CN103080159B - 用于不含单体的离子性油相的新型增稠聚合物 - Google Patents
用于不含单体的离子性油相的新型增稠聚合物 Download PDFInfo
- Publication number
- CN103080159B CN103080159B CN201180030401.6A CN201180030401A CN103080159B CN 103080159 B CN103080159 B CN 103080159B CN 201180030401 A CN201180030401 A CN 201180030401A CN 103080159 B CN103080159 B CN 103080159B
- Authority
- CN
- China
- Prior art keywords
- multipolymer
- stearyl methacrylate
- vinylformic acid
- mol ratio
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 20
- 229920000642 polymer Polymers 0.000 title claims description 8
- 230000008719 thickening Effects 0.000 title description 13
- 230000000699 topical effect Effects 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- -1 alkyl radical Chemical class 0.000 claims abstract description 6
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 45
- 150000002148 esters Chemical class 0.000 claims description 38
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical class CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 36
- 229920001897 terpolymer Polymers 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 15
- 239000003814 drug Substances 0.000 claims description 12
- 229940079593 drug Drugs 0.000 claims description 10
- 230000002500 effect on skin Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000007762 w/o emulsion Substances 0.000 claims description 3
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims description 2
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 235000005305 Nypa fruticans Nutrition 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 241000233803 Nypa Species 0.000 claims 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims 1
- 239000002537 cosmetic Substances 0.000 abstract description 4
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical group [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000008194 pharmaceutical composition Substances 0.000 abstract 1
- 238000000518 rheometry Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 35
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 4
- 210000004761 scalp Anatomy 0.000 description 4
- VCLJODPNBNEBKW-UHFFFAOYSA-N 2,2,4,4,6,8,8-heptamethylnonane Chemical compound CC(C)(C)CC(C)CC(C)(C)CC(C)(C)C VCLJODPNBNEBKW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229940043268 2,2,4,4,6,8,8-heptamethylnonane Drugs 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 210000004209 hair Anatomy 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 210000003491 skin Anatomy 