CN117801316A - Composite polyether silicone oil emulsifier and preparation method and application thereof - Google Patents
Composite polyether silicone oil emulsifier and preparation method and application thereof Download PDFInfo
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- 229920002545 silicone oil Polymers 0.000 title claims abstract description 79
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 77
- 229920000570 polyether Polymers 0.000 title claims abstract description 77
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 19
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- LWWKLKSYKPNLMG-UHFFFAOYSA-N tris(trimethylsilyloxy)silyl acetate Chemical compound CC(=O)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C LWWKLKSYKPNLMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005741 alkyl alkenyl group Chemical group 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- VEJBQZZDVYDUHU-UHFFFAOYSA-N ethenyl-hydroxy-dimethylsilane Chemical compound C[Si](C)(O)C=C VEJBQZZDVYDUHU-UHFFFAOYSA-N 0.000 claims description 2
- FDTBETCIPGWBHK-UHFFFAOYSA-N hydroxy-dimethyl-phenylsilane Chemical compound C[Si](C)(O)C1=CC=CC=C1 FDTBETCIPGWBHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- WVMSIBFANXCZKT-UHFFFAOYSA-N triethyl(hydroxy)silane Chemical compound CC[Si](O)(CC)CC WVMSIBFANXCZKT-UHFFFAOYSA-N 0.000 claims description 2
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 2
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 claims 1
- YBRNUJSXEIBYFU-UHFFFAOYSA-N hydroxy(phenyl)silane Chemical compound O[SiH2]C1=CC=CC=C1 YBRNUJSXEIBYFU-UHFFFAOYSA-N 0.000 claims 1
- -1 polysiloxane Polymers 0.000 abstract description 19
- 230000001804 emulsifying effect Effects 0.000 abstract description 6
- 238000004821 distillation Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 4
- 101150065749 Churc1 gene Proteins 0.000 description 4
- 102100038239 Protein Churchill Human genes 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- 238000011179 visual inspection Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- NRTJGTSOTDBPDE-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C NRTJGTSOTDBPDE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FSIJKGMIQTVTNP-UHFFFAOYSA-N bis(ethenyl)-methyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C=C)C=C FSIJKGMIQTVTNP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 208000024693 gingival disease Diseases 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- FCVNATXRSJMIDT-UHFFFAOYSA-N trihydroxy(phenyl)silane Chemical compound O[Si](O)(O)C1=CC=CC=C1 FCVNATXRSJMIDT-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a composite polyether silicone oil emulsifier and a preparation method and application thereof. The emulsifier comprises polyether modified silicone oil and silanol with the mass ratio of (80-99): 1-20, preferably (90-99): 1-10. The emulsifier has wide application range, strong emulsifying capacity and high emulsifying stability, is particularly suitable for a water-in-oil system containing high-viscosity polysiloxane, and meets market requirements more.
Description
Technical Field
The invention relates to an organosilicon emulsifier, in particular to a composite polyether silicone oil emulsifier and a preparation method and application thereof.
Background
At present, the main structures of the common organosilicon emulsifying agents in the market are two types: polyether modified silicone oils and alkyl/polyether co-modified silicone oils. The polyether modified silicone oil is obtained by performing hydrosilylation reaction on allyl polyether and hydrogen-containing polydimethylsiloxane under the action of transition metal catalysts such as platinum, palladium, rhodium and the like. However, for emulsification of systems containing high viscosity polysiloxanes (viscosity of several hundred thousand to several million cp), or even crude gums (viscosity of several million to several tens of millions cp), it is difficult to achieve good emulsification and dispersion effects by merely changing the structure of the polyether modified silicone oil emulsifier, and thus the molecular weight and HLB value of the emulsifier.
The high-viscosity polysiloxane has excellent softness, hydrophobicity and wettability, so that the high-viscosity polysiloxane is widely applied in the field of cosmetics, and products such as face cream, foundation and the like are endowed with good smoothness. However, the strong hydrophobicity and oil viscosity present in itself lead to difficult emulsification, especially of polysiloxanes with viscosities exceeding one million cp. At present, the method is mainly adopted, when a high-viscosity polysiloxane system is emulsified, ring bodies such as d4, d5 or dm c are added for dilution and viscosity reduction, and the content of the ring bodies is limited in the cosmetic field, so that the amount of the high-viscosity polysiloxane which can be added into the system is limited.
The patent US8258192B2 uses low molecular weight silicone oil and an emulsifier to add to the high viscosity polysiloxane, avoiding the introduction of siloxane rings. However, this method can be used only for dispersing polysiloxanes of 50 ten thousand cp or less, but has little effect on emulsification of polysiloxanes or raw gums of higher viscosity.
The patent CN110885559B adopts a macromolecular amphoteric surfactant and isomeric alcohol polyoxyethylene ether to compound, and the dimethyl silicone oil with the viscosity exceeding 10000cp is emulsified. However, the method is only suitable for an oil-in-water system, and oil return and demulsification are easy to occur when the method is used for a water-in-oil system.
Therefore, a new emulsifier is required to be provided, which has high-efficiency emulsifying capacity for a high-viscosity polysiloxane system and meets the use of the high-viscosity polysiloxane in the field of cosmetics.
Disclosure of Invention
In order to solve the technical problems, the invention provides a composite polyether silicone oil emulsifier and a preparation method and application thereof. The emulsifier has wide application range, strong emulsifying capacity and high emulsifying stability, is particularly suitable for a water-in-oil system containing high-viscosity polysiloxane, and meets market requirements more.
A compound polyether silicone oil emulsifier comprises polyether modified silicone oil shown in formula I, and silanol shown in formula II and/or formula III;
wherein R is 1 、R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aromatic hydrocarbon group, an alkenyl group; r is R 3 Alkyl, alkoxy, alkyl ester groups having 1 to 5 carbon atoms or hydroxyl groups; wherein m, n, o, x, y refers to the polymerization degree, and the value ranges are respectively: m=0-10, n=1-40, o=40-400, x=1-20, y=0-20;
R 4 、R 5 、R 6 each independently represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aromatic hydrocarbon group, an alkylhydroxyl group, an alkylalkenyl group, and wherein at least one of the groups is a hydroxyl group or an alkylhydroxyl group; wherein, p and q refer to polymerization degree, and the value ranges are respectively as follows: p=0-5, q=1-10;
R 7 、R 8 、R 9 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a siloxy group, an alkylhydroxyl group, an alkenyl group, or an aromatic hydrocarbon group.
As a preferable scheme of the invention, the mass ratio of the polyether modified silicone oil to the silanol is (80-99): 1-20, preferably (90-99): 1-10.
As a preferred embodiment of the present invention, the silanol is selected from one or more of tris (trimethylsiloxy) silanol, diphenyl silanediol, trimethylsilanol, phenylsilanetriol, triphenyl silanol, dimethylphenyl silanol, dimethylvinyl silanol, triethylsilanol.
As a preferable scheme of the invention, the polyether modified silicone oil is prepared from hydrogen-containing silicone oil and allyl polyether through hydrosilylation.
As a preferred embodiment of the present invention, the molar ratio of Si-H of the hydrogen-containing silicone oil to vinyl of the allyl polyether is 1 (1.2-2), preferably 1 (1.2-1.5).
As a preferable scheme of the invention, the hydrogen-containing silicone oil has the viscosity of 100-1000cp and the Si-H content of 400-1000ppm.
Preferably, the allyl polyether is of molecular weight 350-1500, EO in structure: the molar ratio of PO is 1 (0-20).
As a preferred embodiment of the present invention, the hydrosilylation reaction is carried out in the presence of a transition metal catalyst, preferably a platinum-containing catalyst;
preferably, the platinum-containing catalyst is selected from one or more of chloroplatinic acid, vinyl siloxane-platinum complexes, more preferably one or more of chloroplatinic acid, tetramethyl divinyl disiloxane-platinum complexes, tetramethyl tetravinyl cyclotetrasiloxane-platinum complexes;
preferably, the platinum-containing catalyst is used in an amount of 1 to 20ppm, preferably 2 to 10ppm, based on the sum of the mass of the hydrogen-containing silicone oil and the allyl polyether, based on the content of metallic platinum in the platinum-containing catalyst.
