CN114539528B - Preparation method of liquid propyl silicone resin blend for personal care - Google Patents
Preparation method of liquid propyl silicone resin blend for personal care Download PDFInfo
- Publication number
- CN114539528B CN114539528B CN202011329423.XA CN202011329423A CN114539528B CN 114539528 B CN114539528 B CN 114539528B CN 202011329423 A CN202011329423 A CN 202011329423A CN 114539528 B CN114539528 B CN 114539528B
- Authority
- CN
- China
- Prior art keywords
- silicone resin
- propyl
- propyl silicone
- liquid
- personal care
- 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
- 229920002050 silicone resin Polymers 0.000 title claims abstract description 110
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 100
- 239000007788 liquid Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002537 cosmetic Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010907 mechanical stirring Methods 0.000 claims description 10
- 238000000526 short-path distillation Methods 0.000 claims description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 10
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 6
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 6
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 3
- 210000004209 hair Anatomy 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 2
- 230000000475 sunscreen effect Effects 0.000 claims description 2
- 239000000516 sunscreening agent Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 231100000614 poison Toxicity 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000005357 flat glass Substances 0.000 description 8
- 210000003491 skin Anatomy 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000005046 Chlorosilane Substances 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008406 cosmetic ingredient Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- -1 phenyl vinyl Chemical group 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005053 propyltrichlorosilane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 230000036548 skin texture Effects 0.000 description 1
- 230000037072 sun protection Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000723 toxicological property Toxicity 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000009853 xinfeng Substances 0.000 description 1
- 239000008096 xylene Substances 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
- C08G77/06—Preparatory processes
-
- 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
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- 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
- A61Q19/08—Anti-ageing preparations
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gerontology & Geriatric Medicine (AREA)
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a liquid propyl silicone resin blend for personal care. The propyl silicone resin provided by the invention is prepared by the following method: n-propyl triethoxy silane is used as raw material, and hydrolysis polymerization reaction is carried out in the presence of water, organic solvent and acid catalyst, thus obtaining the product. The propyl silicone resin developed and produced by the invention has the excellent characteristics of high viscosity, good thermal stability, water resistance, moisture resistance and the like, and is environment-friendly and nontoxic. Even after stretching and washing, the films formed from this resin remain smooth and intact. The propyl groups on the silane chains can be freely bent and rotated, and the D5 or flexible alkane is blended, so that good lubricity, elasticity and stretchability can be provided for the product. In addition, the process route can reduce the generation and emission of strong corrosion and toxic substances in the production process, reduce the production cost by recycling the recovered solvent, and avoid the pollution to the environment.
Description
Technical Field
The invention belongs to the field of preparation of cosmetic intermediates, and particularly relates to a preparation method of a liquid propyl silicone resin blend for personal care.
Background
Under the condition that the scientific technology of China is continuously developed, the variety and the quantity of the raw materials of cosmetics are continuously increased, and how to ensure the safety of the components of the cosmetics and the environment protection in the production process are already important and difficult to study. The toxicological properties of cosmetic ingredients can affect the ingredient safety to a great extent, and thus the cosmetic use safety. The structure and the shape of the components of the cosmetic are similar to those of cells in human bodies, so that the appearance of the cosmetic is formed, and the quality of the components determines the quality and the efficacy of the cosmetic. The silicone resin is used as a novel organosilicon additive, has good film forming property and wear resistance, has better skin texture and hand feeling when being used on skin, and is therefore popular with cosmetic manufacturers in the field of cosmetic application.
The silicone resin can accelerate the absorption of nutrients by skin, and can further repair skin components, so that the skin epidermis is quickly repaired, and the stretching capability of the skin epidermis is enhanced. Zhou Shuchun et al have found that phenyl propyl-containing silicone resins have better refractive properties than conventional phenyl silicone oils, can significantly improve the gloss of lipsticks, and can also improve the absorption of ultraviolet rays by the products.