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 244000004005 Nypa fruticans Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000000058 anti acne agent Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121363 anti-inflammatory agent Drugs 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940124340 antiacne agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008271 cosmetic emulsion Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229940119170 jojoba wax Drugs 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000004379 membrane Anatomy 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003158 myorelaxant agent Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XQPVIMDDIXCFFS-UHFFFAOYSA-N n-dodecylprop-2-enamide Chemical compound CCCCCCCCCCCCNC(=O)C=C XQPVIMDDIXCFFS-UHFFFAOYSA-N 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/064—Water-in-oil emulsions, e.g. Water-in-silicone emulsions
-
- 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
- A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
-
- 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
- A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
-
- 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
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
-
- 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
- A61K8/90—Block copolymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- 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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
- C08F220/68—Esters
-
- 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
- C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
-
- 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
- C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
-
- 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
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Dermatology (AREA)
- Pharmacology & Pharmacy (AREA)
- Inorganic Chemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
- Pyrrole Compounds (AREA)
- Medicinal Preparation (AREA)
Abstract
本发明涉及一种共聚物，特征在于其基于100摩尔%计含有：a)大于70摩尔%和最多99.9摩尔%的从甲基丙烯酸硬脂基酯衍生的疏水性单体单元（A）；和b)0.1-30摩尔%的从至少一种式（I）化合物衍生的单体单元（B），其中R1是含有12-22个碳原子的直链或支化烷基，R2是氢原子或甲基，n是大于或等于0且小于或等于30的整数，其中应当理解所述式（I）化合物不是甲基丙烯酸硬脂基酯。本发明还涉及制备所述共聚物的方法，以及涉及所述共聚物作为流变改进剂用于局部的化妆品组合物、皮肤药物组合物或药物组合物的油相的用途。
Description
本发明涉及一种用于增稠油相的新型化合物，涉及其制备方法，以及涉及其作为增稠剂和/或乳化剂用于皮肤、头发和头皮的护理产品的用途，尤其用于油包水型的化妆品乳液、皮肤化妆品乳液、皮肤药物乳液或药物乳液。
反向胶乳形式的合成增稠聚合物被描述为能用于生产局部组合物，参见欧洲专利申请EP 0 716 594、EP 1 047 716、EP 1 056 805和EP 0 503 853。
