WO1999067216A1 - DERIVATIZED POLYMERS OF α-OLEFIN-MALEIC ANHYDRIDE ALKYL HALF-ESTER OR FULL ACID - Google Patents
DERIVATIZED POLYMERS OF α-OLEFIN-MALEIC ANHYDRIDE ALKYL HALF-ESTER OR FULL ACID Download PDFInfo
- Publication number
- WO1999067216A1 WO1999067216A1 PCT/US1999/009430 US9909430W WO9967216A1 WO 1999067216 A1 WO1999067216 A1 WO 1999067216A1 US 9909430 W US9909430 W US 9909430W WO 9967216 A1 WO9967216 A1 WO 9967216A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- mole
- hours
- maleic anhydride
- ester
- Prior art date
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Abstract
What is described herein are derivatized polymers of α-olefin-maleic anhydride alkyl half-ester or full acid, preferably the isobutylene compound, optionally with repeat units of maleamic acid and/or its corresponding maleimide therein. These polymers are useful as fixatives in personal care products, such as hair spray compositions, particularly as one-phase, low VOC formulations in pump and aerosol systems, and in anhydrous, alcoholic, aqueous-alcoholic and in high hydrocarbon tolerant solvent formulations. In use, these hair spray compositions dry down to form clear, continuous and defectless films.
Description
DERIVATIZED POLYMERS OF α-O EFIN-MALEIC ANHYDRIDE ALKYL HALF-ESTER OR FULL ACID
BACKGROUND OF THE INVENTION This invention relates to polymers of maleic anhydride, and, more particularly, to polymers of α-olefin-maleic anhydride alkyl half-ester or full acid, optionally with repeat units of maleamic acid and/or its maleimide, and to hair spray compositions which include these polymers as fixatives .
Hair spray compositions usually contain film-forming polymers as fixatives in a suitable delivery system. Particularly desirable are polymers which can be formulated as one-phase hair spray compositions and which dry down to form continuous, clear and defectless ilms.
SUMMARY OF THE INVENTION What is described herein are polymers of α-olefin- maleic anhydride alkyl half-ester or full acid, optionally with repeat units of maleamic acid and/or its corresponding maleimide therein. These polymers are particularly useful as fixatives in hair spray compositions, particularly as one-phase, 55-80% VOC ormulations in both pump and aerosol applications , in anhydrous or aqueous-alcoholic formulations, and in high hydrocarbon tolerant formulations. In use, these compositions dry down to form continuous , clear and defectless films.
DETAILED DESCRIPTION OF THE INVENTION The polymers of the invention contain repeat units of an α-olefin-maleic anhydride alkyl half-ester or full acid, optionally with repeat units of maleamic acid and/or maleimide. Their general formula is given below:
FORMULA I
A A
-ϊ-C τ-C
R'
(α-olefιn-maleιc anhydride half (maleamic acid) ester or full acid)
(maleimide)
where A and A' are independently H or C1-C4 alkyl ;
R is H or Cx-Ca alkyl and R' is an α-unsubstituted primary amine or hydroxy-containing α-unsubstituted primary amine having one or more of the following groups therein; hydrogen, silyl, amino, olefinic, carboxy and haloge ; and x is 0.01-1; y is 0-0.95; and z is 0-0.99.
The derivatized polymers of the invention are made by reacting an α-olefin-maleic anhydride copolymer or α- olefin-maleic anhydride alkyl half-ester copolymer, having the formula :
FORMULA II
A A
-PcH2-C HC CHy- -cH2-C HC CH ~
L I I I J L I I I J
A' #C^ /C. A' 0=C C=0
0 0 0 I I
OH OR α-olefιn-maleιc anhydride α-olefin-maleic anhydride alkyl copolymer half-ester or full acid copolymer
in an aqueous, alcohol or aqueous-alcoholic solution, ROH, where R is as defined above, with an α-unsubstituted primary amine , RNH2 , such as n-hexylamine , n-octylamine or 2-ethylhexylamine, or hydroxy-containing α-unsubstituted primary amine. Ammonia, or a silated primary amine, fluorinated primary amine , halogenated primary amine , unsaturated amine , cyanoamine , alcohol amines and amphoteric amines, also may be used. The reaction is carried out at a reaction temperature of about 80-150°C, preferably about 100-130° C, for about 1-25 hours, preferably 2-10 hours.
In one embodiment of the invention, a polymer having no amide repeat unit, i.e. all amide has been converted to the cyclic imide form, can be obtained by carrying out the process at 115° C. for 5 hours or longer. The resultant polymer thus includes only half-ester and cyclic imide repeat units therein.