The existing silicone resins for personal care have the defects of poor adhesion, poor film forming property, poor smoothness and stretchability (poor hand feeling) and the like, so that the wider commercial application of the silicone resins is limited, and a silicone resin with more excellent performance is needed to improve the defects, so that the personal care products have better use value and feel.
In the prior art, chlorosilane is mainly used as a raw material, and silicon resin is prepared by hydrolytic polymerization. Hao Wei vinyl silicone resin is prepared by hydrolysis polymerization of vinyl trichlorosilane serving as a raw material in an ethanol and xylene system. Song Xinfeng phenyl propyl silicone resin is obtained by hydrolysis and polycondensation reaction of phenyl trichlorosilane and propyl trichlorosilane serving as raw materials in toluene and a water system. However, the preparation of silicone resins from chlorosilanes generates a large amount of hydrochloric acid (HCl), which corrodes production equipment and is harmful to the environment, and the generated wastewater needs special treatment, which further increases the process production cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel silicon resin-propyl silicon resin and a preparation method thereof.
The propyl silicone resin provided by the invention is prepared by the following method: n-propyl triethoxysilane is used as a raw material, and hydrolysis polymerization is carried out in the presence of water, an organic solvent and an acid catalyst to obtain the propyl silicone resin.
Wherein, the acid catalyst can be trifluoromethyl sulfonic acid or concentrated sulfuric acid with the mass concentration of 98 percent;
the organic solvent can be one or a mixture of more of ethanol, cyclohexane and toluene;
the molar ratio of the n-propyl triethoxysilane to the water to the acid catalyst can be as follows: 3:11-12:0.056-0.08;
the hydrolysis polymerization reaction is operated as follows: under the condition of room temperature, adding water and an organic solvent into a three-port reactor with a thermometer, starting mechanical stirring, and stirring until the water and the organic solvent are uniformly mixed; adding n-propyl triethoxysilane, continuously stirring, then dropwise adding trifluoromethanesulfonic acid or 98% concentrated sulfuric acid, stirring, starting circulating water, heating to 50-60 ℃, and reacting for 30-50 min under the condition; continuously heating to 80-85 ℃, continuously reacting for 5-6 h after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished, separating liquid, and obtaining the propyl silicone resin after short-path distillation. The synthetic process route diagram is shown in figure 1.
The obtained propyl silicone resin is clear and transparent viscous liquid, the viscosity of the propyl silicone resin is 10000-30000 mPas (25 ℃), and the refractive index of the propyl silicone resin is 1.4400-1.4500 (25 ℃).
The invention also provides a liquid propyl silicone resin blend product.
The liquid propyl silicone resin blend product comprises propyl silicone resin and a blend solvent;
the blending solvent is any one of decamethyl cyclopentasiloxane (D5) and isododecane;
the mass ratio of the propyl silicone resin to the blend solvent can be: 1:1/3-1, and can be specifically 1:1 or 1:1/3.
The liquid propyl silicone resin blend product is prepared by bubble-free blending of propyl silicone resin and a blend solvent. The preparation process route diagram is shown in fig. 2.
The liquid propyl silicone resin blend product is clear and transparent liquid, the viscosity of the liquid propyl silicone resin blend product is 100-300 mPas (25 ℃), and the refractive index of the liquid propyl silicone resin blend product is 1.4100-1.4400 (25 ℃).
The use of the propyl silicone resin, liquid propyl silicone resin blend products described above in personal care products is also within the scope of the present invention.
In such applications, the personal care product may be: make-up, liquid foundations, lotions, sunscreens, lipsticks, hair care agents.
In the personal care products, propyl silicone resin, liquid propyl silicone resin blend products are used to improve the slip, abrasion, mar and gloss properties of personal care products.
The present invention also provides a personal care product comprising the propyl silicone resin or liquid propyl silicone resin blend product described above.
The invention adopts a brand new process route, and uses n-propyl triethoxysilane as a raw material to prepare the propyl silicone resin through hydrolysis polymerization reaction in a system of an organic solvent, water and an acid catalyst. The developed propyl silicone resin has the excellent characteristics of high viscosity, good thermal stability, water resistance, moisture resistance and the like, and is environment-friendly and nontoxic (slightly toxic). The silicone resin has better film forming property, and the formed film can be flexibly transferred and is resistant to flushing, and even if the film is stretched and washed, the film formed by the resin still remains smooth and intact. The propyl groups on the silane chains can be freely bent and rotated, and the D5 or flexible alkane is blended, so that good lubricity, elasticity and stretchability can be provided for the product. In addition, the process route can reduce the generation and emission of strong corrosion and toxic substances in the production process, reduce the production cost by recycling the recovered solvent, and avoid the pollution to the environment.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) The invention aims to overcome the defects of environmental protection, complex process, high cost and the like in the production process of products. The preparation of silicone resins from chlorosilanes produces large amounts of hydrochloric acid (HCl), is not environmentally friendly, and corrodes equipment, increasing process costs. The invention adopts a brand new process route, reduces the generation and emission of strong corrosion and toxic substances in the production process, reduces the production cost by recycling the recovered solvent, and avoids the pollution to the environment.
(2) With the present invention, the synthesized propyl silicone resin has high viscosity, high refractive index, high thermal stability and water resistance (as shown in FIG. 3, si 29 NMR characterization of Si-OH) without hydrophilic groups. The prepared liquid propyl silicone resin blend product for personal care has the advantages of slightly viscosity, higher refractive index, good film forming property, heat resistance, moisture resistance and water repellency (Si 29 The NMR represents that the hydrophilic group Si-OH is not dispersed in water, small oil drops are formed by deposition (shown in figure 4), and the coating has good hand feeling when being smeared on skin, can prevent skin aging, protect the skin from being threatened by harmful radiation and irritants, and has good application potential in the cosmetic industry.
(3) The preparation process is simple, easy to operate and low in cost, and the prepared liquid propyl silicone resin blend product for personal care has good film forming property, lubricity, heat resistance, moisture resistance, water repellency and high refractive index, is suitable for the field of cosmetics, and can be used as a makeup formula, liquid foundation, skin care, sun protection, hair care and the like.
Drawings
FIG. 1 is a scheme of the synthetic process of propyl silicone resin of the present invention.
Fig. 2 is a process route diagram for the preparation of the liquid propyl silicone resin blend product for personal care of the present invention.
FIG. 3 shows Si of propyl silicone resin prepared in example 1 of the present invention 29 -NMR spectrum.
FIG. 4 shows the water repellency of the liquid propyl silicone resin blend prepared in example 1 of this invention.
Detailed Description
The present invention will be described with reference to the following specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, biological materials, etc. used in the examples described below are commercially available unless otherwise specified.
The viscosities in the examples below were measured by using a digital viscometer at a test temperature of 25 ℃ (calibrated with standard samples prior to measurement); the refractive index was measured by a digital Abbe refractometer at a test temperature of 25℃and a thickness of 2mm.
Example 1,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water, 7.49mol of cyclohexane and 1.52mol of absolute ethyl alcohol into a three-port reactor with a thermometer, and starting mechanical stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.056mol of trifluoromethanesulfonic acid, setting the stirring speed to 280rpm, starting circulating water, heating to 60 ℃, and reacting for 50min under the condition; continuously heating to 85 ℃, continuously reacting for 6 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (285.4 g), wherein the viscosity of the resin can reach 20000mPas (25 ℃), the refractive index is 1.4445 (25 ℃), and the molecular weight is 30000 (Mw).
Adding an equal mass blending solvent D5 (285 g) into the prepared propyl silicone resin according to a mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 120mPas (25 ℃), the refractive index is 1.4190 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
FIG. 3 shows Si of propyl silicone resin prepared in example 1 of the present invention 29 -NMR spectrum.
FIG. 4 shows the water repellency of the liquid propyl silicone resin blend prepared in example 1 of this invention.
EXAMPLE 2,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water, 7.49mol of cyclohexane and 1.52mol of absolute ethyl alcohol into a three-port reactor with a thermometer, and starting mechanical stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.056mol of trifluoromethanesulfonic acid, setting the stirring speed to 280rpm, starting circulating water, heating to 60 ℃, and reacting for 50min under the condition; continuously heating to 85 ℃, continuously reacting for 6 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (283.2 g), wherein the viscosity of the resin can reach 20000mPas (25 ℃), the refractive index is 1.4445 (25 ℃), and the molecular weight is 30000 (Mw).
Adding isododecane (about 95 g) as a blending solvent into the prepared propyl silicone resin according to a mass ratio of 3:1, and carrying out bubble-free blending to obtain a liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 220mPas (25 ℃), the refractive index is 1.4335 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
EXAMPLE 3,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water, 7.49mol of toluene and 1.52mol of absolute ethyl alcohol into a three-port reactor with a thermometer, starting mechanical stirring, and stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.064mol of trifluoromethanesulfonic acid, setting stirring speed to 275rpm, starting circulating water, heating to 55 ℃, and reacting for 40min under the condition; continuously heating to 85 ℃, continuously reacting for 6 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (283.9 g), wherein the viscosity of the resin can reach 22000mPas (25 ℃), the refractive index is 1.4450 (25 ℃), and the molecular weight is 33000 (Mw).
Adding an equal mass blending solvent D5 (285 g) into the prepared propyl silicone resin according to a mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 130mPas (25 ℃), the refractive index is 1.4197 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
EXAMPLE 4,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water, 7.49mol of toluene and 1.52mol of absolute ethyl alcohol into a three-port reactor with a thermometer, starting mechanical stirring, and stirring until the mixture is uniformly mixed; adding 3mol of n-propyl trimethoxy silane into a container, continuously stirring, dropwise adding 0.064mol of trifluoromethyl sulfonic acid, setting stirring speed to 275rpm, starting circulating water, heating to 55 ℃, and reacting for 40min under the condition; continuously heating to 85 ℃, continuously reacting for 6 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (284.6 g), wherein the viscosity of the resin can reach 22000mPas (25 ℃), the refractive index is 1.4450 (25 ℃), and the molecular weight is 33000 (Mw).
Adding isododecane (about 95 g) as a blending solvent into the prepared propyl silicone resin according to a mass ratio of 3:1, and carrying out bubble-free blending to obtain a liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 230mPas (25 ℃), the refractive index is 1.4337 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
EXAMPLE 5,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water, 7.49mol of cyclohexane and 1.52mol of absolute ethyl alcohol into a three-port reactor with a thermometer, and starting mechanical stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.08mol of trifluoromethanesulfonic acid, setting stirring speed to 270rpm, starting circulating water, heating to 50 ℃, and reacting for 30min under the condition; continuously heating to 80 ℃, continuously reacting for 5 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (285.1 g), wherein the viscosity of the resin can reach 25000mPas (25 ℃), the refractive index is 1.4452 (25 ℃), and the molecular weight is 35000 (Mw).
Adding an equal mass blending solvent D5 (285 g) into the prepared propyl silicone resin according to a mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 150mPas (25 ℃), the refractive index is 1.4200 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
EXAMPLE 6,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water, 7.49mol of cyclohexane and 1.52mol of absolute ethyl alcohol into a three-port reactor with a thermometer, and starting mechanical stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.08mol of trifluoromethanesulfonic acid, setting stirring speed to 270rpm, starting circulating water, heating to 50 ℃, and reacting for 30min under the condition; continuously heating to 80 ℃, continuously reacting for 5 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (283.7 g), wherein the viscosity of the resin can reach 25000mPas (25 ℃), the refractive index is 1.4452 (25 ℃), and the molecular weight is 35000 (Mw).
Adding isododecane (about 95 g) as a blending solvent into the prepared propyl silicone resin according to a mass ratio of 3:1, and carrying out bubble-free blending to obtain a liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 250mPas (25 ℃), the refractive index is 1.4340 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
EXAMPLE 7,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water and 7.49mol of toluene into a three-port reactor with a thermometer, starting mechanical stirring, and stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.08mol of 98% concentrated sulfuric acid, setting the stirring speed to 280rpm, starting circulating water, heating to 50 ℃, and reacting for 50min under the condition; continuously heating to 85 ℃, continuously reacting for 6 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (285.9 g), wherein the viscosity of the resin can reach 15000mPas (25 ℃), the refractive index is 1.4420 (25 ℃), and the molecular weight is 25000 (Mw).
Adding an equal mass blending solvent D5 (285 g) into the prepared propyl silicone resin according to a mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 100mPas (25 ℃), the refractive index is 1.4185 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
EXAMPLE 8,
A method for preparing a liquid propyl silicone resin blend for personal care, which comprises the following steps:
under the condition of room temperature, adding 11.66mol of deionized water and 7.49mol of toluene into a three-port reactor with a thermometer, starting mechanical stirring, and stirring until the mixture is uniformly mixed; adding 3mol of n-propyl triethoxysilane into a container, continuously stirring, dropwise adding 0.08mol of 98% concentrated sulfuric acid, setting the stirring speed to 280rpm, starting circulating water, heating to 50 ℃, and reacting for 50min under the condition; continuously heating to 85 ℃, continuously reacting for 6 hours after the solvent is distilled off, washing with a large amount of deionized water after the reaction is finished until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the washing liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain the propyl silicone resin (284.8 g), wherein the viscosity of the resin can reach 15000mPas (25 ℃), the refractive index is 1.4420 (25 ℃), and the molecular weight is 25000 (Mw).
Adding isododecane (about 95 g) as a blending solvent into the prepared propyl silicone resin according to a mass ratio of 3:1, and carrying out bubble-free blending to obtain a liquid propyl silicone resin blend product for personal care, wherein the viscosity of the blend is 200mPas (25 ℃), the refractive index is 1.4333 (25 ℃), and a film can be formed on a clean and flat glass plate (the film is processed in a blast drying box at 50 ℃ for 24 hours).
Compared with phenyl silicone resin, phenyl vinyl silicone resin and liquid phenyl silicone resin blends prepared in a laboratory by a similar method, the prepared propyl silicone resin and liquid blend thereof have better adhesiveness (high viscosity and strong adhesive force), film forming property (rapid film forming, no falling off and no bonding), elasticity and lubricity (propyl is more flexible compared with phenyl and propyl can be freely bent and rotated).
EXAMPLE 9,
The liquid propyl silicone resin blend product prepared in the example 1 is used for replacing a film forming agent polyvinylpyrrolidone/hexadecene copolymer commonly used in eye shadow cosmetics, other components are unchanged, and after the liquid propyl silicone resin blend product is placed for 7 days at normal temperature, the film type is not changed substantially compared with the film type, and the film type has luster;
eyebrows containing polyvinylpyrrolidone/hexadecene copolymer film former developed cracks and were matt after 3 days of placement.
EXAMPLE 10,
The liquid propyl silicone resin blend product prepared in the example 1 is used for replacing a film forming agent acrylic resin and dimethyl siloxane copolymer commonly used in lipstick, other components are unchanged, and after the liquid propyl silicone resin blend product is placed for 7 days at normal temperature, the film type is not changed substantially compared with the film type, and the film type has luster;
lipsticks containing an acrylic resin and dimethicone copolymer developed cracking and matt after 2 days of standing.
EXAMPLE 11,
The liquid propyl silicone resin blend product prepared in the example 2 is used for replacing film forming agent acrylic copolymer emulsion commonly used in lipstick, other components are unchanged, and after the film is placed for 7 days at normal temperature, the film type is not changed substantially compared with the initial film type, and the film has luster;
whereas lipsticks containing the acrylic copolymer emulsion develop cracks and are matt after 3 days of standing.
