CN115073742B - 发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液 - Google Patents
发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液 Download PDFInfo
- Publication number
- CN115073742B CN115073742B CN202210785869.6A CN202210785869A CN115073742B CN 115073742 B CN115073742 B CN 115073742B CN 202210785869 A CN202210785869 A CN 202210785869A CN 115073742 B CN115073742 B CN 115073742B
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- polyether
- foaming
- based silicone
- carboxylated
- 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.)
- Active
Links
- 229920000570 polyether Polymers 0.000 title claims abstract description 94
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 92
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229920002545 silicone oil Polymers 0.000 title claims abstract description 74
- 238000005187 foaming Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 25
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims abstract description 57
- 229920002674 hyaluronan Polymers 0.000 claims abstract description 57
- 229960003160 hyaluronic acid Drugs 0.000 claims abstract description 57
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- -1 alcohol amine Chemical class 0.000 claims description 13
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002453 shampoo Substances 0.000 claims description 10
- 230000001954 sterilising effect Effects 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 229940014800 succinic anhydride Drugs 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 230000000844 anti-bacterial effect Effects 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 5
- 101150065749 Churc1 gene Proteins 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 5
- 102100038239 Protein Churchill Human genes 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims description 4
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 claims description 4
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 229960002233 benzalkonium bromide Drugs 0.000 claims description 3
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 3
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 3
- 229960003333 chlorhexidine gluconate Drugs 0.000 claims description 3