Higher reaction temperatures and longer reaction times enhance the conversion of amide into the corresponding cyclic imide repeating unit by loss of a water molecule .
The α-olefin-maleic anhydride or α-olefin-maleic anhydride alkyl half-ester copolymers used as starting materials in the process of the invention are made by a suspension polymerization method in a hydrocarbon solvent. In this method, the suspending agent and a free radical polymerization initiator are charged to a reactor and purged with nitrogen gas . Then the reactor is heated to 60°C and a predetermined amount of molten maleic anhydride is introduced into the reactor vessel. Then the reactor is heated to 80°C and isobutylene is fed in continuously over a predetermined amount of time. The resultant feed rate is based on the efficiency of removal of heat from the system which is evolved during the polymerization reaction. Upon completion of the reaction, a white suspension of the polymer in the solvent is obtained which can be dried to provide a free- flowing, white powder of the desired copolymer.
Alternatively, the suspension can be pumped into a reactor and sparged with heated ethanol or water to remove the lower boiling hydrocarbon solvent and effect conversion of the anhydride polymer to its corresponding ethyl half-ester or diacid derivative.
Preferably the suspension polymerization is carried out under these conditions :
(a) the reactant solids are maintained at about 20 to 50%, preferably about 30%;
(b) the suspending agent is a hydrocarbon soluble resin, preferably containing maleic anhydride, e.g. p (octadecylvinylether-co-maleic anhydride) or p (octadecylene-co-maleic anhydride) ;
(c) the suspending agent is present in an amount of about 0.25 to 3 wt. % solids;
(d) the isobutylene reactant is fed into molten maleic anhydride over a period of about 2 to 6 hours , most preferably about 4 hours;
(e) the initiator is an azo or peroxide initiator, with a half-life of at least 10 hours at a reaction temperature between about 60° and 90° C, preferably, a peroxide initiator;
(f) the reaction temperature is at least 80° C; and
(g) the hydrocarbon solvent is pentane or hexane. Alternatively, the starting polymers of FORMULA I may be made by precipitation polymerization in a solvent such as isopropyl acetate.
HAIR SPRAY COMPOSITIONS During drying, hair spray compositions containing polymers of the invention derivatized with long chain amines form films which go through a gel-like state upon f rther drying . The resultant film is a continuous , clear, defectless film.
The invention will now be illustrated by the following examples .
1. Preparation of Starting Materials
EXAMPLE 1
To a 2-liter, high pressure reactor was added: 98.06 g maleic anhydride monomer, 2.94 g decanoylperoxide initiator, 3.85 g octadecylvinylether as suspending agent and 240 g of pentane as solvent. Then the reactor was sealed and purged 3 times with nitrogen gas . The reactor was .heated to 80 °C over a 30 minute period. Upon reaching 80°C, 141.64 ml of isobutylene monomer was fed into the reactor over a 4-hour period. The reaction was continued for another 1 hour at 80°C and then cooled and discharged. The resultant product was a finely divided, off-white slurry of poly (isobutylene-maleic anhydride) copolymer in pentane .
2. Preparation of Copolymers of Formula I
EXAMPLE 2 Into a high pressure reactor was added: 75.4 g (0.490 mole) P (isobutylene-MAn) powder, 19.8 g octadecylamine (0.0735 mole) and 222.1 g ethanol . The reaction mixture was then purged with N2 gas and the temperature was raised to 50°C and held there for 1 hour. Then the temperature was increased to 75°C, held for 2 hours, and thereafter to 100°C for 3 hours. Upon cooling the resultant product had a slightly green color and a slight haze. The dried polymer had an acid of 225 mg KOH/g polymer and contained about 2 wt. % free amine.
EXAMPLE 3 Copolymer of Formula I In a high pressure reactor was added: 60.86 g (0.395 mole) p (isobutylene-MAn) powder, 15.90 g (0.0590 mole) n-octadecylamine , 4.32 g (0.0590 mole) n-butylamine , and 270.3 g ethanol.
The resultant reaction slurry was stirred, sealed and purged with N2 gas . The temperature was raised to and kept at 75°C for 2 hours and then raised to and kept at 100°C for 5 hours. Upon cooling, the reaction product was a clear slightly yellow solution. The resultant polymer had an Acid No. of 202 mg KOH/g polymer and 0.142 meq. free amine/g of product.
EXAMPLE 4
In a high pressure reactor was added:
65 g (0.422 mole) p (isobutylene-MAn) powder,
11.4 g (0.0423 mole) octadecylamine,
10.9 g (0.0843 mole) octylamine, and
204 g ethanol.