As a preferred embodiment of the present invention, the hydrosilylation reaction is carried out at a reaction temperature of 60 to 130 ℃, preferably 80 to 110 ℃ for a reaction time of 1 to 120min, preferably 10 to 40min. The catalyst may be deactivated when the reaction temperature is too high, and part of polyether is decomposed to generate aldehyde ketone micromolecules; too low reaction temperature results in too low reaction speed, resulting in low reaction conversion rate; the reaction time is 1-120min, preferably 10-40min, and too short reaction time can result in low reaction conversion rate and too long reaction time can result in high system color number.
After the hydrosilylation reaction, the polyether modified silicone oil is purified by a post-treatment method commonly used in the field, such as adsorption filtration, and then reduced pressure distillation to remove impurities to obtain a pure product.
Wherein the purpose of adsorption filtration is to remove gel suspended matters generated by side reaction and reduce color number, preferably, one of activated carbon, diatomite, calcium carbonate and silica micropowder is used for adsorption, more preferably, activated carbon is used for adsorption; the adsorption condition is 40-70 ℃/1-5h, preferably 50-60 ℃/2-4h, and the filtration operation adopts a 1-5 μm filter membrane, preferably a 1-3 μm filter membrane.
The purpose of the reduced pressure distillation is to remove unreacted allyl polyether and isomerized propenyl polyether and reduce the odor source of the product, preferably, short-path devolatilization equipment is selected to realize the separation process, and the reduced pressure distillation condition is 150-200 ℃ and the gauge pressure is 20-50Pa.
A process for preparing the composite polyether-silicone oil emulsifier as described above, which comprises mixing polyether-modified silicone oil and silanol at 10-60deg.C, preferably 20-40deg.C for 10-60min, preferably 20-40min.
The use of a compound polyether silicone oil emulsifier as hereinbefore described in highly viscous silicone systems, in particular in silicone systems having a viscosity in excess of 100 tens of kilocp.
The invention has the beneficial effects that:
1. the composite polyether modified silicone oil emulsifier obtained by the invention can efficiently emulsify a high-viscosity polysiloxane-containing system due to containing silanol small molecules, and has strong emulsifying capacity;
2. in the emulsifier product obtained by the invention, the silanol small molecules have a certain HLB value, and the emulsifier product has good compatibility with polyether modified silicone oil, stable storage performance and high emulsion stability;
3. the preparation method adopted by the invention is simple and easy to operate, and is suitable for industrial mass production.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw materials and the reagents of the invention are all commercially available without any particular description.
The main test methods employed in the following examples of the present invention are as follows:
the method for testing the content of the silicon and the hydrogen comprises the following steps: determination was performed by infrared spectroscopy (IR) and nuclear magnetic resonance (29 Si-NMR);
the viscosity test method comprises the following steps: measuring by using a rotary viscometer;
the color number testing method comprises the following steps: measuring by using a colorimeter;
volatile matter testing method: the mass change was measured using a forced air oven 105 ℃/3 h.
Preparation of Hydrogen-containing Silicone oil
In a reactor with a stirrer and a thermometer, 930g of octamethyl cyclotetrasiloxane, 30g of high hydrogen silicone oil (DC-1107) and 35g of hexamethyldisiloxane were successively added, and 1g of trifluoromethanesulfonic acid was allowed to equilibrate at 60℃for 4 hours. After the reaction is finished, adding 2g of calcium carbonate to neutralize the trifluoromethanesulfonic acid in the system, filtering to obtain clear transparent oily liquid, and carrying out reduced pressure distillation on the obtained product by adopting short-path devolatilization equipment to remove unreacted octamethyl cyclotetrasiloxane, wherein the reduced pressure distillation condition is 150 ℃/50Pa, so as to obtain the hydrogen-containing silicone oil I. The viscosity of the hydrogen-containing silicone oil I is 230cp, the volatile component is less than 0.5%, and the Si-H content is 480ppm.