- YZIYKJHYYHPJIB-UUPCJSQJSA-N chlorhexidine gluconate Chemical group OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O.C1=CC(Cl)=CC=C1NC(=N)NC(=N)NCCCCCCNC(=N)NC(=N)NC1=CC=C(Cl)C=C1 YZIYKJHYYHPJIB-UUPCJSQJSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 2
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 230000003020 moisturizing effect Effects 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 5
- 241000700605 Viruses Species 0.000 abstract description 3
- 230000001580 bacterial effect Effects 0.000 abstract description 2
- 210000003491 skin Anatomy 0.000 description 24
- 239000006260 foam Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 101100172720 Rattus norvegicus Ces1e gene Proteins 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 8
- 101000799554 Homo sapiens Protein AATF Proteins 0.000 description 6
- 102100034180 Protein AATF Human genes 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000008240 homogeneous mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 101000898025 Mus musculus Acylcarnitine hydrolase Proteins 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical class [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 4
- 101100388509 Caenorhabditis elegans che-3 gene Proteins 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003906 humectant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 208000035139 partial with pericentral spikes epilepsy Diseases 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- LYOFHYLVYHTGBK-UHFFFAOYSA-N 4-chloro-1,5-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=C(Cl)C=CC(C)(O)C1 LYOFHYLVYHTGBK-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 102000004533 Endonucleases Human genes 0.000 description 1
- 108010042407 Endonucleases Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
-
- 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
- A61K8/046—Aerosols; Foams
-
- 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
- A61K8/73—Polysaccharides
- A61K8/735—Mucopolysaccharides, e.g. hyaluronic acid; Derivatives thereof
-
- 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
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- 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