The resultant slurry was stirred, sealed and purged with N2 gas . The temperature was raised to and kept at 75°C for 2 hours and then raised to and kept at 100°C for 5 hours. Upon cooling, the reaction product was a clear slight yellow solution. The resultant polymer had an Acid No. of 198 mg KOH/g polymer and 0.146 meq. free amine/g product.
EXAMPLE 5 To a 2-liter, high pressure reactor was added:
60.0 g (0.390 mole) p (isobutylene-maleic anhydride), 8.54 g (0.117 mole) n-butylamine, 10.82 g dodecylamine , 15.73 g (0.0584 mole) octadecylamine and 285 g ethanol. The reactor was purged with N2 gas . The reactor was heated to 75°C and held for 2 hours and then heated to 100 °C and held for 5 hours. The resultant material possessed an acid number of 146 mg KOH/g polymer.
EXAMPLE 6 To a 2-liter, high pressure reactor was added:
66.1 g (0.429 mole) p (isobutylene-maleic anhydride), 10.96 g (0.150 mole) n-butylamine, 11.90 g (0.0642 mole) dodecylamine, 5.77 g (0.0214 mole) octadecylamine and 285 g ethanol. The reactor was purged with N2 gas. The reactor was heated to 75°C and held for 2 hours and then heated to 100°C and held for 5 hours. The resultant material possessed an acid number of 160 mg KOH/g polymer .
EXAMPLE 7 To a 2-liter, high pressure reactor was added: 64.7 g (0.420 mole) p (isobutylene-maleic anhydride), 8.14 g (0.0630 mole) 2-ethylhaxylamine and 16.97 g (0.0630 mole) octadecylamine and 200 g ethanol. The reactor was purged with N2 gas . The reactor was heated to 75°C and held for 2 hours and then heated to 100°C and held for 5 hours . The resultant material possessed an acid number of 205 mg KOH/g polymer.
EXAMPLE 8 To a 2-liter, high pressure reactor was added: 73.4 g (0.477 mole) p (isobutylene-maleic anhydride), 10.45 g (0.143 mole) n-butylamine and 12.83 g (0.0476 mole) octadecylamine and 171 g ethanol. The reactor was purged with N2 gas. The reactor was heated to 75°C and held for 2 hours and then heated to 100 °C and held for 5 hours . The resultant material possessed an acid number of 195 mg KOH/g polymer.
EXAMPLE 9 To a 2-liter, high pressure reactor was added: 66.0 g p (isobutylene-maleic anhydride and 198 g ethanol. The reactor was purged with N2 gas . The reactor was heated to 130°C and held for 8 hours. The resultant material possessed an acid number of 265 mg KOH/g polymer .
EXAMPLE 10 To a 2-liter, high pressure reactor was added: 66.0 g (0.429 mole) p (isobutylene-maleic anhydride, 5.80 g (0.129 mole) ethylamine, 9.40 g (0.129 mole) n-butylamine and 198 g ethanol. The reactor was purged with N2 gas. The reactor was heated to 100°C and held for 3 hours and then the reactor was heated to 130°C and held for 5 hours. The resultant material possessed an acid number of 120 mg KOH/g polymer.
EXAMPLE 11 Into a high pressure reactor was added: 22.8 g (0.148 mole) p(IB-MAn), 3.33 g ethylamine (0.0517 mole) (70%), 2.96 g water and 45.62 g ethanol. The reaction was purged with N2 gas and the temperature raised to 100°C over 1 hour. Upon reaching 100°C, 5.44 g (0.0891 mole) ethanolamine dissolved in 19.85 g water was added to the reaction mixture . The reaction was held at 100°C for 1 hour and then raised to 130°C over 1 hour and held for an additional 8 hours . Cooling provided a clear yellow solution. The dried polymer had an acid number of only about 25 mg KOH/g polymer, indicating substantially all maleimide repeat units in the polymer.
EXAMPLE 12 Into a high pressure reactor was added: 154.0 g (1.00 mole) p(IB-MAn), 9.02 g ((0.140 mole) ethylamine (70%), 10.97 g (0.150 mole) butylamine and 316 g ethanol. The reaction was purged with N2 gas and the temperature raised to 130°C over 2 hours and held for 3 hours . The reaction mixture was cooled to which was added 36.65 g (0.600 mole) of ethanolamine dissolved in 176 g of water. The reactor was gradually reheated to 130°C over 3 hours and held for 8 hours. A clear yellow solution provided a polymer having an acid number of about 65 mg KOH/g polymer.