In a reactor with a stirrer and a thermometer, 900g of octamethyltetrasiloxane, 57g of 1,3,5, 7-tetramethylcyclotetrasiloxane and 12g of tetramethyldisiloxane were successively added, and 1g of trifluoromethanesulfonic acid was allowed to react in equilibrium at 60℃for 4 hours. After the reaction is finished, adding 2g of calcium carbonate to neutralize the trifluoromethanesulfonic acid in the system, filtering to obtain clear transparent oily liquid, and carrying out reduced pressure distillation on the obtained product by adopting short-path devolatilization equipment to remove unreacted octamethyl cyclotetrasiloxane, wherein the reduced pressure distillation condition is 150 ℃/50Pa, so as to obtain hydrogen-containing silicone oil II. The viscosity of the hydrogen-containing silicone oil II is 960cp, the volatile component is less than 0.5%, and the Si-H content is 970ppm.
In a reactor with a stirrer and a thermometer, 900g of octamethyl cyclotetrasiloxane, 55g of high hydrogen silicone oil (DC-1107) and 50g of divinyl tetramethyldisiloxane are added in sequence, and 1g of trifluoromethanesulfonic acid is subjected to an equilibrium reaction at 60℃for 4 hours. After the reaction is finished, adding 2g of calcium carbonate to neutralize the trifluoromethanesulfonic acid in the system, filtering to obtain clear transparent oily liquid, and carrying out reduced pressure distillation on the obtained product by adopting short-path devolatilization equipment to remove unreacted octamethyl cyclotetrasiloxane, wherein the reduced pressure distillation condition is 150 ℃/50Pa, so as to obtain the hydrogen-containing silicone oil III. The viscosity of the hydrogen-containing silicone oil III is 120cp, the volatile component is less than 0.5%, and the Si-H content is 720ppm.
[ PREPARATION EXAMPLE 2 ]
400g of hydrogen-containing silicone oil I and 160g of allyl polyether ZS-950 (CH) are sequentially added into a 1L three-neck flask 2 ＝CHCH 2 (OC 2 H 4 ) 15 (OC 3 H 6 ) 3 OH), at N 2 Heating to 80 ℃ under the atmosphere, adding a Kanster catalyst (5 ppm of the total mass of hydrogen-containing silicone oil and allyl polyether based on platinum), and reacting for 0.5h at 80 ℃ to obtain light yellow slightly turbid liquid. Adding 6g of active carbon into the system, adsorbing for 3 hours at 60 ℃, filtering at positive pressure to obtain clear transparent oily liquid, and carrying out reduced pressure distillation by adopting short-path devolatilization equipment to remove unreacted allyl polyether and propylene polyether generated by rearrangement, wherein the distillation condition is 150 ℃/50Pa, so as to obtain polyether modified silicone oil I. In the structural formula, R 1 Is methyl, R 2 Is a hydrogen atom, R 3 For hydroxyl, m=0, n=2, o=58, x=15, y=3.
Into a 1L three-necked flask, 300g of hydrogen-containing silicone oil II and 200g of allyl polyether APEG-900 (CH) were sequentially added 2 ＝CHCH 2 (OC 2 H 4 ) 20 OH), at N 2 Heating to 80 ℃ under the atmosphere, adding a Kanster catalyst (5 ppm of the total mass of hydrogen-containing silicone oil and allyl polyether based on platinum), and reacting for 0.5h at 80 ℃ to obtain light yellow slightly turbid liquid. Adding 6g of diatomite into the system, adsorbing for 3 hours at 60 ℃, filtering at positive pressure to obtain clear transparent oily liquid, and carrying out reduced pressure distillation by adopting short-path devolatilization equipment to remove unreacted allyl polyether and propylene polyether generated by rearrangement, wherein the distillation condition is 150 ℃/50Pa, so as to obtain polyether modified silicone oil II. In the structural formula, R 1 Is methyl, R 2 Is a hydrogen atom, R 3 For hydroxyl, m=2, n=10, o=164, x=20, y=0.
Into a 1L three-necked flask, 400g of hydrogen-containing silicone oil I and 150g of allyl polyether ZRB-1500 (CH) 2 ＝CHCH 2 (OC 2 H 4 ) 14 (OC 3 H 6 ) 14 OCH 3 ) At N 2 Heating to 80 ℃ under the atmosphere, adding a Kanster catalyst (6 ppm of the total mass of hydrogen-containing silicone oil and allyl polyether based on platinum), and reacting for 0.5h at 80 ℃ to obtain light yellow slightly turbid liquid. Adding 6g of active carbon into the system, adsorbing for 3 hours at 60 ℃, filtering at positive pressure to obtain clear transparent oily liquid, and carrying out reduced pressure distillation by adopting short-path devolatilization equipment to remove unreacted allyl polyether and propylene polyether generated by rearrangement, wherein the distillation condition is 150 ℃/50Pa, so as to obtain polyether modified silicone oil III. In the structural formula, R 1 Is vinyl, R 2 Is a hydrogen atom, R 3 Methoxy, m=1, n=1, o=58, x=14, y=14.
350g of hydrogen-containing silicone oil III and 250g of allyl polyether DS-3 (CH) are sequentially added into a 1L three-neck flask 2 ＝CHCH 2 (OC 2 H 4 ) 12 (OC 3 H 6 ) 3 OH), at N 2 Heating to 80 ℃ under the atmosphere, adding a Kanster catalyst (5 ppm of the total mass of hydrogen-containing silicone oil and allyl polyether based on platinum), and reacting for 0.5h at 80 ℃ to obtain light yellow slightly turbid liquid. Adding 6g of active carbon into the system, adsorbing for 3 hours at 60 ℃, filtering at positive pressure to obtain clear transparent oily liquid, and carrying out reduced pressure distillation by adopting short-path devolatilization equipment to remove unreacted allyl polyether and propylene polyether generated by rearrangement, wherein the distillation condition is 150 ℃/50Pa, so as to obtain polyether modified silicone oil IV. In the structural formula, R 1 Is methyl, R 2 Is a hydrogen atom, R 3 For hydroxyl, m=0, n=3, o=45, x=12, y=3.
[ example 1 ]
100g of polyether modified silicone oil I and 5g of tris (trimethylsiloxy) silanol are mixed, stirred and mixed for 40min at 20 ℃ to obtain the composite polyether modified silicone oil emulsifier, wherein the appearance (visual inspection) of the composite polyether modified silicone oil emulsifier is colorless transparent liquid, the refractive index is 1.417, the viscosity is 750cp, the volatile component is 1%, and the color number is 16.
[ example 2 ]
100g of polyether modified silicone oil II and 3g of diphenyl silicon glycol are mixed, stirred and mixed for 30min at 30 ℃ to obtain the composite polyether modified silicone oil emulsifier, wherein the appearance (visual inspection) of the composite polyether modified silicone oil emulsifier is colorless transparent liquid, the refractive index is 1.42, the viscosity is 900cp, the volatile component is 1.2%, and the color number is 18.
[ example 3 ]
100g of polyether modified silicone oil III and 4g of trimethylsilanol are mixed, stirred and mixed for 20min at 40 ℃ to obtain the composite polyether modified silicone oil emulsifier, wherein the appearance (visual inspection) of the composite polyether modified silicone oil emulsifier is colorless transparent liquid, the refractive index is 1.418, the viscosity is 840cp, the volatile component is 0.97%, and the color number is 12.
[ example 4 ]
100g of polyether modified silicone oil IV and 4g of phenyl silicone triol are mixed, stirred and mixed for 40min at 30 ℃ to obtain the composite polyether modified silicone oil emulsifier, wherein the appearance (visual inspection) of the composite polyether modified silicone oil emulsifier is colorless transparent liquid, the refractive index is 1.422, the viscosity is 1050cp, the volatile component is 1.1%, and the color number is 15.
[ application examples 1 to 4 ]
The compound polyether modified silicone oil prepared in each example is used as an emulsifier, and different foundation solutions in application examples 1-4 are prepared by adopting the formula in Table 1. The preparation method comprises the following steps:
and (3) uniformly mixing the material A and the material B at 75 ℃, uniformly mixing by using a homogenizer, cooling to room temperature, adding the material C into the system, and uniformly mixing by using the homogenizer to obtain the powder base solution.
Table 1, foundation liquid formulation
[ comparative application example 1 ]
A powder base solution was prepared in substantially the same manner as in application example 1 except that 105g of tris (trimethylsiloxy) silanol was substituted for the emulsifier.
[ comparative application example 2 ]
A powder base liquid was prepared in substantially the same manner as in application example 1 except that 105g of polyether-modified silicone oil I was replaced with the emulsifier.
The compositions provided in application examples 1-4 and comparative application examples 1-2 were subjected to the performance test in Table 2, and the results were as follows:
TABLE 2 Performance test results
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. A compound polyether silicone oil emulsifier is characterized by comprising polyether modified silicone oil shown in a formula I and silanol shown in a formula II and/or a formula III;
wherein R is 1 、R 2 Each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aromatic hydrocarbon group, an alkenyl group; r is R 3 Alkyl, alkoxy, alkyl ester groups having 1 to 5 carbon atoms or hydroxyl groups; wherein m, n, o, x, y refers to the polymerization degree, and the value ranges are respectively: m=0-10, n=1-40, o=40-400, x=1-20, y=0-20;
R 4 、R 5 、R 6 each independently represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aromatic hydrocarbon group, an alkylhydroxyl group, an alkylalkenyl group, and wherein at least one of the groups is a hydroxyl group or an alkylhydroxyl group; wherein, p and q refer to polymerization degree, and the value ranges are respectively as follows: p=0-5, q=1-10;
R 7 、R 8 、R 9 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group, a siloxy group, an alkylhydroxyl group, an alkenyl group, or an aromatic hydrocarbon group.
2. The composite polyether silicone oil emulsifier according to claim 1, wherein the mass ratio of the polyether modified silicone oil to silanol is (80-99): 1-20, preferably (90-99): 1-10.
3. The composite polyether silicone oil emulsifier according to claim 1 or 2, wherein the silanol is selected from one or more of tris (trimethylsiloxy) silanol, diphenyl silanol, trimethylsilanol, phenyl silanol, triphenyl silanol, dimethylphenyl silanol, dimethylvinyl silanol, triethylsilanol.
4. A composite polyether silicone oil emulsifier according to any one of claims 1 to 3, wherein the polyether modified silicone oil is prepared from hydrogen-containing silicone oil and allyl polyether by hydrosilylation reaction.
5. The compound polyether silicone oil emulsifier according to claim 4, wherein the molar ratio of Si-H of the hydrogen-containing silicone oil to vinyl of the allyl polyether is 1 (1.2-2), preferably 1 (1.2-1.5).
6. The composite polyether silicone oil emulsifier according to claim 4, wherein the hydrogen-containing silicone oil has a viscosity of 100-1000cp and a si-H content of 400-1000ppm.
Preferably, the allyl polyether is of molecular weight 350-1500, EO in structure: the molar ratio of PO is 1 (0-20).
7. The composite polyether silicone oil emulsifier according to any one of claims 4 to 6, wherein the hydrosilylation reaction is carried out in the presence of a transition metal catalyst, preferably a platinum-containing catalyst;
preferably, the platinum-containing catalyst is selected from one or more of chloroplatinic acid, vinyl siloxane-platinum complexes, more preferably one or more of chloroplatinic acid, tetramethyl divinyl disiloxane-platinum complexes, tetramethyl tetravinyl cyclotetrasiloxane-platinum complexes;
preferably, the platinum-containing catalyst is used in an amount of 1 to 20ppm, preferably 2 to 10ppm, based on the sum of the mass of the hydrogen-containing silicone oil and the allyl polyether, based on the content of metallic platinum in the platinum-containing catalyst.
8. The composite polyether silicone oil emulsifier according to any one of claims 4 to 7, wherein the hydrosilylation reaction is carried out at a reaction temperature of 60 to 130 ℃, preferably 80 to 110 ℃ for a reaction time of 1 to 120min, preferably 10 to 40min.
9. A process for the preparation of a composite polyether silicone oil emulsifier according to any one of claims 1 to 8, characterised in that polyether modified silicone oil and silanol are mixed at 10 to 60 ℃, preferably 20 to 40 ℃ for 10 to 60min, preferably 20 to 40min.
10. Use of a composite polyether silicone oil emulsifier according to any one of claims 1 to 8 in highly viscous silicone systems, in particular in silicone systems having a viscosity of more than 100 gcp.
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