000, the method consists in copolymerizing acrylic or methacrylic acid and the monomer leading to repeating units of formula (lc) in solution in an alcohol aliphatic capable of partially esterifying the repeating units of formula (la), in the presence of hydrogen peroxide and a factor accelerating the formation of free radicals. This accelerating factor can be UV irradiation or an inorganic or organic compound endowed with reducing properties.

Among the latter compounds, mention may in particular be made of ferrous chloride, cuprous chloride, ascorbic acid, etc.

 If it is desired to obtain a higher rate of esterification of the repeating units of formula (la), the copolymerization reaction must then be carried out in the presence of a strong acid such as for example sulfuric acid or paratoluene acid sulfonic.

 The present invention also relates to new cosmetic compositions containing the polymers according to the invention as defined above, either as the main active ingredient, or as an additive.

 These cosmetic compositions can be aqueous solutions, hydroalcoholic solutions (the alcohol being in particular a lower alcohol such as ethanol or isopropanol), emulsions, creams, milks, gels and can be packaged as an aerosol. containing a propellant such as for example nitrogen, nitrous oxide or fluorochlorinated hydrocarbons of the "reaction" type.

 In general, the polymer concentration in the cosmetic compositions according to the invention is between 0.1 and 30% by weight, preferably between 0.5 and 10%.

 In the cosmetic compositions for hair, the polymers according to the invention facilitate the obtaining of swelling hairstyles and confer on dry hair qualities of nervousness, a shiny appearance and an ease of disentangling.

 The polymers can be present in the cosmetic compositions for hair according to the invention either as an additive or as a main active ingredient in styling lotions, treatment compositions, styling lotions, creams or gels. styling, either as an additive in shampoo compositions, styling, perm, dye, bleaching, restructuring lotion, antiseborrhoeic treatment lotion or hair spray.

 Lotions are aqueous or hydroalcoholic solutions whose pH is close to neutral and can vary between around 5 and 8.

 The treating creams are produced with a support formulated based on soap or fatty alcohol in the presence of emulsifier. Soaps can be made from natural or synthetic C12-C20 fatty acids (such as lauric acid, myristic acid, palmitic acid, oleic acid, ricinoleic acid, stearic acid, isostearic acid and their mixture) at concentrations between 10 and 30% and basifying agents (such as soda, potash, ammonia, monoethanolamine, triethanolamine and their mixture).

 The treating gels contain thickening agents such as sodium alginate or gum arabic or cellulose derivatives in the presence or absence of solvent. The thickener concentration can vary from 0.5 to 30% and preferably from 0.5 to 15% by weight.

 The solvents used can be lower aliphatic alcohols, glycols and their ethers, the concentration of these solvents varying between 2 and 20Z.

 According to a preferred form of the invention, the compositions are in the form of shampoos, characterized in that they contain at least one polymer according to the invention as defined above and at least one cationic, nonionic detergent , anionic, amphoteric or a mixture thereof.

 These compositions in the form of shampoos can also contain various adjuvants, such as, for example, perfumes, dyes, preservatives, thickening agents, foam stabilizing agents, softening agents. In these shampoos the detergent concentration is generally between 3 and 50% by weight and the polymer concentration preferably between 0.1 and 4% by weight.

 The compositions according to the invention can also be styling lotions or so-called brushing lotions, characterized in that they comprise at least one polymer as defined above in aqueous or hydroalcoholic solution.

 The compositions according to the invention can also be applied before or after shampooing or even between two shampoos by acting as formulations for the treatment of hair.

 They may also contain at least one cosmetic resin with an anionic or cationic nature, the cosmetic resins which can be used in such lotions are known and described in cosmetology works.

 The compositions according to the invention can also be hair dye compositions, characterized in that they contain at least one polymer as defined above and at least one hair coloring agent and a support.

 The dye compositions are preferably gelling liquids; they contain, in addition to the polymer, the dye or dye precursor, either polyoxyethylene or polyglycerolated nonionic derivatives and solvents, or soaps of liquid fatty acids such as those of oleic or isostearic acid and solvents. Soaps are soda, potash, ammonium, or mono-, di- or triethanolamine soaps.

 The compositions according to the invention intended for the treatment of the skin are preferably in the form of creams, milks, emulsions, gels or aqueous or hydroalcoholic solutions.