EXAMPLE 13 Into a high pressure reactor was added: 60.0 g (0.390 mole) p(IB-MAn) powder (acid # 280 in ethanol), 14.5 g (0.198 mole) n-butylamine and 175 g ethanol. The reaction was purged with N2 gas and the temperature raised to 130°C over 3 hours and held for 5 hours to provide the p(IB-MAn) half acid/ester. The reaction mixture then was cooled to 30°C and 11.9 g (0.195 mole) of ethanolamine dissolved in 25 g water was added slowly to the reaction mixture. The reactor was gradually reheated to 130°C over 3 hours and held for 5 hours. Upon cooling, a clear yellow solution was obtained. The dried polymer had an acid number of only about 35 mg KOH/g polymer. The reduced acid number indicating the predominance of the maleimide repeat unit therein over the maleamic acid unit.
EXAMPLE 14 Into a high pressure reactor was added: 154.0 g (1.00 mole) p(IB-MAn) and 326 g ethanol. The reaction was purged with N2 gas and the temperature raised to 130 °C over 2 hours and held or 3 hours . The reaction mixture was cooled to which was added 28.5 g (0.379 mole) 3-amino-l-propanol and 34.82 g (0.570 mole) of ethanolamine dissolved in 181 g water. The reactor was gradually reheated to 130 °C over 3 hours and held for 8 hours. Upon cooling, a clear yellow solution was obtained. The dried polymer had an acid number of about 125 mg KOH/g polymer, indicating the presence of both maleamic acid and maleimide repeat units in the polymer.
EXAMPLE 15 Into a high pressure reactor was added: 154.0 g (1.00 mole) p(IB-MAn) and 320 g ethanol. The reaction was purged with N2 gas and the temperature raised to 130°C over 2 hours and held for 3 hours . The reaction mixture was cooled to which was added 7.51 g (0.100 mole) 3-amino-l-propanol and 51.92 g (0.850 mole) of ethanolamine dissolved in 178 g of water. The reactor was gradually reheated to 130°C over 3 hours and held for 8 hours . The resultant product was a clear yellow solution. The dried polymer had an acid number of about 75 mg KOH/g polymer.
EXAMPLE 16 Into a high pressure reactor was added: 123 g (0.615 mole) onoethyl half ester of p(IB-MAn), 35.6 g (0.583 mole) ethanolamine, 88 g water and 199 g ethanol. The reaction was purged with N2 gas and the temperature raised to 130°C over 2 hours and held for 8 hours. The resultant product was a clear yellow solution. The dried polymer had an acid number of about 70 mg KOH/g polymer.
EXAMPLE 17 Into a high pressure reactor was added: 22.8 g (0.148 mole) p(IB-MAn), 3.33 g ethylamine (0.0517 mole) (70%), 2.96 g water and 45.62 g ethanol. The reaction was purged with N2 gas and the temperature raised to 100°C over 1 hour. Upon reaching 100°C, 5.44 g (0.0891 mole) ethanolamine dissolved in 19.85 g water was added to the reaction mixture. The reaction was held at 100°C for 1
hour and then raised to 130°C over 1 hour and held for an additional 8 hours . Cooling provided a clear yellow solution. The dried polymer had an acid number of only about 25 mg KOH/g polymer, indicating substantially all maleimide repeat units in the polymer .
EXAMPLE 18 Into a high pressure reactor was added: 154.0 g (1.00 mole) p(IB-MAn), 9.02 g (0.140 mole) ethylamine (70%), 10.97 g (0.150 mole) butylamine and 316 g ethanol. The reaction was purged with N2 gas and the temperature raised to 130°C over 2 hours and held for 3 hours. The reaction mixture was cooled to which was added 36.65 g (0.600 mole) of ethanolamine dissolved in 176 g of water. The reactor was gradually reheated to 130 °C over 3 hours and held for 8 hours . A clear yellow solution provided a polymer having an acid number of about 65 mg KOH/g polymer .
EXAMPLE 19 Into a high pressure reactor was added: 100 g (0.500 mole) monoethyl half ester of p(IB-MAn), 24.40 g (0.399 mole) ethanolamine, 3.66 g (0.0500 mole) butylamine, 4.63 g (0.0250 mole) dodecylamine, 84 g water and 150 g ethanol . The reaction was purged with N2 gas and the temperature raised to 130°C over 2 hours and held for 8 hours . Upon cooling the resultant product was a clear yellow solution. The dried polymer had an acid number of about 65 mg KOH/g polymer.
EXAMPLE 20 Into a high pressure reactor was added: 60.0 g (0.390 mole) p(IB-MAn) powder, 6.26 g (0.0972 mole) ethylamine (70%), 7.13 g (0.0975 mole) butylamine and 175 g ethanol . The reaction was purged with N2 gas and the temperature raised to 130°C over 3 hours and held for 5 hours. The reaction mixture was cooled to 30 °C and 11.91 g (0.195 mole) of ethanolamine dissolved in 20 g water and 30 g ethanol was added slowly to the reaction mixture. The reactor was gradually reheated to 130°C over 3 hours and held for 5 hours . Upon cooling the resultant product was a clear yellow solution . The dried polymer had an acid number of about 45 mg KOH/g polymer.
EXAMPLE 21 60 g (0.390 mole) of a p (isobutylene-co-maleic anhydride) prepolymer and 150 g of water was charged into a 1-liter pressure reactor and purged with nitrogen. The reactor was gradually heated to 100°C and held for 1-hour. Then the reactor was heated to 130°C over a 1-hour period while 22.13 g (0.362 mole) ethanolamine was gradually added to the reaction mixture . Upon reaching 130° C, the reaction mixture was held for 8 hours and cooled. The product was a slight hazy, orange solution. Analysis of the product showed the presence of both maleamic acid and maleimide repeat units , with a higher molar ratio of maleamic acid units as compared to similar products obtained in an ethanol/water solvent.
EXAMPLE 22 Hair/Spray/Compositions Containing the Polymers of Examples 1-10 Low VOC hair spray compositions containing 5% by weight of each of the polymers of Examples 1-10 are prepared in ethanol and, optionally a hydrocarbon system. The polymers are neutralized with organic amines . Typical formulations thus contained 65% ethanol, 15% hydrocarbon, 15% water and 5% polymer (80% VOC) ; or 55% ethanol, 40% water and 5% polymer (50% VOC) . The observed high humidity curl retentions for these systems were excellent.
EXAMPLE 22A
The polymers of the invention is formulated into a hydroalcoholic pump hair spray system containing as little as 3.5% water and a maximum of 91% water
(VOC 4-92%) .
Formula I
SD Alcohol 40B 200, Anhydrous 87.50% Deionized Water 0.00
Imidized IB/MA Copolymer 12.50
(40% solids, 27% H20, 33% EtOH)
Formula II
SD Alcohol 40B 200, Anhydrous 0.00%
Deionized Water 87.50
Imidized IB/MA Copolymer 12.50 (40% solids, 27% H20, 33% EtOH)
EXAMPLE 22B The polymers of the invention is formulated into a single phase hydroalcoholic aerosol hair spray system having a VOC content of 35% to 95%, with dimethyl ether as the propellant.
Formula III
SD Alcohol 40B 200, Anhydrous 52.50%
Deionized Water 0.00
Imidized IB/MA Copolymer 12.50 (40% solids, 27% H20, 33% EtOH)
Dimethyl Ether 35.00
Resin solids 5%
Formula IV
SD Alcohol 40B 200, Anhydrous 0.00%
Deionized Water 52.50
Imidized IB/MA Copolymer 12.50 (40% solids, 27% H20, 33% EtOH)
Dimethyl Ether 35.00
Resin solids 5%
Formula V
SD Alcohol 40B 200, Anhydrous 15.88%
Deionized Water 35.92
Imidized IB/MA Copolymer 12.50
(40% solids, 27% H20, 33% EtOH)
Ammonium Hydroxide 0.30
MEA Borate (and) MIPA Borate 0.40
Dimethyl Ether 35.00 Resin solids 5%
(Corrosion resistant in unlined tinplate cans)
Formula VI
SD Alcohol 40B 200, Anhydrous 15.88%
Deionized Water 35.92
Imidized IB/MA Copolymer 12.50 (40% solids, 27% H20, 33% EtOH)
Ammonium Hydroxide 0.15
Dimethyl Oxazolidine 0.15
MEA (and) MIPA Borate 0.40
Dimethyl Ether 35.00 Resin solids 5%
The Formulas I-VI above also provide stiff feel on the hair at 5% resin solids comparable to an 80% VOC maximum hold, obtained with conventional retail hair sprays. In addition, advantageous humidity resistance (95% curl retention after exposure to 90% relative humidity, 80°F for 4 hours) is achieved in these 55% VOC hair sprays .
Claims
1. A derivatized polymer which contains repeat units of an ╬▒-olefin-maleic anhydride alkyl half-ester or full acid, and optionally, maleamic acid and/or maleimide repeat units , having the formula :
CH2 
(╬▒-olefin-maleic anhydride half (maleamic acid) ester or full acid)
(maleimide)
where A is independently H or C1-C4 alkyl;
R is H or C1-C4 alkyl, and R' is an ╬▒-unsubstituted primary amine; or hydroxy-containing ╬▒-unsubstituted primary amine havine one or more of the following groups therein: hydrogen, silyl, amino, olefinic, carboxy and halogen; and x is 0.01-1; y is 0-0.95; and z is 0-99.