但是，大多数这些增稠剂不能增稠油相。
欧洲专利申请EP 0 406 042公开了油包水型乳液形式的化妆品组合物，其含有具有低比例的含离子性基团的单元的聚合物作为增稠剂，例如重量比为96.5/3.5的N-十二烷基丙烯酰胺和2-丙烯酰氨基-2-甲基丙磺酸(AMPS)的共聚物，或者重量比为97.9/2.1的N-叔丁基丙烯酰胺和2-丙烯酰氨基-2-甲基丙磺酸的共聚物。这些共聚物难以用于化妆品工业中，这是因为它们必须在使用之前中和，以及因为它们在油中的溶解通常需要使用助溶剂。此外，它们的油增稠能力差。
因此，迄今公知的仅仅具有此性能的化合物是以商品名Intelimer销售的共聚物，其是带有长烷基侧链的疏水性共聚物，其在冷条件下结晶形成簇，导致介质的增稠。这种类型的聚合物，例如丙烯酸烷基酯和（甲基）丙烯酸的共聚物，描述在美国专利US 7101928B1和US 5736125中。但是，这些产物的使用不是简单的，这是因为这些聚合物需要在热条件下溶解在油中，然后冷却以使这些链结晶。此外，它们本质上是对热敏感的，并且用这种类型聚合物增稠的组合物难以在热带国家销售。
所以，申请人寻求开发新型聚合物，其能增稠有机相和油相，并且不存在上述缺点。
因此，本发明涉及基于甲基丙烯酸硬脂基酯的共聚物，以及涉及在非极性相中制备所述共聚物的方法。
所述共聚物的特征在于其基于100摩尔%计含有：
a)大于70摩尔%和最多99.9摩尔%的从甲基丙烯酸硬脂基酯衍生的疏水性单体单元（A）；和
b)0.1-30摩尔%的从至少一种式（I）化合物衍生的单体单元（B）：
其中R1表示含有12-22个碳原子的直链或支化烷基，R2表示氢原子或甲基，n是大于或等于0且小于或等于30的整数，其中应当理解所述式（I）化合物不是甲基丙烯酸硬脂基酯。
在上述定义中，术语“共聚物”表示从至少两种具有不同化学结构的单体衍生的单体单元的聚合物。术语“共聚物”因此也包括三元共聚物、四元共聚物，以及从大于四种具有不同化学结构的单体衍生的单体单元的聚合物。
在上述定义的式（I）中，当基团R1表示含有12-22个碳原子的直链烷基时，其更尤其是选自十二烷基、十四烷基、十六烷基、十八烷基、二十烷基和二十二烷基的基团。
在上述定义的式（I）中，当基团R1表示含有12-22个碳原子的支化烷基时，其可以是下式的基团：
CH(CnH2n+1)(CmH2m+1)-CH2-
其中m是1-4的整数，n是9-16的整数；
或是下式的基团：
CH(CpH2p+1)2-CH2-
其中p是5-10的整数。
根据本发明的一个具体方面，在上述定义的式（I）中，基团R1表示选自十二烷基和二十二烷基的直链烷基。
根据本发明的一个具体方面，在上述定义的式（I）中，基团R2表示甲基。
根据本发明的一个具体方面，在上述定义的式（I）中，n是大于0；更尤其是n大于或等于4且小于或等于25。
根据本发明的一个具体方面，单体单元（B）是衍生自二十五乙氧基化甲基丙烯酸山嵛基酯，此化合物对应于上述定义的式（I）化合物，其中R1表示二十二烷基，R2表示甲基，n等于25。
根据本发明的另一个具体方面，单体单元（B）是衍生自四乙氧基化甲基丙烯酸月桂基酯，此化合物对应于上述定义的式（I）化合物，其中R1表示十二烷基，R2表示甲基，n等于4。
根据本发明的另一个具体方面，在上述定义的共聚物中，（A）/（B）的摩尔比是80/20至95/5。
本发明的一个主题更尤其是以下共聚物：
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[（A）/（B）的摩尔比=95/5]，
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[（A）/（B）的摩尔比=90/10]，
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[（A）/（B）的摩尔比=85/15]，或
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[（A）/（B）的摩尔比=80/20]。
本发明的一个主题还是上述定义的共聚物，其特征在于其基于100摩尔%计还含有0.1-30摩尔%的从以下至少一种中性单体衍生的单体单元（C）：丙烯酰胺，甲基丙烯酰胺，N,N-二甲基丙烯酰胺，N,N-二乙基丙烯酰胺，N-异丙基丙烯酰胺，丙烯酸2-羟基乙基酯，丙烯酸2,3-二羟基丙基酯，甲基丙烯酸2-羟基乙基酯，甲基丙烯酸2,3-二羟基丙基酯，以及N-乙烯基吡咯烷酮，更尤其是N,N-二甲基丙烯酰胺或N,N-二乙基丙烯酰胺。
根据一个具体模式，本发明的一个主题是上述定义的共聚物，其基于100摩尔%计含有：
a)80-95摩尔%的疏水性单体单元（A）；
b)2.5-10摩尔%的单体单元（B）；和
c)2.5-10摩尔%的单体单元（C）；
和更尤其是以下共聚物：
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[（A）/（B）/（C）的摩尔比=87/5/8]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[（A）/（B）/（C）的摩尔比=80/5/15]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[（A）/（B）/（C）的摩尔比=85/10/5]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[（A）/（B）/（C）的摩尔比=80/10/10]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[（A）/（B）/（C）的摩尔比=90/5/5]，或
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[（A）/（B）/（C）的摩尔比=95/2.5/2.5]。
本发明的一个主题也是一种制备上述定义的共聚物的方法，包括：
-步骤（a）：通过按照所需的摩尔比例将至少一种油与甲基丙烯酸硬脂基酯、式（I）单体和任选地中性单体混合来制备有机相；
-步骤（b）：通过向从步骤（a）得到的混合物中引入热引发剂来引发聚合反应，获得所需共聚物在油中的溶液；和任选地，
-步骤（c）：从由步骤（b）获得的共聚物溶液除去油。
在上述定义的方法中，所用的油可以是矿物油或植物来源的油，或是矿物油和/或植物来源的油的混合物。在本发明方法中使用的油或油混合物必须在室温下是液体，更通常在15-45℃的温度下是液体，或对于特定应用而言在4-45℃下是液体。
在上述定义的方法中，术语“矿物油”尤其表示链烷烃，异链烷烃，或环烷烃，其在室温下具有0.7-0.9的密度和大于约150的沸点，例如：
-IsoparTM H,IsoparTM G或IsoparTM M；
-MarcolTM 52，其是对应于在French Codex中的凡士林（petroleumjelly oil）定义的商业油，其是白色矿物油，符合FDA法规21 CFR 172.878和CFR 178.3620（a）。其登记在美国药典US XXIII（1995）和欧洲药典（1993）中；
-异十六烷，在化学文摘中确认为编号RN=4390-04-9，其是C12、C16和C20异链烷烃的混合物，含有至少97%的C16异链烷烃，其中主要成分是2,2,4,4,6,8,8-七甲基壬烷（RN=4390-04-9）；
-异十二烷。
在上述定义的方法中，术语“植物油”尤其表示酯或甘油三酯类型的植物油，例如己酸辛酸椰油基酯，例如由Dubois公司销售的DubTM 810C，或霍霍巴油。
上述定义的工艺步骤（a）是在搅拌下进行直到所用单体完全溶解。
上述定义的工艺步骤（b）通常在约80℃的温度下进行，并且进行直到聚合完成。
在上述定义的工艺步骤（c）中，术语“热引发剂”尤其表示偶氮二异丁腈（AIBN）或过氧化月桂酰。
在上述定义的本发明方法中任选进行的步骤c)除去操作一般如下进行：先用合适的沉淀溶剂沉淀在步骤b)之后形成的共聚物，例如用丙酮，然后过滤沉淀物。油也可以通过将在步骤b)中获得的溶液进行雾化来除去。
本发明的一个主题还是在上述定义的工艺步骤b)之后直接获得的共聚物溶液。
本发明的一个主题还是上述定义的共聚物或上述定义的聚合物溶液作为流变改进剂在化妆品局部组合物、皮肤药物局部组合物或药物局部组合物中的用途；更尤其是上述定义的用途，其中所述化妆品局部组合物、皮肤药物局部组合物或药物局部组合物是油包水型的乳液。
本发明的局部组合物，要施用于人或动物的皮肤、头发、头皮或者粘膜上，可以含有局部乳液，所述乳液含有至少一种水相和至少一种油相。这种局部乳液更尤其是油包水类型的。局部乳液的油相可以含有一种或多种油的混合物。
本发明的局部组合物可以用于化妆品用途，或可以用于制备用于处理皮肤、头皮和粘膜疾病的药物。在后一种情况下，局部组合物则含有活性成分，其例如包括抗炎剂、肌肉松弛剂、抗真菌剂或抗细菌剂。
当局部组合物要作为化妆品组合物施用于皮肤、头皮或粘膜时，其可以含有或不含活性成分，例如保湿剂、晒黑剂、防晒剂、抗皱剂、纤细剂、自由基清除剂、抗粉刺剂或抗真菌剂。
局部组合物也可以含有通常包含在这类组合物中的化合物，例如香料、防腐剂、抗氧化剂、着色剂、软化剂或表面活性剂。
本发明的一个主题也是一种改进含有脂肪相的化妆品局部组合物、皮肤药物局部组合物或药物局部组合物的流变性能的方法，其特征在于将有效量的上述定义的共聚物或上述定义的聚合物溶液加入所述脂肪相中。
最后，本发明的一个主题也是一种化妆品局部组合物、皮肤药物局部组合物或药物局部组合物，更尤其是根据本发明的油包水型乳液，其通常含有按照100%其总质量计的0.1-10质量%、更尤其1-5质量%的上述共聚物。
以下实施例用于说明本发明。
实施例1：在IsoparTM H中的甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物
制备：
a)–先将56.2g的IsoparTM H放入反应器中。然后在搅拌下逐步加入35.5g甲基丙烯酸硬脂基酯和8.3g的二十五乙氧基化甲基丙烯酸山嵛基酯，同时保持温度为约30℃。
b)–在氮气下脱气约30分钟之后，温度升高到80℃，然后通过加入0.5摩尔%的偶氮二异丁腈来引发聚合。聚合进行7小时，作为在油中的溶液获得预期的共聚物。
获得了甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物（摩尔比A/B=95/5）在油中的溶液，下面称为化合物1A。
通过改变所述单体的摩尔比例，按照相同方式制备以下共聚物在油中的溶液：
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物（摩尔比A/B=90/10），下面称为化合物1B；
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物（摩尔比A/B=85/15），下面称为化合物1C；
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物（摩尔比A/B=80/20），下面称为化合物1D。
性能评价：
将MarcolTM 52加入共聚物1A至1D的每种溶液中，从而获得含有5质量%共聚物的溶液，使其然后按照100%油相计含有1质量%水。
然后将每个脂肪相样品在水浴中于80℃放置30秒，然后于500rpm搅拌约3小时。在共聚物溶液的外观和所得凝胶的稠度方面的观察结果列在下表中。
粘度评价：＊:粘稠不足，＊＊：粘稠，＊＊＊：更粘稠
实施例2：在IsoparTM H中的甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物
制备：
a)–先将56.2g的IsoparTM H放入反应器中。然后在搅拌下逐步加入34.16g甲基丙烯酸硬脂基酯、8.72g的二十五乙氧基化甲基丙烯酸山嵛基酯和0.792g的N,N-二甲基丙烯酰胺，同时保持温度为约30℃。
b)–在氮气下脱气约30分钟之后，温度升高到80℃，然后通过加入0.5摩尔%的偶氮二异丁腈来引发聚合。聚合进行7小时，作为在油中的溶液获得预期的共聚物。
获得了甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物（摩尔比A/B=87/5/8）在油中的溶液，下面称为化合物2A。
通过改变所述单体的摩尔比例，按照相同方式制备以下共聚物在油中的溶液：
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物（摩尔比A/B/C=80/5/15），下面称为化合物2B；
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物（摩尔比A/B/C=85/10/5），下面称为化合物2C；
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物（摩尔比A/B/C=80/10/10），下面称为化合物2D；
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物（摩尔比A/B/C=90/5/5），下面称为化合物2E；
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物（摩尔比A/B/C=95/2.5/2.5），下面称为化合物2F。
性能评价
将MarcolTM 52加入共聚物2A至2F的每种溶液中，从而获得含有5质量%共聚物的溶液，使其然后按照100%油相计含有1质量%水。
然后将每个脂肪相样品在水浴中于80℃放置30秒，然后于500rpm搅拌约3小时。在共聚物溶液的外观和所得凝胶的稠度方面的观察结果列在下表中。
粘度评价：＊:粘稠不足，＊＊：粘稠，＊＊＊：更粘稠
对比实施例：在IsoparTM H中的甲基丙烯酸硬脂基酯和N,N-二甲基丙烯酰胺的共聚物
制备：
a)–先将56.2g的IsoparTM H放入反应器中。然后在搅拌下逐步加入41.6g甲基丙烯酸硬脂基酯和1.1g的N,N-二甲基丙烯酰胺，同时保持温度为约30℃。
b)–在氮气下脱气约30分钟之后，温度升高到80℃，然后通过加入0.5摩尔%的偶氮二异丁腈来引发聚合。聚合进行7小时，作为在油中的溶液获得预期的共聚物。
获得了甲基丙烯酸硬脂基酯和N,N-二甲基丙烯酰胺的共聚物（摩尔比A/B=87/15）在油中的溶液，下面称为化合物C。
性能评价
将MarcolTM 52加入共聚物C的溶液中，从而获得含有5质量%共聚物的溶液，使其然后按照100%油相计含有1质量%水。
然后将每个脂肪相样品在水浴中于80℃放置30秒，然后于500rpm搅拌约3小时。在共聚物溶液的外观和所得凝胶的稠度方面的观察结果列在下表中。
| 共聚物C | |
| 在油中的溶液的外观 | 透明 |
| 最终凝胶的稠度 | ＊ |
粘度评价：＊:粘稠不足
这些实验证明本发明的共聚物是优良的油增稠剂，与现有技术的共聚物相比，它们能改进流变性能并同时需要最少量的水，因此使得能获得透明的凝胶。
与对比例的共聚物C相比也证明了在本发明共聚物中存在从式（I）化合物衍生的单体单元是必要的。
Claims (17)
1.一种共聚物，特征在于其基于100摩尔％计含有：
a)大于70摩尔％和最多99.9摩尔％的从甲基丙烯酸硬脂基酯衍生的疏水性单体单元(A)；和
b)0.1-30摩尔％的从至少一种式(I)化合物衍生的单体单元(B)：
其中R1表示含有12-22个碳原子的直链或支化烷基，R2表示氢原子或甲基，n是大于或等于0且小于或等于30的整数，其中应当理解所述式(I)化合物不是甲基丙烯酸硬脂基酯。
2.权利要求1的共聚物，其中在式(I)中，基团R1表示选自十二烷基和二十二烷基的直链烷基。
3.权利要求1或2的共聚物，其中在式(I)中，n大于或等于4且小于或等于25。
4.权利要求3的共聚物，特征在于所述共聚物是甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物，或是甲基丙烯酸硬脂基酯和四乙氧基化丙烯酸月桂基酯的共聚物。
5.权利要求1或2的共聚物，其中摩尔比(A)/(B)是80/20至95/5。
6.权利要求4的共聚物，特征在于其是以下共聚物：
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[(A)/(B)的摩尔比＝95/5]，
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[(A)/(B)的摩尔比＝90/10]，
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[(A)/(B)的摩尔比＝85/15]，或
-甲基丙烯酸硬脂基酯和二十五乙氧基化甲基丙烯酸山嵛基酯的共聚物[(A)/(B)的摩尔比＝80/20]。
7.权利要求1或2的共聚物，特征在于其基于100摩尔％计还含有0.1-30摩尔％的从选自以下的至少一种中性单体衍生的单体单元(C)：丙烯酰胺，甲基丙烯酰胺，N,N-二甲基丙烯酰胺，N,N-二乙基丙烯酰胺，N-异丙基丙烯酰胺，丙烯酸2-羟基乙基酯，丙烯酸2,3-二羟基丙基酯，甲基丙烯酸2-羟基乙基酯，甲基丙烯酸2,3-二羟基丙基酯，以及N-乙烯基吡咯烷酮。
8.权利要求7的共聚物，其中所述单体单元(C)是衍生自N,N-二甲基丙烯酰胺或N,N-二乙基丙烯酰胺。
9.权利要求7的共聚物，其中所述共聚物基于100摩尔％计含有：
a)80-95摩尔％的疏水性单体单元(A)；
b)2.5-10摩尔％的单体单元(B)；和
c)2.5-10摩尔％的单体单元(C)。
10.权利要求8的共聚物，其特征在于所述共聚物是：
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[(A)/(B)/(C)的摩尔比＝87/5/8]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[(A)/(B)/(C)的摩尔比＝80/5/15]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[(A)/(B)/(C)的摩尔比＝85/10/5]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[(A)/(B)/(C)的摩尔比＝80/10/10]，
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[(A)/(B)/(C)的摩尔比＝90/5/5]，或
-甲基丙烯酸硬脂基酯、二十五乙氧基化甲基丙烯酸山嵛基酯和N,N-二甲基丙烯酰胺的三元共聚物[(A)/(B)/(C)的摩尔比＝95/2.5/2.5]。
11.一种制备权利要求1-10中任一项定义的共聚物的方法，包括：
-步骤(a)：通过按照所需的摩尔比例将至少一种油与甲基丙烯酸硬脂基酯、式(I)单体和任选地中性单体混合来制备有机相；
-步骤(b)：通过向从步骤(a)得到的混合物中引入热引发剂来引发聚合反应，获得所需共聚物在油中的溶液；和任选地，
-步骤(c)：从由步骤(b)获得的共聚物溶液除去油。
12.一种在权利要求11定义的方法的步骤b)之后直接获得的共聚物溶液。
13.如权利要求1-10中任一项定义的共聚物或如权利要求12定义的聚合物溶液作为流变改进剂在化妆品局部组合物、皮肤药物局部组合物或药物局部组合物中的用途。
14.一种改进含有脂肪相的化妆品局部组合物、皮肤药物局部组合物或药物局部组合物的流变性能的方法，其特征在于将有效量的如权利要求1-10中任一项定义的共聚物或如权利要求12定义的聚合物溶液加入所述脂肪相中。
15.一种化妆品局部组合物、皮肤药物局部组合物或药物局部组合物，其含有按照100质量％计的0.1-10质量％的如权利要求1-10中任一项定义的共聚物。
16.根据权利要求15的化妆品局部组合物、皮肤药物局部组合物或药物局部组合物，其中所述组合物是油包水型乳液。
17.根据权利要求15或16的化妆品局部组合物、皮肤药物局部组合物或药物局部组合物，其含有按照100质量％计的1-5质量％的如权利要求1-10中任一项定义的共聚物。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1054933 | 2010-06-22 | ||
| FR1054933A FR2961513B1 (fr) | 2010-06-22 | 2010-06-22 | Nouveau polymere epaississant de phases grasses sans monomere ionique |
| PCT/FR2011/051275 WO2011161349A1 (fr) | 2010-06-22 | 2011-06-06 | Nouveau polymere epaississant de phases grasses sans monomere ionique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103080159A CN103080159A (zh) | 2013-05-01 |
| CN103080159B true CN103080159B (zh) | 2015-06-10 |
Family
ID=42733627
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180030401.6A Expired - Fee Related CN103080159B (zh) | 2010-06-22 | 2011-06-06 | 用于不含单体的离子性油相的新型增稠聚合物 |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US8937101B2 (zh) |
| EP (1) | EP2585504B1 (zh) |
| KR (1) | KR101850563B1 (zh) |
| CN (1) | CN103080159B (zh) |
| FR (1) | FR2961513B1 (zh) |
| WO (1) | WO2011161349A1 (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2992323B1 (fr) * | 2012-06-25 | 2015-07-03 | Soc Dexploitation De Produits Pour Les Industries Chimiques Seppic | Nouveau latex inverse auto-inversible exempt de tensioactif, son utilisation comme agent epaississant dans une composition cosmetique |
| TWI689548B (zh) * | 2015-04-30 | 2020-04-01 | 德商艾朗希歐德意志有限公司 | 具改良低溫性質及良好耐油性之丙烯酸酯橡膠，由其製得之可硫化混合物及硫化物 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101080422A (zh) * | 2004-12-16 | 2007-11-28 | 化工产品开发公司Seppic | 新型浓缩反相胶乳、其制备方法及其工业应用 |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE629904A (zh) * | 1962-03-23 | |||
| US4062817A (en) | 1977-04-04 | 1977-12-13 | The B.F. Goodrich Company | Water absorbent polymers comprising unsaturated carboxylic acid, acrylic ester containing alkyl group 10-30 carbon atoms, and another acrylic ester containing alkyl group 2-8 carbon atoms |
| US4606834A (en) * | 1985-09-10 | 1986-08-19 | Texaco Inc. | Lubricating oil containing VII pour depressant |
| LU87534A1 (fr) | 1989-06-09 | 1991-02-18 | Oreal | Compositions cosmetiques contenant un agent epaississant un polymere ayant une faible proportion de motifs a groupements ioniques |
| GB9104878D0 (en) | 1991-03-08 | 1991-04-24 | Scott Bader Co | Thickeners for personal care products |
| FR2721511B1 (fr) | 1994-06-22 | 1996-07-19 | Seppic Sa | Composition topique comprenant une phase aqueuse et un agent épaississant. |
| US5736125A (en) | 1997-01-10 | 1998-04-07 | National Starch And Chemical Investment Holding Corporation | Compositions containing copolymers as a thickening agent |
| ES2277680T3 (es) | 1998-01-16 | 2007-07-16 | Societe D'exploitation De Produits Pour Les Industries Chimiques-Seppic | Latex espesante, procedimiento de fabricacion y aplicaciones en cosmetica. |
| FR2774996B1 (fr) | 1998-02-17 | 2001-02-09 | Seppic Sa | Homopolymere epaississant, procede de preparation et applications en cosmetique |
| US7101928B1 (en) | 1999-09-17 | 2006-09-05 | Landec Corporation | Polymeric thickeners for oil-containing compositions |
| DE102004032304A1 (de) | 2004-07-03 | 2006-02-16 | Construction Research & Technology Gmbh | Wasserlösliche sulfogruppenhaltige Copolymere, Verfahren zu deren Herstellung und ihre Verwendung |
| FR2910899B1 (fr) * | 2006-12-27 | 2009-10-09 | Seppic Sa | Nouveau polymere en poudre comportant un monomere tensio-actif, procede pour sa preparation et utilisation comme epaississant |
| ES2456494T3 (es) | 2008-09-02 | 2014-04-22 | Basf Se | Copolímeros útiles como modificadores de la reología y composiciones para el cuidado personal y del hogar |
-
2010
- 2010-06-22 FR FR1054933A patent/FR2961513B1/fr active Active
-
2011
- 2011-06-06 US US13/701,641 patent/US8937101B2/en not_active Expired - Fee Related
- 2011-06-06 CN CN201180030401.6A patent/CN103080159B/zh not_active Expired - Fee Related
- 2011-06-06 EP EP11728359.8A patent/EP2585504B1/fr active Active
- 2011-06-06 WO PCT/FR2011/051275 patent/WO2011161349A1/fr active Application Filing
- 2011-06-06 KR KR1020127032567A patent/KR101850563B1/ko active IP Right Grant
-
2014
- 2014-12-09 US US14/564,446 patent/US9243094B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101080422A (zh) * | 2004-12-16 | 2007-11-28 | 化工产品开发公司Seppic | 新型浓缩反相胶乳、其制备方法及其工业应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130079420A1 (en) | 2013-03-28 |
| CN103080159A (zh) | 2013-05-01 |
| FR2961513B1 (fr) | 2012-07-13 |
| KR101850563B1 (ko) | 2018-04-19 |
| WO2011161349A1 (fr) | 2011-12-29 |
| US9243094B2 (en) | 2016-01-26 |
| KR20130135728A (ko) | 2013-12-11 |
| FR2961513A1 (fr) | 2011-12-23 |
| EP2585504A1 (fr) | 2013-05-01 |
| EP2585504B1 (fr) | 2014-08-06 |
| US8937101B2 (en) | 2015-01-20 |
| US20150094440A1 (en) | 2015-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102174140B (zh) | 新型浓缩反相胶乳、其制备方法及其工业应用 | |
| DE60020098T2 (de) | Flüssige polymerdispersionen, ihre herstellung und verwendung | |
| EP1330477A2 (en) | Rheology modifying copolymer composition | |
| CN102421809B (zh) | 梳状、阳离子共聚物，其制备及其在化妆品、药物和皮肤病配制剂中的用途 | |
| DE69127886T2 (de) | Copolymere auf Basis von N-Alkylacrylamid, deren Herstellung und deren Verwendung als Verdickungsmittel in Shampoozusammensetzungen | |
| US3860700A (en) | Certain copolymers and their use in cosmetics | |
| JP2017528545A (ja) | 界面活性剤相溶性星形高分子 | |
| CN103080159B (zh) | 用于不含单体的离子性油相的新型增稠聚合物 | |
| JPH03162442A (ja) | ゲル組成物及びこれを含有する化粧料 | |
| EP1889856B1 (en) | Inverse emulsions useful as thickeners for cosmetics | |
| TWI683672B (zh) | 化粧料 | |
| KR20100133111A (ko) | 안정한 역상 에멀젼 | |
| DE60306686T2 (de) | Synthetische verdickungsmittel für kosmetika | |
| BR112014004280B1 (pt) | Copolímero modificador de reologia | |
| CN107810212A (zh) | 作为增稠剂和悬浮剂的聚合物 | |
| CN102884036B (zh) | 由三羟甲基丙烷的聚烷氧基化衍生物和脂肪醇构成的组合物,所述组合物的制备方法,及其在自可逆反相胶乳中作为反相剂的用途 | |
| JP2014507461A (ja) | 増粘剤として非水溶性両親媒性共重合体を含有する化粧料製剤 | |
| KR20140133528A (ko) | 글리세린-기재 화장품 포뮬러의 끈적임을 감소시키는 신규한 실리콘 아크릴레이트 및 아크릴산 증점 중합체 | |
| KR20140130684A (ko) | 신규한 실리콘 아크릴레이트 및 트리플루오로에틸 메타크릴레이트 중합체, 이의 제조 및 화장품에서 이의 용도 | |
| EP2678375A1 (de) | Polymere basierend auf glycerincarbonat | |
| DK2582734T3 (en) | NEW thickening polymers FOR FAT PHASES | |
| JP2006045432A (ja) | 新規共重合体及びこれを配合する化粧料 | |
| WO2024106407A1 (ja) | ポリマー粒子を含む組成物およびポリマー粒子を含む組成物の製造方法 | |
| JP6182543B2 (ja) | グリセリンベースの化粧品処方の粘着性を低減する新たな増粘ポリマー | |
| JP6124879B2 (ja) | （メタ）アクリレートに基づく会合性増粘剤 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150610 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |