CN114539526B - 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
- CN114539526B CN114539526B CN202011327379.9A CN202011327379A CN114539526B CN 114539526 B CN114539526 B CN 114539526B CN 202011327379 A CN202011327379 A CN 202011327379A CN 114539526 B CN114539526 B CN 114539526B
- 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 116
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 title claims abstract description 106
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000007788 liquid Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002537 cosmetic Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 claims description 8
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 8
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 238000000526 short-path distillation Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 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
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect 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
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000005357 flat glass Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 210000003491 skin Anatomy 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000005046 Chlorosilane Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 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
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 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
- 238000012512 characterization method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 210000004709 eyebrow Anatomy 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 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
- 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
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 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
- 239000007858 starting material Substances 0.000 description 1
- 230000037072 sun protection 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
- 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
-
- 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
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
-
- 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
-
- 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
- A61Q19/001—Preparations for care of the lips
-
- 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
-
- 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
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: the preparation method comprises the steps of taking n-propyl trimethoxy silane as a raw material, and carrying out hydrolytic polymerization reaction in the presence of water, an organic solvent and an acidic catalyst. 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 trimethoxy silane 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.
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 a mixture of two or more of ethanol, cyclohexane and toluene;
the molar ratio of the n-propyl trimethoxy silane to the water to the acid catalyst can be as follows: 4:11-12:0.056-0.08, specifically 4:11.66:0.056, 4:11.66:0.064 or 4:11.66:0.08;
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 trimethoxy silane, continuously stirring, dropwise adding trifluoromethyl sulfonic acid or concentrated sulfuric acid with the mass concentration of 98%, stirring, 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 out, 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 20000 to 30000mPas (25 ℃), and the refractive index of the propyl silicone resin is 1.4400 to 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, takes n-propyl trimethoxy silane as a raw material, and prepares the propyl silicone resin through hydrolytic 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) The synthetic propyl silicone resin has high viscosity (20000-30000 mPas), high refractive index (1.4400-1.4500), high thermal stability and water resistance (Si as shown in figure 3 a) 29 Characterization by NMR of Si-OH free of hydrophilic groups and free of methoxy residues (C as shown in FIG. 3 b) 13 Characterization of Si-OCH free by NMR 3 ) Is also substantially free of pungent odor and toxic methanol (gas chromatography determination<10 ppm). The prepared liquid propyl silicone resin blend product for personal care has micro viscosity (100-300 mPas), 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 (a) Si of the propyl silicone resin prepared in example 1 of the present invention 29 -NMR spectrum and (b) C 13 -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; the reagents, 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 4mol of n-propyl trimethoxy silane into a container, continuously stirring, dropwise adding 0.056mol of trifluoromethyl sulfonic 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 out, washing with a large amount of deionized water until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the liquid, and preparing propyl silicone resin (approximately 360 g) by short-path distillation (120-160 ℃ and 9-20 Pa). The resin had a viscosity of 22000mPas (25 ℃) and a refractive index of 1.4440 (25 ℃) and a molecular weight of 33000 (Mw).
Adding an equal mass blending solvent D5 (approximately 360 g) into the prepared propyl silicone resin according to the mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 120mPas (25 ℃) and a refractive index of 1.4195 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
Adding isododecane (about 120 g) as a blending solvent into the prepared propyl silicone resin according to the mass ratio of 3:1, and blending the mixture in a bubble-free way to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 220mPas (25 ℃) and a refractive index of 1.4368 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
FIG. 3 shows (a) Si of the propyl silicone resin prepared in example 1 of the present invention 29 -NMR spectrum and (b) C 13 -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 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 4mol of propyltrimethoxysilane into a container, continuously stirring, dropwise adding 0.064mol of trifluoromethanesulfonic 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 out, washing with a large amount of deionized water until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the liquid, and preparing propyl silicone resin (approximately 375 g) by short-path distillation (120-160 ℃ and 9-20 Pa). The resin had a viscosity of 24000mPas (25 ℃ C.), a refractive index of 1.4446 (25 ℃ C.) and a molecular weight of 35000 (Mw).
Adding an equal mass blending solvent D5 (approximately 375 g) into the prepared propyl silicone resin according to the mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 130mPas (25 ℃) and a refractive index of 1.4197 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
Adding isododecane (125 g) as a blending solvent into the prepared propyl silicone resin according to the mass ratio of 3:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 250mPas (25 ℃) and a refractive index of 1.4366 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
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, 3.745mol of cyclohexane, 3.745mol of toluene 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 4mol of propyltrimethoxysilane into a container, continuously stirring, dropwise adding 0.08mol of trifluoromethanesulfonic 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 out, washing with a large amount of deionized water until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (approximately 385 g). The resin had a viscosity of 28000mPas (25 ℃) and a refractive index of 1.4443 (25 ℃) and a molecular weight of 40000 (Mw).
Adding an equal mass blending solvent D5 (approximately 385 g) into the prepared propyl silicone resin according to the mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 140mPas (25 ℃) and a refractive index of 1.4200 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
Adding isododecane (about 128.33 g) as a blending solvent into the prepared propyl silicone resin according to the mass ratio of 3:1, and blending in a bubble-free way to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 270mPas (25 ℃) and a refractive index of 1.4367 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
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 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 4mol of propyltrimethoxysilane 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 out, washing with a large amount of deionized water until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (approximately 380 g). The resin had a viscosity of 25000mPas (25 ℃) and a refractive index of 1.4432 (25 ℃) and a molecular weight of 36000 (Mw).
Adding an equal mass blending solvent D5 (about 380 g) into the prepared propyl silicone resin according to the mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 140mPas (25 ℃) and a refractive index of 1.4176 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
Adding isododecane (about 126.67 g) as a blending solvent into the prepared propyl silicone resin according to the mass ratio of 3:1, and blending in a bubble-free way to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 260mPas (25 ℃) and a refractive index of 1.4345 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
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 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 4mol of propyltrimethoxysilane 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 out, washing with a large amount of deionized water until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (approximately 380 g). The resin had a viscosity of 25000mPas (25 ℃) and a refractive index of 1.4432 (25 ℃) and a molecular weight of 36000 (Mw).
Adding an equal mass blending solvent D5 (about 380 g) into the prepared propyl silicone resin according to the mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 140mPas (25 ℃) and a refractive index of 1.4176 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
Adding isododecane (about 126.67 g) as a blending solvent into the prepared propyl silicone resin according to the mass ratio of 3:1, and blending in a bubble-free way to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 260mPas (25 ℃) and a refractive index of 1.4345 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
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, 3.745mol of toluene, 3.745mol 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 4mol of propyltrimethoxysilane 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 out, washing with a large amount of deionized water until the PH of the washing liquid is more than 5 (measured by a PH meter), separating the liquid, and carrying out short-path distillation (120-160 ℃ and 9-20 Pa) to obtain propyl silicone resin (approximately 382 g). The resin had a viscosity of 27000mPas (25 ℃) and a refractive index of 1.4433 (25 ℃) and a molecular weight of 38000 (Mw).
Adding an equal mass blending solvent D5 (about 380 g) into the prepared propyl silicone resin according to the mass ratio of 1:1, and carrying out bubble-free blending to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 130mPas (25 ℃) and a refractive index of 1.4177 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
Adding isododecane (about 126.67 g) as a blending solvent into the prepared propyl silicone resin according to the mass ratio of 3:1, and blending in a bubble-free way to obtain the liquid propyl silicone resin blend product for personal care. The blend had a viscosity of 250mPas (25 ℃) and a refractive index of 1.4347 (25 ℃) and a film was formed on a clean and flat glass plate (24 h in a 50℃forced air oven).
EXAMPLE 7,
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 eyebrows (eye shadow), other components are unchanged, and after the blend product is placed for 7 days at normal temperature, the film is not substantially changed and still has luster compared with the beginning;
eyebrows containing polyvinylpyrrolidone/hexadecene copolymer film former developed cracks and were matt after 3 days of placement.
EXAMPLE 8,
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 is still glossy;
lipsticks containing an acrylic resin and dimethicone copolymer developed cracking and matt after 2 days of standing.
EXAMPLE 9,
The liquid propyl silicone resin blend product prepared in the example 2 is used for replacing the 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 is still glossy;
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.
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).
The preparation of the propyl silicone resin by taking the n-propyl trimethoxy silane as the raw material has the following advantages:
(1) Since methoxy groups hydrolyze more readily than ethoxy groups, the same amount of starting material, less acid catalyst is required for hydrolysis of n-propyl trimethoxysilane;
(2) The propyl silicone resin prepared by taking the n-propyl trimethoxy silane as the raw material has larger viscosity (better adhesiveness);
(3) The methanol contained in the propyl silicone resin prepared by taking the n-propyl trimethoxy silane as a raw material is easier to remove (the molecular weight of the methanol is smaller than that of the ethanol).
Claims (10)
1. A method of preparing propyl silicone resin comprising: n-propyl trimethoxy silane 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 trimethoxy silane to the water to the acid catalyst is as follows: 4:11-12:0.056-0.08;
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 trimethoxy silane, continuously stirring, dropwise adding trifluoromethyl sulfonic acid, stirring, 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 out, 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 a mixture of more than two 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 20000 to 30000mPas, and the refractive index of the propyl silicone resin is 1.4400 to 1.4500.
5. A liquid propyl silicone resin blend product comprising the propyl silicone resin of claim 3 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 |
---|---|---|---|
CN202011327379.9A CN114539526B (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 |
---|---|---|---|
CN202011327379.9A CN114539526B (en) | 2020-11-24 | 2020-11-24 | Preparation method of liquid propyl silicone resin blend for personal care |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114539526A CN114539526A (en) | 2022-05-27 |
CN114539526B true CN114539526B (en) | 2023-11-07 |
Family
ID=81660637
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011327379.9A Active CN114539526B (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) | CN114539526B (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1914277A (en) * | 2004-02-02 | 2007-02-14 | 陶氏康宁公司 | MQ and T-propyl siloxane resins compositions |
CN1914251A (en) * | 2004-02-02 | 2007-02-14 | 陶氏康宁公司 | MQ-T propyl siloxane resins |
CN101980693A (en) * | 2007-12-05 | 2011-02-23 | 莱雅公司 | Cosmetic make-up and/or care method using a siloxane resin and a non-volatile oil |
FR2954157A1 (en) * | 2009-12-21 | 2011-06-24 | Oreal | Method for makeup, and/or care of skin and/or lips, comprises depositing, on skin and/or lips, at least one layer of composition comprising silicone resin and volatile oil in medium, and artificially accelerating the drying of the deposit |
CN103804688A (en) * | 2013-12-24 | 2014-05-21 | 北京化工大学 | High-activity organic silicon resin and preparation method thereof |
CN104490629A (en) * | 2008-05-08 | 2015-04-08 | 迈图高新材料日本合同公司 | Cosmetic |
WO2015185329A1 (en) * | 2014-06-04 | 2015-12-10 | Beiersdorf Ag | Cosmetic shampoos having a content of silicone resins dispersed in silicone oil |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140227213A1 (en) * | 2013-02-14 | 2014-08-14 | L'oreal | Cosmetic compositions for deeper ethnic skin tones |
-
2020
- 2020-11-24 CN CN202011327379.9A patent/CN114539526B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1914277A (en) * | 2004-02-02 | 2007-02-14 | 陶氏康宁公司 | MQ and T-propyl siloxane resins compositions |
CN1914251A (en) * | 2004-02-02 | 2007-02-14 | 陶氏康宁公司 | MQ-T propyl siloxane resins |
CN101980693A (en) * | 2007-12-05 | 2011-02-23 | 莱雅公司 | Cosmetic make-up and/or care method using a siloxane resin and a non-volatile oil |
CN104490629A (en) * | 2008-05-08 | 2015-04-08 | 迈图高新材料日本合同公司 | Cosmetic |
FR2954157A1 (en) * | 2009-12-21 | 2011-06-24 | Oreal | Method for makeup, and/or care of skin and/or lips, comprises depositing, on skin and/or lips, at least one layer of composition comprising silicone resin and volatile oil in medium, and artificially accelerating the drying of the deposit |
CN103804688A (en) * | 2013-12-24 | 2014-05-21 | 北京化工大学 | High-activity organic silicon resin and preparation method thereof |
WO2015185329A1 (en) * | 2014-06-04 | 2015-12-10 | Beiersdorf Ag | Cosmetic shampoos having a content of silicone resins dispersed in silicone oil |
Non-Patent Citations (2)
Title |
---|
"乙烯基及烷基硅树脂合成、表征及氛围下N2热老化对比研究";祝文亲,等;《粘接》;20141231;第67-72,103页 * |
祝文亲,等."乙烯基及烷基硅树脂合成、表征及氛围下N2热老化对比研究".《粘接》.2014, * |
Also Published As
Publication number | Publication date |
---|---|
CN114539526A (en) | 2022-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102993404B (en) | Photosensitive fluorosilicone segmented urethane acrylate oligomer and preparation method thereof | |
CN101003686B (en) | Curable silicone rubber composition and cured product thereof | |
WO2016109992A1 (en) | Organic silicon composition for uv curing | |
CN101787244A (en) | Antifouling flash insulator coating and preparation method thereof | |
KR0135514B1 (en) | Organosilicone resin coating compositions | |
CN112062964A (en) | UV/moisture dual-curing acrylate polysiloxane and preparation method and application thereof | |
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 | |
CN105754087B (en) | A kind of preparation method of end polyether silicon | |
CN109251301A (en) | A kind of preparation method and composition of the aqueous oligomer of photopolymerization organosilicon polyurethane acrylate | |
CN107033296A (en) | Extra-weather-proof polysiloxane-modified acrylic resin and finish paint preparation method | |
CN115449235B (en) | Modified titanium dioxide and preparation method thereof | |
CN104140533A (en) | Vinyl-containing phenyl hydro silicone resin and preparation method thereof | |
CN105218822B (en) | Phenyl hydrogen-containing silicon oil for high folding LED liquid-packing glue and preparation method thereof | |
CN101508852B (en) | Glass-hard organosilicon protective coating, preparation and uses thereof | |
EP2655480B1 (en) | Polysiloxane-n, n-dihydrocarbylene sugar-modified multiblock copolymer and method for producing the same | |
US5248750A (en) | Organopolysiloxanes and methods of making | |
CN114539526B (en) | Preparation method of liquid propyl silicone resin blend for personal care | |
CN114539528B (en) | Preparation method of liquid propyl silicone resin blend for personal care | |
GB2443626A (en) | Fluorosilicones | |
EP4065630A1 (en) | Processes for making polysiloxazanes and using same for producing amino-functional polyorganosiloxanes | |
JP2715652B2 (en) | Method for producing hydrogen polysiloxane | |
Zheng et al. | UV-curable optical transparent, aging resistance, liquid-repellent coatings based on a novel photosensitive fluorinated polysiloxane with long perfluoroalkyl side chains | |
CN114907767B (en) | Antibacterial silicone rubber coating and preparation method thereof | |
CN114106333B (en) | Polyurethane acrylate hybrid multi-arm star-shaped silicone resin, and preparation method and application 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 |