2. A polymer according to claim 1 wherein R is ethyl .
3. A polymer according to claim 1 wherein A and A' = H.
4. A polymer according to claim 1 wherein A = H and A' = CH3.
5. A polymer according to claim 1 wherein A and A' = CH3.
6. A personal care product which includes the polymer of claim 1.
7. A hair spray composition which includes the polymer of claim 1 as fixative therein.
8. A hair spray composition according to claim 6 in a pump or aerosol formulation.
9. A hair spray composition according to claim 8 in which the polymer is present in a hair gel or mousse formulation .
10. A shampoo or hair conditioner product which includes the polymer of claim 1.
11. A skin care product which includes the polymer of claim 1.
12. A process of making the polymer of claim 1 which comprises reacting:
- 
in aqueous or aqueous-alcoholic solution, where R, Ri, R2, R3 and R4 are as defined above, with an ╬▒-unsubstituted primary amine , RNH2 , such as n-hexylamine , n-octylamine or 2-ethylhexylamine, or a hydroxy-containing ╬▒-unsubstituted primary amine, R'NH2, where R' is as defined above, at a temperature of about 60┬░ -160┬░ C, for a reaction period of about 1-25 hours.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002334307A CA2334307A1 (en) | 1998-06-24 | 1999-04-29 | Derivatized polymers of .alpha.-olefin-maleic anhydride alkyl half-ester or full acid |
| JP2000555870A JP2002518554A (en) | 1998-06-24 | 1999-04-29 | Derivative polymers of α-olefin-alkyl maleic anhydride half ester or complete acid |
| EP99920192A EP1098877A4 (en) | 1998-06-24 | 1999-04-29 | Derivatized polymers of alpha-olefin-maleic anhydride alkyl half-ester or full acid |
| AU37749/99A AU3774999A (en) | 1998-06-24 | 1999-04-29 | Derivatized polymers of alpha-olefin-maleic anhydride alkyl half-ester or full acid |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/103,856 US6025501A (en) | 1997-04-25 | 1998-06-24 | Derivatized polymers of α-olefin-maleic anhydride alkyl half-ester or full acid |
| US09/103,386 | 1998-06-24 | ||
| US09/103,386 US5886194A (en) | 1998-03-04 | 1998-06-24 | Hydroxyamino-derivatized polymers of olefin-maleic anhydride in the form of their maleimide maleamic acid and α- olefin-maleic anhydride half-acid/half ester or full acid repeat units process for making same |
| US09/104,309 US5959122A (en) | 1997-04-25 | 1998-06-24 | Process for making derivatized polymers of maleic anhydride |
| US09/104,309 | 1998-06-24 | ||
| US09/103,856 | 1998-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999067216A1 true WO1999067216A1 (en) | 1999-12-29 |
Family
ID=27379532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1999/009430 WO1999067216A1 (en) | 1998-06-24 | 1999-04-29 | DERIVATIZED POLYMERS OF α-OLEFIN-MALEIC ANHYDRIDE ALKYL HALF-ESTER OR FULL ACID |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1098877A4 (en) |
| JP (1) | JP2002518554A (en) |
| AU (1) | AU3774999A (en) |
| CA (1) | CA2334307A1 (en) |
| WO (1) | WO1999067216A1 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6589510B2 (en) | 2000-11-10 | 2003-07-08 | Wella Ag | Volume-imparting hair treatment product for strengthening the hair shaft |
| WO2004019858A2 (en) * | 2002-08-30 | 2004-03-11 | Isp Investments Inc. | Natural feel polymers |
| WO2007059828A1 (en) * | 2005-11-23 | 2007-05-31 | Henkel Kommanditgesellschaft Auf Aktien | Hair-setting compositions containing derivatized maleic anhydride polymer and amphoteric film-forming polymer |
| WO2007096400A1 (en) * | 2006-02-23 | 2007-08-30 | Intercos S.P.A. | Cosmetic composition comprising functionalised poly(alpha olefin-copolymer- maleic anhydride) |
| WO2008032342A1 (en) * | 2006-09-12 | 2008-03-20 | Intercos S.P.A. | Cosmetic composition comprising multifunctionalised poly(alpha olefin- copolymer- maleic anhydride) |
| EP1942226A1 (en) | 2001-12-18 | 2008-07-09 | Kimberly-Clark Worldwide, Inc. | A paper product comprising a polyvinylamine polymer |
| US7994079B2 (en) | 2002-12-17 | 2011-08-09 | Kimberly-Clark Worldwide, Inc. | Meltblown scrubbing product |
| EP2407145A1 (en) * | 2010-07-13 | 2012-01-18 | The Procter & Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| EP2407144A1 (en) * | 2010-07-13 | 2012-01-18 | The Procter & Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| US9986809B2 (en) | 2013-06-28 | 2018-06-05 | The Procter & Gamble Company | Aerosol hairspray product comprising a spraying device |