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3328—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- General Chemical & Material Sciences (AREA)
- Dermatology (AREA)
- Dispersion Chemistry (AREA)
- Cosmetics (AREA)
Abstract
本发明公开了一种发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液，属于日用化工技术领域。本发明以新合成的CES作为柔软发泡硅油组分、分子量相对较小的玻尿酸或水解玻尿酸作保湿组分，然后将二者有机结合用于免洗酒精洗手液的配制，不仅可获得一种易用、发泡效果好且对常见细菌病毒有快速灭杀作用的免洗酒精洗手液，且该洗手液涂抹于肌肤表面无干裂感，还能赋予消杀后皮肤以舒适柔软和保湿的作用。
Description
技术领域
本发明涉及日用化工技术领域，具体涉及一种发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液及其制备方法。
背景技术
众所周知，市售的聚有机硅氧烷，俗称硅油，表面能低且有良好的柔软作用，但市售的聚有机硅氧烷同时也有明显消泡、破泡作用，故将其直接添加于发泡酒精洗手液中必然会导致洗手液破泡消泡、迅速流失，因此急需本身具有良好发泡功能的聚有机硅氧烷或硅油来满足市场需要。
酒精洗手液作为家庭和公共场所如机场、海关、公共卫生间、医院等场所广泛应用的消杀细菌病毒的日用物品之一，具有使用方便、杀菌效果好、挥发速度快等优点。但医护、检疫人员反复用酒精试搽手指、手掌等肌肤表面，虽能消毒，但酒精对皮肤的脱脂作用极易导致皮肤发生皴裂、表皮干燥且表皮代谢加快，这显然已对使用者皮肤造成了伤害，急需解决此问题。
发明内容
为解决现有市售硅油不发泡而消泡的缺陷，以及抗疫杀菌用免洗酒精洗手液因反复使用后易导致皮肤表面皴裂的缺陷，本发明公开了一种发泡羧基化聚醚基硅油及其制备方法，以及内含上述柔软、润肤、发泡作用的羧基化聚醚硅油以及玻尿酸天然保湿组分的免洗发泡酒精洗手液及其制备方法。
第一方面，本发明提供了一种发泡羧基化聚醚基硅油(即具有发泡作用的羧基化聚醚基硅油的简称，CES)，结构为式(I)或式(II)所示，式中R＝-CH3或-C2H5，PE＝(OC2H4)a(OC3H6)b， A＝(CH2)x，n＝0-25、a＝6-15，b＝0-3，a+b＝6-15，(a+b)/b≥5，x＝2-4；
第二方面，本发明提供了上述发泡羧基化聚醚基硅油的制备方法，结构为式(I)所示的发泡羧基化聚醚基硅油(CES)，为羧基化聚醚基聚二甲基硅氧烷(又名α,ω-羧基聚醚改性聚二甲基硅氧烷)或羧基化聚醚基聚二乙基硅氧烷(又名α,ω-羧基聚醚改性聚二乙基硅氧烷)，系用线性羟基封端聚醚基聚硅氧烷(HO-PEPS)与脂肪族二元酸酐(ABA)的开环反应制备得到。反应中HO-PEPS中的-OH与ABA的摩尔比控制为n(-OH):n(ABA)＝1:1-1.1，反应温度为 70-125℃、反应时间为2-4h。
线性羟基封端聚醚基聚硅氧烷(HO-PEPS)，又名α,ω-羟基封端聚醚硅油，结构式为 HO(C3H6O)b(C2H4O)aC3H6SiMe2O(R2SiO)nSiMe2C3H6(OC2H4)a(OC3H6)bOH，式中R、n、a、b 的取值范围同式(I)。优选地，所述线性羟基封端聚醚基聚硅氧烷选自羟基封端聚醚基聚二甲基硅氧烷或羟基封端聚醚基聚二乙基硅氧烷。HO-PEPS可直接市购(如浙江汉邦化工有限公司、浙江润禾新材料有限公司等)，也可用n＝0-25的端含氢聚二甲基硅氧烷 HSiMe2O(SiMe2O)nSiMe2H[又名端含氢硅油，HPS]与羟基封端的烯丙基聚醚 [CH2＝CHCH2(OC2H4)a(OC3H6)bOH，APE-OH]的硅氢化加成反应制备得到，式中R、n、a、b 的取值范围均同式(I)。
优选地，结构为式(II)所示的环状结构的发泡羧基化聚醚基硅油，又名1,3,5,7-四甲基 -1,3,5,7-羧基化聚醚基环四硅氧烷，系用环状1,3,5,7-四甲基-1,3,5,7-羟基封端聚醚基环四硅氧烷(D4 PE)与脂肪族二元酸酐(ABA)的开环反应制备得到，而反应中D4 PE中的-OH与ABA 的摩尔比、反应温度、反应时间等均同前述式(I)。
优选地，所述环状1,3,5,7-四甲基-1,3,5,7-羟基封端聚醚基环四硅氧烷(D4 PE)，用1,3,5,7- 四甲基环四硅氧烷(D4 H)与羟基封端的烯丙基聚醚[CH2＝CHCH2(OC2H4)a(OC3H6)bOH， APE-OH]进行硅氢化加成反应制备得到，式中，聚醚基的结构、a、b的取值范围等同式(II)。
优选地，所述羟基封端的烯丙基聚醚的结构式为CH2＝CHCH2(OC2H4)a(OC3H6)bOH，式中a、b的取值范围同式(II)；优先地，所述羟基封端的烯丙基聚醚(APE-OH)选自b＝0-3，a+b＝6-15，(a+b)/b≥5的羟基封端烯丙基聚氧乙烯聚氧丙烯醚或羟基封端烯丙基聚氧乙烯醚。
优选地，所述脂肪族二元酸酐为结构中含有4-6碳原子的脂肪族小分子二元酸酐，选自丁二酸酐、戊二酸酐或己二酸酐。
第三方面，本发明提供了一种含上述发泡羧基化聚醚基硅油的免洗发泡酒精洗手液，按质量份，包括以下组分：70-75份乙醇、1-4份发泡羧基化聚醚基硅油、0.1-2.0份其他杀菌组分、19-28.6份固含量为0.3-0.5wt％的玻尿酸水溶液以及中和剂，中和剂的用量以使体系pH 控制为6-7为宜；所述发泡羧基化聚醚基硅油采用结构为式(I)、式(II)所示的发泡羧基化聚醚基硅油中的一种或两种。
式(I)与式(II)所示的羧基化聚醚硅油可任意比例混合，混合物可用下列方法获得：1) 用式(I)与式(II)所示的羧基化聚醚硅油按任意质量比进行混合而得；2)将n＝0-25的端含氢聚硅氧烷(HPS)与1,3,5,7-四甲基环四硅氧烷(D4 H)先按比例共混，然后再按共混物 (HPS+D4 H)中的Si-H键与羟基封端的烯丙基聚醚APE-OH中的C＝C键的摩尔比＝1：1-1.05，将(HPS+D4 H)共混物与APE-OH在铂催化剂作用下进行硅氢化加成反应，先制得羟基封端聚醚基低聚硅氧烷的线性与环状前体混合物，即羟基封端聚醚硅油(HO-PEPS)+1,3,5,7-四甲基 -1,3,5,7-四(羟基封端聚醚基)环四硅氧烷(D4 PE)的混合物，然后再按(HO-PEPS+D4 PE)中的-OH 与脂肪族二酸酐ABA的摩尔比n(-OH):n(ABA)＝1:1-1.1在70-125℃下反应2-4h制得。
所述玻尿酸，又名透明质酸，结构中含有式(III)所示的结构片段，选取平均分子量≤40 万、分子量相对较小的玻尿酸或水解玻尿酸，可直接市购。而水解玻尿酸也可用平均分子量约为100万-500万高分子量的玻尿酸在内切酶(又名玻尿酸酶)作用下于40℃左右水解反应制备，水解反应温度为70-80℃，水解时间为24-48h。
平均分子量相对较小的玻尿酸或水解玻尿酸在水中溶解度应较好，用该玻尿酸制成的低浓度水溶液，其与醇溶剂共混时不产生沉淀絮凝作用；而涂抹于肌肤表面可快速渗入肌肤表层，发挥保湿、防衰老、柔嫩光滑肌肤等作用。且与前述式(I)、式(II)所示的具有柔软作用的发泡羧基聚醚硅油复合后协同用于免洗酒精洗手液，因聚醚硅油分子内羧基-COOH与玻尿酸保湿剂分子内羧基、羟基、-NHCO-基团之间的强烈氢键网络作用，可有效发挥二者协同柔软肌肤、保湿、防肌肤皴裂等功效。
优选地，所述其他杀菌组分为本身具有杀菌作用且对人体无明显伤害，而少量添加于免洗发泡酒精洗手液中、在酒精挥发完后仍能微量留在肌肤表面继续发挥杀菌作用的有机化合物或纳米银类物质。可选自葡萄糖酸氯己定、水杨酸(又名邻羟基苯甲酸)、对氯间二甲苯酚、苯扎溴铵(又名十二烷基二甲基苄基溴化铵)、苯扎氯铵(又名十二烷基二甲基苄基氯化铵)或水性纳米银溶液。
优选地，所述中和剂为有机醇胺；优选地，所述中和剂选自N,N-二甲基氨基乙醇、N,N- 二甲基异丙醇胺、一乙醇胺、二乙醇胺或三乙醇胺。
第四方面，本发明还提供了上述免洗发泡酒精洗手液的制备方法，包括以下步骤：
(1)固含量为0.3-0.5wt％的玻尿酸水溶液的配制：取玻尿酸和去离子水，搅拌溶解，分散30-60min，得固含量为0.3-0.5wt％的透明玻尿酸溶液，用中和剂调pH为6-7，备用；
(2)免洗发泡酒精洗手液的配制：按质量比，依次称取乙醇、发泡羧基化聚醚基硅油以及其他杀菌组分，搅拌溶解成透明状，再加入步骤(1)配制的玻尿酸水溶液，搅拌混匀得均匀透明液体，用中和剂调pH为6-7，得均匀透明液体，即为免洗发泡酒精洗手液。
本发明与现有技术相比，具有以下有益效果：
本发明利用线性或环状羟基封端聚醚基低聚硅氧烷如n＝0-25的α,ω-羟基封端聚醚硅油 HO-PEPS或环状低聚体1,3,5,7-四甲基-1,3,5,7-羟基封端聚醚基环四硅氧烷(D4 PE)分别与脂肪族二酸酐(ABA)的开环反应首先合成既有发泡作用、与水/醇可溶、又有良好柔软润肤作用的羧基化聚醚硅油CES。该硅油可克服现有市售聚醚硅油或其他硅油用于酒精洗手液体系易产生的消泡、破泡现象，又能提供肌肤适度的柔软作用而无粘腻感。其次，以新合成的CES 作为柔软发泡硅油组分、分子量相对较小的玻尿酸或水解玻尿酸作保湿组分，然后将二者有机结合用于免洗酒精洗手液的配制。通过CES分子中羧基与玻尿酸HA分子内羧基、羟基、酰胺基之间氢键所形成的超分子聚合物网络及其优异的锁水保湿与柔软作用，再辅助加入适量无机或有机杀菌组分，不仅可获得一种易用、发泡效果好且对常见细菌病毒有快速灭杀作用的免洗酒精洗手液，且该洗手液涂抹于肌肤表面无干裂感，还能赋予消杀后皮肤以舒适柔软和保湿的作用，从而为解决现售免洗酒精洗手液反复使用易出现的皮肤皴裂问题提供了一条有效的解决思路。
具体实施方式
为解决市售硅油不发泡、仅消泡的问题，本发明设计合成了式(I)、(II)所示的两种创新结构的硅油，并通过疏水性聚硅氧烷链段结构、聚合度n与亲水性聚醚链段链长的筛选调控，使新的硅油用于免洗酒精洗手液的配制，可克服市售大分子硅油或聚硅氧烷只具有消泡、而不能发泡的缺陷。
下面结合实施例对本发明做进一步说明，但是本发明并不局限于以下实施例。
实施例1
(1)羧基化聚醚硅油CES-1的合成
在装有温度计、回流冷凝管、搅拌器的三颈瓶中，加入0.1mol的R＝C2H5、n＝12、a＝10、 b＝0，结构为HO(C2H4O)10C3H6Si(CH3)2O[(C2H5)2SiO]12Si(CH3)2C3H6(OC2H4)10OH的前体羟基封端聚醚硅油(HO-PEPS-1，陕西科技大学氟硅研究团队提供)，搅拌，加热至125℃；然后再分批加入0.22mol丁二酸酐(SA)，控制HO-PEPS-1中的-OH与SA的摩尔比为1:1.1，再在125℃保温反应2h。反应结束，减压脱低沸，得浅黄透明液体，即为结构如下式所示的R＝C2H5、 n＝12、a＝10、b＝0、x＝2的羧基化聚醚硅油，记作CES-1。用乙醇胺中和调pH值约为7.0，备用。
(2)免洗发泡酒精洗手液CHE-1的配制
0.5wt％玻尿酸的配制：取0.5g平均分子量40万的玻尿酸，加入30.0g去离子水，用转速为600r/min的分散机搅拌分散30min，再加入69.5g去离子水搅拌10min，然后用乙醇胺调 pH值约为7.0，静置24h；翌日再搅拌10min，得透明均匀液体，即为固含量为0.5wt％的玻尿酸水溶液(HA-1)。
CHE-1的配制：按质量份，称取70.0g乙醇、4.0g CES-1、0.10g葡萄糖酸氯己定，搅拌溶解混匀；然后再加入25.9g固含量为0.5wt％的玻尿酸水溶液HA-1，搅拌混匀，用乙醇胺调体系pH值约为7，得透明状均相混合物，即为含羧基化聚醚硅油CES-1和玻尿酸HA-1的免洗发泡酒精洗手液，记作CHE-1。
实施例2
(1)羧基化聚醚硅油CES-2的合成
在装有温度计、回流冷凝管、搅拌器的三颈瓶中，加入0.1mol的a＝15、b＝3的前体1,3,5,7- 四甲基-1,3,5,7-四(羟基封端聚氧乙烯聚氧丙烯醚基)环四硅氧烷(D4 PE，陕西安迪吉尔新材料有限公司)，搅拌，加热至70℃；再分批加入0.4mol己二酸酐(AA)，控制D4 PE中的-OH与 AA的摩尔比为1:1，然后再在70℃保温反应4h。反应结束，减压脱低沸，得浅棕黄透明液体，即为结构如下式所示的A＝(CH2)4、a＝15、b＝3、x＝4的环状羧基化聚醚基低聚硅氧烷—— 1,3,5,7-四甲基-1,3,5,7-四(羧基化聚氧乙烯聚氧丙烯醚基)环四硅氧烷，记作CES-2。用N,N- 二甲基乙醇胺中和调pH值约为7.0，备用。
(2)免洗发泡酒精洗手液CHE-2的配制
0.5wt％水解玻尿酸的配制：取0.5g平均分子量5000D的水解玻尿酸(又名水解透明质酸，广州潺湲生物科技有限公司)，加入29.5g去离子水，用转速为500r/min的分散机搅拌分散 30min，再加入70.0g去离子水搅拌10min，然后用N,N-二甲基乙醇胺调pH约为7，静置24h；翌日再搅拌10min，得透明液体，即为固含量为0.5wt％的水解玻尿酸溶液(HA-2)。
CHE-2的配制：按质量份，称取75.0g乙醇、1.5g CES-1、2.0g CES-2、0.5g苯扎溴铵，搅拌溶解混匀；再加入21.0g固含量为0.5wt％水解玻尿酸的水溶液HA-2，搅拌均匀，用N,N- 二甲基乙醇胺调体系pH值约为7，得透明状均相混合物，即为含羧基化聚醚硅油(CES-1+CES-2)和玻尿酸HA-2的免洗发泡酒精洗手液，记作CHE-2。
实施例3
(1)羧基化聚醚硅油CES-3的合成
在装有温度计、回流冷凝管、搅拌器的三颈瓶中，加入0.1mol的n＝0、a＝9、b＝1、结构为HO(C3H6O)1(C2H4O)9C3H6SiMe2OSiMe2C3H6(OC2H4)9(OC3H6)1OH的前体α,ω-双(羟基封端聚氧乙烯聚氧丙烯醚基)四甲基二硅氧烷(D2 EP)，陕西安迪吉尔新材料有限公司)，搅拌，加热至 70℃；再分批加入0.2mol戊二酸酐GA，控制D2 EP中的-OH与GA的摩尔比为1:1，然后再在70℃保温反应3h。反应结束，减压脱低沸，得浅黄透明液体，即为结构如下式所示的n＝0、 a＝9、b＝1、x＝3的羧基化聚醚硅油——α,ω-双(羧基化聚氧乙烯聚氧丙烯醚基)四甲基二硅氧烷，记作CES-3。用乙醇胺中和调pH值约为7.0，备用。
(2)免洗发泡酒精洗手液CHE-3的配制
0.3wt％水解玻尿酸的配制：取0.3g平均分子量5000D的水解玻尿酸(又名水解透明质酸，广州潺湲生物科技有限公司)，加入29.7g去离子水，用转速为500r/min的分散机搅拌分散 30min，再加入70.0g去离子水搅拌10min，然后用二乙醇胺调pH约为7，静置24h；翌日再搅拌10min，得透明液体，即固含量为0.3wt％的水解玻尿酸溶液(HA-3)。
CHE-3的配制：按质量份，称取70.0g乙醇、1.5g CES-1、1.5gCES-3、0.25g水杨酸，搅拌溶解混匀；再加入26.75g固含量为0.3wt％的水解玻尿酸的水溶液HA-3，搅拌均匀，用二乙醇胺调体系pH值约为7，得透明状均相混合物，即为含羧基化聚醚硅油(CES-1+CES-3)和玻尿酸HA-3的免洗发泡酒精洗手液，记作CHE-3。
实施例4
(1)羧基化聚醚硅油CES-4的合成
在装有温度计、回流冷凝管、搅拌器的三颈瓶中，加入0.1mol的a＝6，b＝0的前体1,3,5,7- 四甲基-1,3,5,7-四(羟基封端聚氧乙烯醚基)环四硅氧烷(D4 PE，陕西安迪吉尔新材料有限公司)，搅拌，加热至120℃；然后再分批加入0.4mol丁二酸酐SA，控制前体D4 PE中的-OH与SA的摩尔比为1:1，然后再在120℃保温反应2h。反应结束，减压脱低沸，得浅棕黄透明液体，即为结构如下式所示的a＝6、b＝0、x＝2的羧基化聚醚基低聚硅氧烷——1,3,5,7-四甲基-1,3,5,7- 四(羧基化聚氧乙烯醚基)环四硅氧烷，记作CES-4。用二乙醇胺中和调pH值约为7，备用。
(2)免洗发泡酒精洗手液组合料CHE-4的配制
0.35wt％玻尿酸的配制：取0.35g平均分子量约40万的玻尿酸，加入29.65g去离子水，用转速为600r/min的分散机搅拌分散60min，再加入70.0g去离子水搅拌10min，然后用二乙醇胺调pH约为7，静置24h；翌日再搅拌10min，得透明液体，即固含量约为0.35wt％的玻尿酸水溶液(HA-4)。
CHE-4的配制：按质量份，称取71.0g乙醇、4.0g CES-4、2.0g苯扎氯铵杀菌剂，搅拌溶解混匀；再加入23.0g固含量为0.35wt％的玻尿酸水溶液HA-4，搅拌均匀，用二乙醇胺调体系pH值约为7，得透明状均相混合物，即为含羧基化聚醚硅油CES-4和玻尿酸HA-4的免洗发泡酒精洗手液，记作CHE-4。
实施例5
(1)羧基化聚醚硅油CES-5的合成
在装有温度计、回流冷凝管、搅拌器的三颈瓶中，加入0.1mol的R＝CH3(即Me)、n＝20 结构式为HMe2SiO(Me2SiO)20SiMe2H的端含氢聚硅氧烷HPS、0.1mol的1,3,5,7-四甲基环四硅氧烷D4 H以及0.6mol的a＝9、b＝1、结构为CH2＝CHCH2(OC2H4)9(OC3H6)1OH的羟基封端烯丙基聚氧乙烯聚氧丙烯醚APE-OH，搅拌混匀，加热升温至80℃；再加入催化剂量的络合铂催化剂KP22，控温80℃搅拌反应4h，得透明状R＝CH3、n＝20、a＝9、b＝1、结构为 HO(C3H6O)1(C2H4O)9C3H6SiMe2O(Me2SiO)20SiMe2C3H6(OC2H4)9(OC3H6)1OH的前体羟基封端聚氧乙烯聚氧丙烯醚基硅油(HO-PEPS-2)与a＝9、b＝1的1,3,5,7-四甲基-1,3,5,7-四(羟基封端聚氧乙烯聚氧丙烯醚基)环四硅氧烷(D4 PE)的混合物。
将上述HO-PEPS-2+D4 PE混合物搅拌混匀，加热升温至80℃，再分批加入0.6mol戊二酸酐GA，控制前体HO-PEPS-2+D4 PE中的-OH与GA的摩尔比为1:1，然后在80℃保温反应2.5h。反应结束，减压脱低沸，得浅棕黄透明液体，即为结构如式(I)所示的R＝CH3、n＝20、a＝9、b＝1、x＝3的羧基化聚氧乙烯聚氧丙烯醚基硅油及结构如式(II)所示的a＝9、b＝1、x＝3的1,3,5,7- 四甲基-1,3,5,7-四(羧基化聚氧乙烯聚氧丙烯醚基)环四硅氧烷的混合物，记作CES-5。用N,N- 二甲基丙醇胺中和调pH值约为7.0，备用。
(2)免洗发泡酒精洗手液CHE-5的配制
0.45wt％水解玻尿酸的配制：取0.45g平均分子量5000D的水解玻尿酸(广州潺湲生物科技有限公司)，加入29.55g去离子水，用转速为600r/min的分散机搅拌分散45min，再加入 70.0g去离子水搅拌10min，然后用二乙醇胺调pH约为7.0，静置24h；翌日再搅拌10min，得透明液体，即固含量为0.45wt％的水解玻尿酸水溶液(HA-5)。
CHE-5的配制：按质量份，称取70.0g乙醇、4.0g CES-5、0.5g中性纳米银溶液杀菌剂JL-119 (pH＝7，佛山市丽源化工有限公司)，搅拌溶解混匀；再加入25.5g固含量为0.45wt％的水解玻尿酸水溶液HA-5，搅拌均匀，用二乙醇胺调体系pH值约为7，得透明状均相混合物，即为含羧基化聚醚硅油混合物CES-5和玻尿酸HA-5的免洗发泡酒精洗手液，记作CHE-5。
对比例1
与实施例1的区别在于：对比例1以黏度约为2760mPa.s的市售聚醚改性硅油204(济南兴隆达化工有限公司)代替实施例1的羧基聚醚硅油CES-1进行实验，所配制的酒精洗手液记作CHE-6。
对比例2
与实施例1的区别在于：对比例2以聚醚改性三硅氧烷表面活性剂(江西海多化工有限公司)代替实施例1的羧基聚醚硅油CES-1进行实验，所配制的酒精洗手液记作CHE-7。
对比例3
与实施例1的区别在于：对比例3未添加羧基聚醚硅油，所配制的酒精洗手液记作CHE-8。
应用性能测试
取用实施例1-5及对比例1-3所制备的酒精洗手液CHE-1～CHE-8，按下列方法进行性能测定：
酒精洗手液透明性，以透光率(T％)表示，用Cary 5000型紫外-可见分光光度计测定，波长范围为200～800nm。
发泡性：取50mL免洗酒精洗手液置于带空气压缩喷头的100mLPET塑料瓶内(类似于透明带喷头的啫喱水瓶)，震荡3-4次再压出酒精，观察酒精发泡情况，发泡量越多、泡沫越绵密细小、破泡速度越慢，表明发泡性越好。
酒精洗手液对皮肤的保湿和柔软作用：用带空气压缩喷头的PET塑料瓶，压出1-2mL CHE-1～CHE-8洗手液，均匀涂抹于手表面，停3min待酒精完全挥发后用触摸法评价皮肤表面的柔软性和保湿滋润性，记录初次洗手后皮肤表面的触感与效果；然后重复上述洗手过程50次，每次洗涤间隔5min，再记录50次洗手后皮肤表面的触感与观感。
杀菌性评价：参照GB26373-2010标准用菌落计数法测定，实验菌种为金黄色葡萄球菌、大肠杆菌、白色念珠菌，测试样为CHE-1～CHE-8原液。
各实施例与对比例的测试结果见表1。
表1酒精洗手液CHE-1～CHE-8的性能评价结果
表中，杀菌性：用原液测定，杀菌作用时间≤1min；★：泡沫绵密不易流失，★越多表示泡沫越丰富绵密、不易破裂、易涂抹；◎：无检出(即检测不出)。
由表1性能检测结果可见，实施例1-5所制备的免洗酒精洗手液CHE-1～CHE-5均有良好的发泡作用，经泵头压出的酒精泡沫绵密、破泡速度慢、不易流失，经50次洗手后肌肤表面依然柔软滋润不皴裂、且无黏腻感。而对比例1用市售较高粘度的聚醚改性硅油配制的洗手液，不发泡而消泡明显，压出的酒精无法成泡沫故极易流失，且多次洗手后皮肤表面会有黏腻感。对比例2用聚醚三硅氧烷表面活性剂配制的洗手液，略有发泡性，但泡大持久性差、破泡迅速，且因体系中水的存在聚醚三硅氧烷易水解发生醚链断裂而生成三硅氧烷硅醇，故样品室温存储过程易出现略浑浊现象。对比例3的酒精洗手液，因不含柔软滋润性有机硅和玻尿酸保湿组分，故性能上仅有杀菌消毒作用而无柔软、保湿、防皮肤皲裂等作用，因此多次洗手后皮肤表面因脱脂严重而会出现表面发干、皴裂、疼痛等现象。
尽管通过参考优选实施例的方式对本发明进行了详细描述，但本发明并不限于此。在不脱离本发明的精神和实质的前提下，本领域普通技术人员可以对本发明的实施例进行各种等效的修改或替换，而这些修改或替换都应在本发明的涵盖范围内/任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应所述以权利要求的保护范围为准。
Claims (10)
1.发泡羧基化聚醚基硅油，其特征在于，结构为式(II)所示，式中PE＝(OC2H4)a(OC3H6)b，A＝(CH2)x，a＝6-15，b＝0-3，a+b＝6-15，(a+b)/b≥5，x＝2-4；
2.如权利要求1所述的发泡羧基化聚醚基硅油的制备方法，其特征在于，结构为式(II)所示的发泡羧基化聚醚基硅油，用环状1,3,5,7-四甲基-1,3,5,7-羟基封端聚醚基环四硅氧烷与脂肪族二元酸酐的开环反应制备得到。
3.如权利要求2所述的发泡羧基化聚醚基硅油的制备方法，其特征在于，所述环状1,3,5,7-四甲基-1,3,5,7-羟基封端聚醚基环四硅氧烷，用1,3,5,7-四甲基环四硅氧烷与羟基封端的烯丙基聚醚进行硅氢化加成反应制备得到。
4.如权利要求3所述的发泡羧基化聚醚基硅油的制备方法，其特征在于，所述羟基封端的烯丙基聚醚的结构式为CH2＝CHCH2(OC2H4)a(OC3H6)bOH，式中a、b的取值范围同式(II)。
5.如权利要求4所述的发泡羧基化聚醚基硅油的制备方法，其特征在于，所述羟基封端的烯丙基聚醚选自b＝0-3，a+b＝6-15，(a+b)/b≥5的羟基封端烯丙基聚氧乙烯聚氧丙烯醚或羟基封端烯丙基聚氧乙烯醚。
6.如权利要求2所述的发泡羧基化聚醚基硅油的制备方法，其特征在于，所述脂肪族二元酸酐选自丁二酸酐、戊二酸酐或己二酸酐。
7.含如权利要求1所述的发泡羧基化聚醚基硅油的免洗发泡酒精洗手液，其特征在于，按质量份，包括以下组分：70-75份乙醇、1-4份发泡羧基化聚醚基硅油、0.1-2.0份其他杀菌组分、19-28.6份固含量为0.3-0.5wt％的玻尿酸水溶液以及中和剂；所述发泡羧基化聚醚基硅油采用结构为式(II)所示的发泡羧基化聚醚基硅油。
8.如权利要求7所述的免洗发泡酒精洗手液，其特征在于，所述其他杀菌组分选自葡萄糖酸氯己定、水杨酸、对氯间二甲苯酚、苯扎溴铵、苯扎氯铵或水性纳米银溶液；所述中和剂为有机醇胺。
9.如权利要求8所述的免洗发泡酒精洗手液，其特征在于，所述中和剂选自N,N-二甲基氨基乙醇、N,N-二甲基异丙醇胺、一乙醇胺、二乙醇胺或三乙醇胺。
10.如权利要求7-9任一项所述的免洗发泡酒精洗手液的制备方法，其特征在于，包括以下步骤：
(1)固含量为0.3-0.5wt％的玻尿酸水溶液的配制：取玻尿酸和去离子水，搅拌溶解，分散30-60min，得固含量为0.3-0.5wt％的透明玻尿酸溶液，用中和剂调pH为6-7，备用；
(2)免洗发泡酒精洗手液的配制：按质量比，依次称取乙醇、发泡羧基化聚醚基硅油以及其他杀菌组分，搅拌溶解成透明状，再加入步骤(1)配制的玻尿酸水溶液，搅拌混匀得均匀透明液体，用中和剂调pH为6-7，得均匀透明液体，即为免洗发泡酒精洗手液。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210785869.6A CN115073742B (zh) | 2022-07-04 | 2022-07-04 | 发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210785869.6A CN115073742B (zh) | 2022-07-04 | 2022-07-04 | 发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115073742A CN115073742A (zh) | 2022-09-20 |
| CN115073742B true CN115073742B (zh) | 2023-05-09 |
Family