 The polymer concentration in these compositions can vary between 0.1 and 10% by weight and preferably between 0.25 and 5%. The adjuvants generally present in these compositions are, for example, perfumes, dyes, preserving agents, thickening agents, sequestering agents, emulsifying agents, sunscreens, etc.

 These compositions give the skin a softness pleasant to the touch and make the skin smooth.

 These compositions constitute in particular treating creams or lotions for the hands or the face, sunscreen creams, tinted creams, cleansing milks, foaming bath liquids, aftershave lotions, toilet waters, foams to shave, pencils for eyeshadows, colored or non-colored sticks in particular for the lips, for makeup or for personal hygiene or also deodorant compositions.

 The polymers as defined above can be present in the compositions for the treatment of the skin either as an additive or as a main active ingredient.

 These skin compositions can also contain various active substances such as sunscreen agents, healing agents, etc., and can be in the form of aqueous or hydroalcoholic solutions, creams, milks, etc.

 In order to better understand the invention, we will now give by way of illustration and without any limiting character, several examples of preparation of the copolymers according to the invention as well as several examples of cosmetic compositions containing them.

EXAMPLE 1 Preparation of a polymer containing 68% acrylic acid / 8% ethyl acrylate / 12; allyl alcohol (the remainder consisting of repeating units of undetermined structures).

 320 g of acrylic acid, 800 ml of ethanol, 80 g of liquid are introduced into a 2-liter reactor fitted with a stirrer or a cooler with a nitrogen inlet and a tube for the introduction of the reactants. 'allyl alcohol, and 60g of a 30% solution of hydrogen peroxide.

 The mixture is then brought to 800 C. When the temperature is obtained, the heating is then stopped and a dispersion of 400 mg of cuprous chlorur in 400 ml of water is introduced. As soon as the first drops of the dispersion are added, the temperature of the reaction medium rises to 830C and a strong reflux of the ethanol is then observed. The addition of the dispersion is then adjusted so that it is completed in 40 minutes, possibly heating, in order to maintain the reflux of the solvent.

 The polymerization reaction is then continued at reflux of the solvent for approximately 2 h 30 min.

 After cooling, the reaction mixture is concentrated by half on a rotary evaporator then poured into trays and dried in an oven at 500C at 26.102Pa.

Analyzes:
Acid number: 532
Viscosity of a 50% solution of the polymer in water at 250C: 217cPo.

 The ester and alcohol levels are determined by proton NMR.

EXAMPLE 2 Preparation of the polymer containing 64% of acrylic acid 8% of ethyl acrylate / 12X of allyl alcohol (the remainder consisting of repeating units of undetermined structures).

 320 g of acrylic acid, 800 ml of ethanol, 80 g of liquid are introduced into a 2 liter reactor fitted with a stirrer, a condenser, a nitrogen inlet and a tube for introducing the reactants. allyl alcohol, 60g of a 30% solution of hydrogen peroxide.

 The mixture is then brought to a temperature of 800 C. When this temperature is reached, the heating is suppressed and a sprite of 20 g of ascorbic acid in 40 ml of water is introduced.

 As soon as the first drops of the solution are added, the temperature of the reaction medium rises to 860C and a strong reflux of the ethanol is observed.

The addition of the solution is then regulated so that it is complete after 40 minutes, possibly heating so as to maintain the reflux of the solvent. The polymerization reaction is then continued at reflux of the solvent for approximately 2 h 30 min.

 After cooling, the reaction mixture is diluted with 1500 g of ethyl cellosolve, then concentrated to 1200 g to completely remove the skin, the ethanol and the residual allylic alcohol. The polymer solution is then poured into 15 liters of an acetone-petroleum ether mixture (60/40) with vigorous stirring. The recovered polymer is then dried at 500C under 26.lO2Pa.

Analyzes:
Acid number: 497
Viscosity of a 50% polymer solution in water at 25 C: 740cPo.

 The ester and alcohol levels are determined by proton NMR.

EXAMPLE 3 Preparation of a polymer containing 62% acrylic acid / 8% methyl acrylate / 13% allyl acetate (the remainder consisting of repeating units of undetermined structures).

 297.5 g of acrylic acid, 127.5 g of allyl acetate are introduced into a 4-liter reactor fitted with a quartz dip tube containing a 2000 W WQ 2020 emitting lamp from the company ORIGINAL HANAU (RFA). 2518g of methanol and 40g of a 30% solution of hydrogen peroxide. This solution, kept under stirring and under nitrogen, is then irradiated for 2 hours while maintaining its temperature at 500 C.

 Analysis of the reaction mixture shows that after this time, the consumption of acrylic acid is complete.

 The reaction mixture is then concentrated to 1000 g and then poured into 20 liters of sulfuric ether with vigorous stirring. The polymer is then dried in an oven at 500C.

Analyzes
Acid number: 487
Viscosity of a 50% solution in water at 250C: 265cPo.

 The methyl ester level was determined by proton NMR.

EXAMPLE 4 Preparation of a polymer containing 70% of acrylic acid / 9Z of methyl acrylate / 20X of N-allyl-urea (the remainder consisting of repeating units of undetermined structures).

 In the same type of reactor and according to a process analogous to that described in Example 3, 160 g of acrylic acid, 40 g of N-allyl-urea, 2240 g of methanol and 40 g of a 30% peroxide solution are introduced. hydrogen.

 The polymerization reaction is then continued for 4 h 30 min at 500 ° C., the time necessary for the total consumption of acrylic acid.

 The reaction mixture is then concentrated to 1000 g and then poured into 20 liters of sulfuric ether with vigorous stirring. The polymer is then dried in a vacuum oven.

Analyzes
Acid number: 547
Viscosity of a 50% solution in water at 25 C: 97cPo.

 The level of methyl ester was determined by proton NMR.

 The level of N-allyl-urea was deduced from the percentage of nitrogen found by microanalysis: 5.72%.

EXAMPLE 5 Preparation of a polymer containing 67% acrylic acid / 9% methyl acrylate / 12% allyl alcohol (the remainder consisting of repeating units of undetermined structures).

 In the same type of reactor and according to a process analogous to that of Example 3, 340 g of acrylic acid, 85 g of allyl alcohol, 2524 g of methanol and 40 g of a 30% solution of hydrogen peroxide are introduced. .

 The polymerization reaction is continued for 2 hours at 500C, time necessary for the total consumption of acrylic acid.

 The reaction mixture is then concentrated to 1000 g and then poured into 20 liters of sulfuric ether with vigorous stirring. The polymer is then dried in an oven at 500C.

Analyzes:
Acid number: 519
Viscosity of a 50% solution in water at 250C: 303cPo.

 The methyl ester Laux was determined by proton NMR.

EXAMPLE 6 Preparation of a polymer containing 56% acrylic acid / 17% ethyl acrylate / J1% allyl alcohol (the remainder consisting of repeating units of undetermined structures).

 160g of acrylic acid, 40g of allyl alcohol, 600g of ethanol and 4g of isobutyronitrile azobis are introduced into a 3-liter reactor fitted with a nitrogen inlet. The reaction mixture is brought to reflux of ethanol for 5 hours. Then added 1 g of azobisisobutyronitrile dissolved in 10 g of ethanol then 100 g of heptane. 300 g of the solvent are then distilled in order to entrain the allyl alcohol which has not polymerized.

 The reaction mixture then contains less than 2% of residual acrylic acid and the polymer is obtained by pouring the crude solution into 10 liters of sulfuric ether with stirring. The polymer is then dried in an oven at 500C.

Analyzes:
Acid number: 435
Viscosity of a 50% solution in water at 250C: 1670cPo.

 The content of ethyl ester was determined by proton RNLN.

EX 1z.ES OF COMPOSITIONS
EXAMPLE A
A styling lotion is prepared by mixing the following ingredients: - polymer prepared according to example 1 ......... 2g
- soda qs pH 7 - water qs .......................... qs 100g
In this example, the polymer of example 1 can be replaced by that of example 5.

EXAMPLE B
A composition is prepared in the form of a shampoo by mixing the following ingredients:
- triethanolamine lauryl sulfate 10g polymer prepared according to Example 2 ........... 2 lg
- soda qs pH 7
- water qs ......................... ..... 100g
In this example, the polymer of Example 2 can be replaced by that of Example 6.

EXAMPLE C
A composition is prepared in the form of a shampoo by mixing the following ingredients:
- lauric alcohol polyglycerolated to 4 moles of glycerol ...
- polymer prepared according to Example 1 ........... 1 2g
- soda qs pH 7 - water qs .................................. qs 100g
In this example, the polymer of Example 1 can be replaced by that of Example 3.

EXAMPLE D
A beauty mask is prepared by mixing the following ingredients: - polymer prepared according to Example 2 ........... 2 15g
- 2-amino-2-methyl-propanol-1 qs pH 7
- propylene glycol 5g
- 4-hydroxy methyl benzoate ............ methyl 0.2g
- ethanol ................................. ethanol 15g
- kaolin .................................. kaolin 10g
- titanium dioxide ............................... titanium 0.5g
- triethanolamine lauryl sulfate 0.6g - perfume .................................. perfume 0.15g
- sterile demineralized water qs 100g
In this example, the polymer of Example 2 can be replaced by that of Example 4.

Claims (18)

 1. Copolymer of acrylic or methacrylic acid, an alkyl acrylate or methacrylate and an allylic derivative, characterized in that it essentially consists of repeating units corresponding to the following formulas:

 in which:  R1 and R2 represent a hydrogen atom or a methyl radical,  R3 represents an allyl radical, linear or branched, having from 1 to 10 carbon atoms,  R4 represents -OH, -NHCONH2, or -OCOR5, R5 representing an allyl radical, linear or branched, having from 1 to 5 carbon atoms,  x representing from 40 to 90% by weight,  representing from 8 to 50% by weight and,  z representing from 2 to 25% by weight.  2. Copolymer according to claim 1, characterized in that it has a molecular weight between 5,000 and 200,000 and preferably between 10,000 and 50,000 measured by the light scattering method.  3. Copolymer according to any one of the preceding claims, characterized in that the repeating units of formula (Ib) derive from a lower alkyl acrylate or methacrylate taken from the group consisting of methyl acrylate or methacrylate , ethyl, propyl, isopropyl, butyl, 2-ethylhexyl or octyl hydroxy.  4. Copolymer according to any one of claims 1 and 2, characterized in that the repeating units of formula (tic) derive from allyl alcohol, allyl acetate, allyl propionate or allyl- urea.  5. Copolymer according to any one of the preceding claims; characterized in that the repeating units of formula (la) represent from 50 to 85% by weight, the repeating units of formula (lb) represent from 10 to 35% by weight and the repeating units of formula (1c) represent from 5 at 15% by weight.  6. Copolymer according to any one of the preceding claims, characterized in that it consists of derived repeating units:  - acrylic acid, methyl acrylate and allyl alcohol,  - methacrylic acid, methyl methacrylate and alcohol  allylic,  - acrylic acid, ethyl acrylate and allyl alcohol,  - methacrylic acid, ethyl methacrylate and alcohol  allylic,  - acrylic acid, isopropyl acrylate and allyl alcohol,  - methacrylic acid, ethyl methacrylate and acetate  allyl,  - acrylic acid, ethyl acrylate and allyl-urea.  7. Copolymer according to any one of the preceding claims, characterized in that the free acid functions are neutralized, totally or partially, using a mineral or organic base.  8. Copolymer according to claim 7, characterized in that the organic base is taken from the group consisting of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, morpholine, 2-amino-2-methylpropanol-1 and 2-amino-2-methylpropanediol-1,3.  9. Cosmetic composition, characterized in that it contains at least one copolymer according to any one of claims 1 to 8, at a concentration between 0.1 and 30% by weight, preferably between 0.5 and 10 %.  10. Composition according to claim 9, characterized in that it is in the form of an aqueous or hydroalcoholic solution of an alcohol such as methanol or isopropanol.  11. Composition according to claim 9 or 10, characterized in that it has a pH of between 5 and 8.  12. Composition according to any one of claims 9 to 11, characterized in that it is in the form of a shampoo and also contains a cationic, non-ionic, anionic, amphoteric detergent or a mixture thereof.  13. Composition according to claim 12, characterized in that the detergent concentration is between 3 and 50% by weight.  14. Composition according to any one of claims 9 to 11, characterized in that it is in the form of a styling lotion and also contains a cosmetic resin.  15. Composition according to any one of claims 9 to 11, characterized in that it is in the form of a composition for dyeing the hair and also contains a coloring agent for hair and a support.  16. Composition according to Claim 9, characterized in that the polymer is present at a concentration of between 0.1 and 10% by weight, the composition being in a form suitable for application to the skin.  17. Composition according to claim 16, characterized in that it is in the form of a cream, a milk, an emulsion, a gel, an aqueous or hydroalcoholic solution.  18. Composition according to any one of the preceding claims, characterized in that it also contains various cosmetic adjuvants such as perfumes, dyes, preservatives, thickening agents, stabilizing agents, softening agents, agents a number of emulsifying agents, anti-sun agents and healing agents.