| US10131488B2 (en) | 2015-06-01 | 2018-11-20 | The Procter And Gamble Company | Aerosol hairspray product comprising a spraying device |
| US10426979B2 (en) | 2011-09-15 | 2019-10-01 | The Procter And Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| WO2019194949A1 (en) * | 2018-04-06 | 2019-10-10 | Dow Global Technologies Llc | Personal care cleaning composition |
| WO2021021978A1 (en) | 2019-07-31 | 2021-02-04 | L'oreal | Compositions containing copolymer of vinylpyrrolidone and acrylic acid and film forming agent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060159642A1 (en) * | 2004-12-22 | 2006-07-20 | Avon Products, Inc. | Mascara composition and method of using |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886194A (en) * | 1998-03-04 | 1999-03-23 | Isp Investments Inc. | Hydroxyamino-derivatized polymers of olefin-maleic anhydride in the form of their maleimide maleamic acid and α- olefin-maleic anhydride half-acid/half ester or full acid repeat units process for making same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2416117C3 (en) * | 1974-04-03 | 1979-09-13 | Texaco Development Corp., New York, N.Y. (V.St.A.) | Process for the preparation of ethylene-maleic acid hydride copolymers containing imide and ester groups and their use |
| DE3319014A1 (en) * | 1983-05-26 | 1984-11-29 | Bayer Ag, 5090 Leverkusen | COPOLYMERS AND THEIR USE AS SIZE |
| DE3405843A1 (en) * | 1984-02-17 | 1985-08-29 | Bayer Ag, 5090 Leverkusen | COPOLYMERS BASED ON MALEINIC ACID ANHYDRIDE AND (ALPHA), (BETA) -UNAUSAUTED COMPOUNDS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS PARAFFIN INHIBITORS |
| US4740561A (en) * | 1985-12-25 | 1988-04-26 | Ube Industries, Ltd. | Process for the preparation of N-(hydroxyphenyl)malemide copolymer |
| JP3374477B2 (en) * | 1993-11-19 | 2003-02-04 | 東ソー株式会社 | Method for producing copolymer |
-
1999
- 1999-04-29 EP EP99920192A patent/EP1098877A4/en not_active Withdrawn
- 1999-04-29 CA CA002334307A patent/CA2334307A1/en not_active Abandoned
- 1999-04-29 WO PCT/US1999/009430 patent/WO1999067216A1/en active Application Filing
- 1999-04-29 AU AU37749/99A patent/AU3774999A/en not_active Abandoned
- 1999-04-29 JP JP2000555870A patent/JP2002518554A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886194A (en) * | 1998-03-04 | 1999-03-23 | Isp Investments Inc. | Hydroxyamino-derivatized polymers of olefin-maleic anhydride in the form of their maleimide maleamic acid and α- olefin-maleic anhydride half-acid/half ester or full acid repeat units process for making same |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP1098877A4 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6589510B2 (en) | 2000-11-10 | 2003-07-08 | Wella Ag | Volume-imparting hair treatment product for strengthening the hair shaft |
| EP1942226A1 (en) | 2001-12-18 | 2008-07-09 | Kimberly-Clark Worldwide, Inc. | A paper product comprising a polyvinylamine polymer |
| KR101168427B1 (en) * | 2002-08-30 | 2012-07-27 | 아이에스피이 인베스트먼츠 인코포레이팃드 | Natural texture polymer |
| WO2004019858A2 (en) * | 2002-08-30 | 2004-03-11 | Isp Investments Inc. | Natural feel polymers |
| WO2004019858A3 (en) * | 2002-08-30 | 2004-07-01 | Isp Investments Inc | Natural feel polymers |
| CN1310985C (en) * | 2002-08-30 | 2007-04-18 | Isp投资有限公司 | Natural feel polymers |
| AU2003259127B2 (en) * | 2002-08-30 | 2008-12-04 | Isp Investments Inc. | Natural feel polymers |
| US7994079B2 (en) | 2002-12-17 | 2011-08-09 | Kimberly-Clark Worldwide, Inc. | Meltblown scrubbing product |
| WO2007059828A1 (en) * | 2005-11-23 | 2007-05-31 | Henkel Kommanditgesellschaft Auf Aktien | Hair-setting compositions containing derivatized maleic anhydride polymer and amphoteric film-forming polymer |
| WO2007096400A1 (en) * | 2006-02-23 | 2007-08-30 | Intercos S.P.A. | Cosmetic composition comprising functionalised poly(alpha olefin-copolymer- maleic anhydride) |
| WO2008032342A1 (en) * | 2006-09-12 | 2008-03-20 | Intercos S.P.A. | Cosmetic composition comprising multifunctionalised poly(alpha olefin- copolymer- maleic anhydride) |
| EP2407145A1 (en) * | 2010-07-13 | 2012-01-18 | The Procter & Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| WO2012009301A1 (en) * | 2010-07-13 | 2012-01-19 | The Procter & Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| WO2012009302A1 (en) * | 2010-07-13 | 2012-01-19 | The Procter & Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| EP2407144A1 (en) * | 2010-07-13 | 2012-01-18 | The Procter & Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| US10426979B2 (en) | 2011-09-15 | 2019-10-01 | The Procter And Gamble Company | Aerosol hairspray product for styling and/or shaping hair |
| US11311749B2 (en) | 2011-09-15 | 2022-04-26 | The Procter And Gamble Company | Aerosol hairspray for styling and/or shaping hair |
| US9986809B2 (en) | 2013-06-28 | 2018-06-05 | The Procter & Gamble Company | Aerosol hairspray product comprising a spraying device |
| US10131488B2 (en) | 2015-06-01 | 2018-11-20 | The Procter And Gamble Company | Aerosol hairspray product comprising a spraying device |
| WO2019194949A1 (en) * | 2018-04-06 | 2019-10-10 | Dow Global Technologies Llc | Personal care cleaning composition |
| WO2021021978A1 (en) | 2019-07-31 | 2021-02-04 | L'oreal | Compositions containing copolymer of vinylpyrrolidone and acrylic acid and film forming agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2334307A1 (en) | 1999-12-29 |
| JP2002518554A (en) | 2002-06-25 |
| AU3774999A (en) | 2000-01-10 |
| EP1098877A4 (en) | 2005-01-12 |
| EP1098877A1 (en) | 2001-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1098877A1 (en) | Derivatized polymers of alpha-olefin-maleic anhydride alkyl half-ester or full acid | |
| US5686066A (en) | Polyaspartic acid Zwitterionic derivatives, preparation processes thereof, hair-treating compositions and cosmetic compositions | |
| US6123933A (en) | Hair cosmetic compositions | |
| JPH0525025A (en) | Hair-care cosmetics | |
| CA2186594C (en) | Film forming antiperspirant polymers | |
| US6025501A (en) | Derivatized polymers of α-olefin-maleic anhydride alkyl half-ester or full acid | |
| AU4528996A (en) | Low voc hair spray compositions | |
| GB2237572A (en) | Vinyl alcohol copolymers containing allylamine functionality | |
| US4956430A (en) | Process for preparing substantially pure high molecular weight vinyl lactam-quaternized acrylamide copolymers | |
| JP4146900B2 (en) | Water-soluble polymers and their use in cosmetics | |
| US5886194A (en) | Hydroxyamino-derivatized polymers of olefin-maleic anhydride in the form of their maleimide maleamic acid and α- olefin-maleic anhydride half-acid/half ester or full acid repeat units process for making same | |
| US4961921A (en) | Non-aerosol pump spray compositions | |
| US3806317A (en) | Hair lacquers and lotions containing n-vinylpyrrolidone copolymers | |
| WO1988005442A1 (en) | Improved hair treating resins | |
| JP3590217B2 (en) | Polyaspartic acid derivative, method for producing the same, hair treatment composition and cosmetic composition | |
| EP0857054B1 (en) | Process for making substantially homogeneous copolymers of vinyl pyrrolidone and n-3,3-dimethylaminopropyl methacrylamide for personal care applications | |
| JPH0261494B2 (en) | ||
| US4567035A (en) | Low molecular weight hair spray | |
| US5948882A (en) | Film forming antiperspirant polymers | |
| US20050031574A1 (en) | Cosmetic composition comprising polymers having a star structure, the polymers, and their use | |
| EP1551888A1 (en) | Terpolymer of maleic acid, maleic anhydride and alkylvinylether | |
| US4444749A (en) | Cosmetic compositions for the hair | |
| EP0754029B1 (en) | Compositions containing film forming antiperspirant polymers | |
| US6252026B1 (en) | High molecular weight, homogeneous, branched copolymers of maleic anhydride and alkyl vinyl ether monomers | |
| AU722023B2 (en) | Process for making substantially homogenous copolymers for personal care applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| ENP | Entry into the national phase |
Ref document number: 2334307 Country of ref document: CA |
|
| ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2000 555870 Kind code of ref document: A Format of ref document f/p: F |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 1999920192 Country of ref document: EP |
|
| REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
| WWP | Wipo information: published in national office |
Ref document number: 1999920192 Country of ref document: EP |