Therefore, the propyl silicone resin provided by the invention can obviously improve the film forming effect of cosmetics and prolong the service life of the cosmetics.
Claims (10)
1. A method of preparing propyl silicone resin comprising: n-propyl triethoxysilane is used as a raw material, and hydrolysis polymerization reaction is carried out in the presence of water, an organic solvent and an acid catalyst to obtain propyl silicone resin;
the acid catalyst is trifluoromethyl sulfonic acid;
the molar ratio of the n-propyl triethoxysilane to the water to the acid catalyst is as follows: 3:11-12:0.056-0.08;
the hydrolysis polymerization reaction is operated as follows: under the condition of room temperature, adding water and an organic solvent into a three-port reactor with a thermometer, starting mechanical stirring, and stirring until the water and the organic solvent are uniformly mixed; adding n-propyl triethoxysilane, continuously stirring, then dropwise adding trifluoromethanesulfonic acid, stirring, starting circulating water, heating to 50-60 ℃, and reacting for 30-50 min under the condition; continuously heating to 80-85 ℃, continuously reacting for 5-6 h after evaporating the solvent, washing with deionized water after the reaction is finished, separating liquid, and obtaining the propyl silicone resin after short-path distillation.
2. The method according to claim 1, characterized in that:
the organic solvent is one or a mixture of more of ethanol, cyclohexane and toluene.
3. Propyl silicone resins obtainable by the process of claim 1 or 2.
4. A propyl silicone resin as set forth in claim 3, characterized in that: the obtained propyl silicone resin is clear and transparent viscous liquid, the viscosity of the propyl silicone resin is 10000-30000 mPas, and the refractive index of the propyl silicone resin is 1.4400-1.4500.
5. A liquid propyl silicone resin blend product comprising the propyl silicone resin of claim 3 or 4 and a blend solvent;
the blending solvent is any one of decamethyl cyclopentasiloxane and isododecane;
the mass ratio of the propyl silicone resin to the blend solvent is as follows: 1:1/3-1.
6. The liquid propyl silicone resin blend product of claim 5, wherein: the liquid propyl silicone resin blend product is clear and transparent liquid, the viscosity of the liquid propyl silicone resin blend product is 100-300 mPas, and the refractive index of the liquid propyl silicone resin blend product is 1.4100-1.4400.
7. Use of the propyl silicone resin of claim 3 or 4 or the liquid propyl silicone resin blend product of claim 5 or 6 in a personal care product.
8. The use according to claim 7, characterized in that: the personal care product is: and (5) color cosmetics.
9. The use according to claim 7, characterized in that: the personal care product is: liquid foundations, body lotions, sunscreens, lipsticks, hair care compositions.
10. A personal care product comprising the propyl silicone resin of claim 3 or 4 or the liquid propyl silicone resin blend product of claim 5 or 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011329423.XA CN114539528B (en) | 2020-11-24 | 2020-11-24 | Preparation method of liquid propyl silicone resin blend for personal care |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011329423.XA CN114539528B (en) | 2020-11-24 | 2020-11-24 | Preparation method of liquid propyl silicone resin blend for personal care |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114539528A CN114539528A (en) | 2022-05-27 |
| CN114539528B true CN114539528B (en) | 2023-11-24 |
Family
ID=81660676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011329423.XA Active CN114539528B (en) | 2020-11-24 | 2020-11-24 | Preparation method of liquid propyl silicone resin blend for personal care |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114539528B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0315568D0 (en) * | 2003-07-03 | 2003-08-13 | Dow Corning | Skin care compositions containing functionalized liquid silicone resins |
| CN103804688A (en) * | 2013-12-24 | 2014-05-21 | 北京化工大学 | High-activity organic silicon resin and preparation method thereof |
| CN103965481A (en) * | 2013-02-01 | 2014-08-06 | 常州化学研究所 | Epoxy function group-containing silicone resin preparation method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040202637A1 (en) * | 2003-04-11 | 2004-10-14 | Masato Yoshioka | Hair treatment agent, shampoo and hair coloring agent |
| CN105906810B (en) * | 2016-04-26 | 2019-08-06 | 广东标美硅氟新材料有限公司 | A kind of preparation method of organopolysiloxane resins |
-
2020
- 2020-11-24 CN CN202011329423.XA patent/CN114539528B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0315568D0 (en) * | 2003-07-03 | 2003-08-13 | Dow Corning | Skin care compositions containing functionalized liquid silicone resins |
| CN103965481A (en) * | 2013-02-01 | 2014-08-06 | 常州化学研究所 | Epoxy function group-containing silicone resin preparation method |
| CN103804688A (en) * | 2013-12-24 | 2014-05-21 | 北京化工大学 | High-activity organic silicon resin and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 耐高温硅树脂的合成;赵维等;《有机硅材料》;20080925;第22卷(第5期);第273-276页 * |
| 马振友等.硅树脂.《皮肤美容化妆品制剂手册（第二版）》.中医古籍出版社,2015,第435页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114539528A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102993404B (en) | Photosensitive fluorosilicone segmented urethane acrylate oligomer and preparation method thereof | |
| DE60312194T2 (en) | SILICON ELASTOMER COMPOSITIONS | |
| JPH11222556A (en) | Method for stopping postcuring in silicone elastomer | |
| CN112062964A (en) | UV/moisture dual-curing acrylate polysiloxane and preparation method and application thereof | |
| CN108252102B (en) | A kind of the silicon rubber leather and its coating process of UV resistant and hydrolysis | |
| CN103044683A (en) | Modified MQ silicone resin and preparation method thereof | |
| WO2018066572A1 (en) | Novel resin-linear organopolysiloxane block copolymer, use of same, and method for producing same | |
| CN109608640A (en) | A kind of high molecular weight MQ silicone resin and its synthetic method, application | |
| CN115449235B (en) | Modified titanium dioxide and preparation method thereof | |
| CN107033296A (en) | Extra-weather-proof polysiloxane-modified acrylic resin and finish paint preparation method | |
| CN109251301A (en) | A kind of preparation method and composition of the aqueous oligomer of photopolymerization organosilicon polyurethane acrylate | |
| CN105218822B (en) | Phenyl hydrogen-containing silicon oil for high folding LED liquid-packing glue and preparation method thereof | |
| CN104140533A (en) | Vinyl-containing phenyl hydro silicone resin and preparation method thereof | |
| EP2655480B1 (en) | Polysiloxane-n, n-dihydrocarbylene sugar-modified multiblock copolymer and method for producing the same | |
| CN114106333B (en) | Polyurethane acrylate hybrid multi-arm star-shaped silicone resin, and preparation method and application thereof | |
| CN114539528B (en) | Preparation method of liquid propyl silicone resin blend for personal care | |
| CN114539526B (en) | Preparation method of liquid propyl silicone resin blend for personal care | |
| US5256754A (en) | Hydrogenpolysiloxanes and methods of making | |
| CN105199109A (en) | Preparation method of MDT-type phenyl methyl silicone oil for cosmetics | |
| KR20220111291A (en) | Methods for preparing polysiloxazanes and methods of using polysiloxazanes for preparing amino-functional polyorganosiloxanes | |
| JP2715652B2 (en) | Method for producing hydrogen polysiloxane | |
| CN114907767B (en) | Antibacterial silicone rubber coating and preparation method thereof | |
| JP2000026607A (en) | Fluorosilicone rubber cured material powder and cosmetic containing this | |
| JP2012136587A (en) | Polysiloxane-hydrocarbylene aminohydrocarbylene multiblock copolymer and method for producing the same | |
| CN112194980B (en) | Hydrophobic coating agent for automobile windshield and preparation method thereof |
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 |