ID=83257959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210785869.6A Active CN115073742B (zh) | 2022-07-04 | 2022-07-04 | 发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115073742B (zh) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104693A (zh) * | 2006-07-14 | 2008-01-16 | 戈尔德施米特股份公司 | 直链羧基官能性有机硅氧烷衍生物及其用途 |
| JP5776634B2 (ja) * | 2011-07-06 | 2015-09-09 | 信越化学工業株式会社 | 無水コハク酸基含有環状オルガノシロキサン、その製造方法、オルガノシロキサン組成物及び熱硬化性樹脂組成物 |
| CN104490630A (zh) * | 2014-12-09 | 2015-04-08 | 南阳市汇博生物技术有限公司 | 一种免洗泡沫手消毒液及其制备方法 |
| CN109810261B (zh) * | 2018-12-26 | 2021-06-15 | 福建拓烯新材料科技有限公司 | 一种有机硅树脂微乳液的制备方法 |
-
2022
- 2022-07-04 CN CN202210785869.6A patent/CN115073742B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115073742A (zh) | 2022-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104721069B (zh) | 一种增深染发组合物 | |
| KR101364818B1 (ko) | 실리콘 엘라스토머 겔 | |
| US6355724B1 (en) | Cosmetic compositions containing silicone gel | |
| KR101889696B1 (ko) | 신규한 오르가노폴리실록산 엘라스토머 및 그 이용 | |
| US7521434B2 (en) | Cross-linked gels of hyaluronic acid with hydrophobic polymers and processes for making them | |
| CN106687149A (zh) | 水凝胶组合物 | |
| US6881416B2 (en) | Alkyl group-substituted organopolysiloxane gels | |
| CN106176286A (zh) | 透明质酸皮肤护理膜及制备方法和应用 | |
| TW201038306A (en) | Oil-in-water emulsion-type hair cosmetic | |
| EP3580277B1 (en) | Oil-in-water microemulsions and the preparation thereof | |
| US4855129A (en) | Skin-protecting or skin-care composition | |
| AU779363B2 (en) | Scar treatment composition | |
| CN112107593A (zh) | 一种免洗护手抑菌凝胶及其制备方法 | |
| CN1359672A (zh) | 非粘性的皮肤和毛发用增湿化妆组合物 | |
| CN115181275B (zh) | 发泡聚醚硅油及其制备方法和含该发泡聚醚硅油和玻尿酸的免洗酒精洗手液及其制备方法 | |
| EP1381651B1 (en) | Polyorganosiloxane emulsion composition and a cosmetic material made therefrom | |
| CN1832723A (zh) | 香料油乳液 | |
| CN115073742B (zh) | 发泡羧基化聚醚基硅油及其制备方法和含该发泡羧基化聚醚基硅油的免洗发泡酒精洗手液 | |
| JP4703819B2 (ja) | ポリオルガノシロキサンエマルジョン及びそれを含んでなる化粧料 | |
| CN104011139A (zh) | 有机聚硅氧烷制备过程中酸的用途 | |
| US6174983B1 (en) | Silicone terpolymers with high refractive indices | |
| KR102212025B1 (ko) | 실리콘 에멀젼 및 이의 제조방법 | |
| CN112472630B (zh) | 氨基酸表面活性剂的自增稠组合物 | |
| CN108102102B (zh) | 一种Si-O-C型聚醚基有机硅弹性体凝胶的制备方法和应用 | |
| CN105238261A (zh) | 一种液晶镀膜油及其制作方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |