Thermoplastic polysilsesquioxane resin as well as preparation method and application thereof

Abstract

The invention provides thermoplastic polysilsesquioxane resin as well as a preparation method and application thereof. The thermoplastic polysilsesquioxane resin comprises an M unit represented by R < 13 > SiO < 1 / 2 > and a T unit represented by R < 2 > SiO < 3 / 2 >, the molar ratio of the M unit to the T unit is (0.01-3): 1; r1 is selected from substituted or unsubstituted C1-C8 linear chain or branched chain alkyl, R2 is selected from substituted or unsubstituted C1-C30 alkane, more than 60 mol% of R2 is propyl, and more than 1 mol% of R2 is octyl; the substituted substituent group is selected from any one of aryl, alkyl and alkenyl. The thermoplastic polysilsesquioxane resin can be used as a film-forming agent to solve the problem of skin tightness, has good moisturizing, color fixing and makeup maintaining effects, and can be widely applied to the fields of cosmetics and personal care products.

Description

Technical Field

[0001] The invention belongs to the technical field of organic silicon, and specifically relates to a thermoplastic polysilsesquioxane and a preparation method and application thereof. Background Art

[0002] Cosmetic film formers are mainly used for protecting the skin surface. When applied to the skin surface, they can achieve the effects of moisturizing, fixing color, and lasting makeup. They are widely used in cosmetics and personal care products. Silicone film formers are one of the commonly used film formers. For example, the patent with publication number CN114191318A discloses an anhydrous liquid composition comprising oil, film-forming polymer, monoalcohol and particulate material. The anhydrous liquid composition disclosed therein preferably comprises in a physiologically acceptable medium: a) an oil phase; the oil phase comprises: i) at least one non-volatile oil, and ii) at least one volatile hydrocarbon oil, and b) at least one monoalcohol containing from 2 to 8 carbon atoms, and c) at least one lipophilic film-forming polymer selected from the following: (i) MQ type silicone resin, (ii) silsesquioxane resin, (iii) vinyl polymer grafted with carbosiloxane dendrimer, (iv) mixtures thereof, and d) at least one particulate material, wherein the composition comprises at least 15% by weight of one or more non-volatile oils relative to the total weight of the composition. The organosilicon film-forming agents disclosed in the patent, namely, MQ type organosilicon resin, silsesquioxane resin and vinyl polymer grafted with carbosiloxane dendritic polymer, have good lipophilicity and will not cause discomfort when applied to the skin.

[0003] Patent publication number CN104271110A discloses a cosmetic composition containing MQ silicone resin and propyl silsesquioxane resin, which specifically discloses that the cosmetic composition contains MQ silicone resin and propyl silsesquioxane resin and is used for moisturizing the skin; the cosmetic composition contains MQ silicone resin and propyl silsesquioxane resin and is used for reducing skin tightness; and discloses that a composition containing only MQ resin or only polypropyl silsesquioxane resin has low satisfaction with respect to dryness and tightness.

[0004] Therefore, the current organosilicon film-forming agents have the problem that they need to be used in combination to exhibit excellent moisturizing properties and reduce tightness, and cannot meet the needs of reducing tightness when used alone. Summary of the invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a thermoplastic polysilsesquioxane and a preparation method and application thereof. The thermoplastic polysilsesquioxane resin as a film-forming agent can solve the problem of tightness without being compounded with other film-forming agents, and can achieve good moisturizing, color fixing and makeup holding effects.

[0006] To achieve this object, the present invention adopts the following technical solutions: In a first aspect, the present invention provides a thermoplastic polysilsesquioxane resin, wherein the thermoplastic polysilsesquioxane resin comprises R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 ; The molar ratio between the M unit and the T unit is (0.01-3):1; The R 1 are independently selected from substituted or unsubstituted C1-C8 straight or branched alkyl groups, R 2 are independently selected from substituted or unsubstituted C1-C30 alkane groups, wherein more than 60 mol% of R 2 is propyl, 1 mol% or more of R 2 is octyl; the substituted substituent is selected from any one of aryl, alkyl and alkenyl.

[0007] In the present invention, the molar ratio between the M unit and the T unit can be 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, etc.

[0008] In the present invention, the R 2 The content of propyl group can be 60 mol%, 65 mol%, 68 mol%, 70 mol%, 72 mol%, 75 mol%, 78 mol%, 80 mol%, 82 mol%, 85 mol%, 88 mol%, 90 mol%, 92 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, 99 mol%, etc.

[0009] Preferably, the molar ratio between the M unit and the T unit is (0.03-2):1.

[0010] Preferably, the R 1 Selected from methyl and ethyl.

[0011] Preferably, the R 2 The octyl content is 9 mol% to 40 mol%, for example, 9 mol%, 10 mol%, 12 mol%, 15 mol%, 18 mol%, 20 mol%, 22 mol%, 25 mol%, 28 mol%, 30 mol%, 32 mol%, 35 mol%, 38 mol%, 40 mol%, etc.

[0012] Preferably, the R 2 The content of propyl groups is 60 mol% to 91 mol%, for example, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 91 mol%, etc.

[0013] Preferably, the raw materials for preparing the thermoplastic polysilsesquioxane resin include the following components: (A) a silane having a T structural unit, wherein the silane having a T structural unit is used to form a T unit; The silane having a T structural unit includes a propyl T structural unit silane, an octyl T structural unit silane and optionally other T structural unit silanes; (B) a silane having an M structural unit; the silane having an M structural unit is used to form an M unit; (C) a catalyst; (D) organic solvents; The molar ratio between the silane having the M structural unit and the silane having the T structural unit is (0.01-3):1.

[0014] In the present invention, the molar ratio between the silane having the M structural unit and the silane having the T structural unit can be 0.01:1, 0.02:1, 0.05:1, 0.08:1, 0.1:1, 0.2:1, 0.3:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, etc.

[0015] Preferably, the molar ratio between the silane having the M structural unit and the silane having the T structural unit is (0.03-2):1.

[0016] Preferably, the molar ratio between the propyl T structural unit silane and the octyl T structural unit silane is (0.6-1): (0.05-0.4); Among them, (0.6~1) can take values ​​of 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, etc.; (0.05~0.4) The values ​​can be 0.05, 0.08, 0.1, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, etc.

[0017] Preferably, the propyl T structural unit silane includes propyltrimethyloxysilane and / or propyltriethoxysilane.

[0018] Preferably, the silane of the octyl T structural unit includes octyltrimethoxysilane and / or octyltriethoxysilane.

[0019] Preferably, the silane of the other T structural units includes one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethyloxysilane, phenyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane.

[0020] Preferably, the silane having the M structural unit includes one or more of hexamethyldisiloxane, trimethylethoxysilane, tetramethyldivinyldisiloxane, dimethylvinylethoxysilane and tetramethyldisiloxane.

[0021] Preferably, the organic solvent is one or more of toluene, xylene, heptane, octane, isododecane, isohexadecane, D40 solvent oil, D60 solvent oil, ethanol, isopropanol, butanol, and isopentyl glycol.

[0022] Preferably, the amount of the organic solvent added is 30%-60% of the total weight of component (A) and component (B), for example, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc.

[0023] Preferably, the catalyst is an acid catalyst aqueous solution and / or an alkaline catalyst aqueous solution.

[0024] Preferably, the acid catalyst is any one or more of glacial acetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0025] Preferably, the alkaline catalyst is any one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylphosphine hydroxide.

[0026] Preferably, the concentration of the acid catalyst aqueous solution is 0.1wt%-5wt%; for example, 0.1 wt%, 0.3 wt%, 0.5wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.2 wt%, 4.5 wt%, 4.8wt%, 5 wt%, etc.

[0027] Preferably, the concentration of the acid catalyst aqueous solution is 0.5 wt %-3 wt %.

[0028] Preferably, the concentration of the aqueous base catalyst solution is 0.01 wt %-0.1 wt %; for example, 0.01 wt %, 0.02 wt %, 0.03 wt %, 0.04 wt %, 0.05 wt %, 0.06 wt %, 0.07 wt %, 0.08 wt %, 0.09 wt %, 0.1 wt %, etc.

[0029] Preferably, the concentration of the aqueous base catalyst solution is 0.02 wt %-0.06 wt %.

[0030] In a second aspect, the present invention provides a method for preparing the above-mentioned thermoplastic polysilsesquioxane resin, the preparation method comprising the following steps: The composition formed by silane having T structural units, silane having M structural units, a catalyst and an organic solvent is subjected to a hydrolysis condensation reaction to obtain the thermoplastic polysilsesquioxane resin.

[0031] Preferably, the temperature of the hydrolysis condensation reaction is 70-160° C.; the time of the hydrolysis condensation reaction is 3-12 hours.

[0032] More specifically, the preparation method of the thermoplastic polysilsesquioxane resin comprises the following steps: S1. A silane having a T structural unit, a silane having an M structural unit and an organic solvent are mixed and heated to a first set temperature, an acidic catalyst is added, and the temperature is continued to rise to a second set temperature and then kept warm for reaction, and then the lower layer of acid water is allowed to stand and discharged, an alkaline catalyst is added, and the temperature is continued to rise to a third set temperature, and after reflux reaction, the mixture is cooled and neutralized to obtain a thermoplastic polysilsesquioxane resin solution; S2. removing the solvent from the thermoplastic polysilsesquioxane resin solution at a fourth set temperature to obtain the thermoplastic polysilsesquioxane resin.

[0033] Preferably, the acidic catalyst is any one or more of glacial acetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0034] Preferably, the alkaline catalyst is any one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylphosphine hydroxide.

[0035] Preferably, in step S1, the first set temperature is 70-80°C.

[0036] More preferably, in step S1, the second set temperature is 80-90°C.

[0037] More preferably, in step S1, the insulation temperature time is 2 to 5 hours.

[0038] More preferably, in step S1, the third set temperature is 115-145°C.

[0039] More preferably, in step S1, the reflux time is 1 to 5 hours.

[0040] Preferably, in step S2, the fourth set temperature is 110-160°C.

[0041] More preferably, in step S2, the removal time is 1 to 5 hours.

[0042] In a third aspect, the present invention provides the use of the thermoplastic polysilsesquioxane resin or the thermoplastic polysilsesquioxane resin prepared according to the above preparation method as a cosmetic film-forming agent.

[0043] In a fourth aspect, the present invention provides the use of the thermoplastic polysilsesquioxane resin or the thermoplastic polysilsesquioxane resin prepared according to the above preparation method in cosmetics and personal care products.

[0044] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a thermoplastic polysilsesquioxane resin comprising R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 The molar ratio between the M unit and the T unit is (0.01-3):1; the R 1 is selected from C1-C8 straight or branched alkyl groups, R 2 An alkane group selected from C1-C30, wherein more than 60 mol% of R 2 is propyl, 1 mol% or more of R 2 The thermoplastic polysilsesquioxane resin provided by the present invention has good elasticity, flexibility and moisturizing properties by introducing propyl and octyl groups at the same time and blocking with M units. The thermoplastic polysilsesquioxane resin can be used as a film-forming agent to solve the problem of skin tightness alone without compounding with other film-forming agents, and has good moisturizing, color fixing and makeup holding effects. DETAILED DESCRIPTION

[0045] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0046] Example 1 This embodiment provides a thermoplastic polysilsesquioxane resin, including R 1 3SiO 1 / 2The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 90.9 mol% of R 2 is propyl, 9.1 mol% of R 2 The molar ratio between the M unit and the T unit is 0.1:1.1.

[0047] The preparation method of the thermoplastic polysilsesquioxane resin comprises the following steps: (1) 16.2 g of hexamethyldisiloxane, 206 g of propyltriethoxysilane, 27.6 g of octyltriethoxysilane and 66.7 g of toluene were added to a reaction kettle, stirred and heated to 70°C, 108 g of a 1% hydrochloric acid aqueous solution was slowly dripped in, the temperature was raised to 80°C after the dripping was completed, and the temperature was kept for 4 hours, and the lower layer of acid water was discharged after standing, 10.2 g of a 0.04% potassium hydroxide solution was added, the temperature was raised to 115°C, and the water was removed by refluxing for 2 hours using a water separator, and then cooled, neutralized to neutrality with glacial acetic acid, and filtered to obtain a colorless and transparent polysilsesquioxane resin toluene solution.

[0048] (2) The colorless transparent polysilsesquioxane resin toluene solution obtained in step (1) was subjected to low pressure at 120° C. to remove toluene solvent for 1 hour, and then 40 g of heptane was added. After stirring and dissolving, the toluene was further removed at 120° C. to remove toluene for 1 hour. After cooling, a colorless transparent block-like solid thermoplastic polysilsesquioxane resin was obtained. The melting point was 112° C., the volatile content was 0.13%, and no toluene remained. Example 2

[0049] This embodiment provides a thermoplastic polysilsesquioxane resin, including R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 83.3 mol% of R 2 is propyl, 16.7 mol% of R 2 The molar ratio between the M unit and the T unit is 0.05:1.2.

[0050] The preparation method of the thermoplastic polysilsesquioxane resin comprises the following steps: (1) 8.1 g of hexamethyldisiloxane, 206 g of propyltriethoxysilane, 55.2 g of octyltriethoxysilane and 96.4 g of xylene were added to a reaction kettle, stirred and heated to 80°C, 122.4 g of 1.2% acetic acid aqueous solution was slowly dripped in, the temperature was raised to 90°C after the dripping was completed, and the temperature was kept at reflux for 3.5 hours, and the lower layer of acid water was discharged after standing, 12 g of 0.05% potassium hydroxide solution was added, the temperature was raised to 120°C, and refluxed for 3 hours using a water separator to remove water, and then cooled, neutralized to neutrality with concentrated sulfuric acid, and filtered to obtain a colorless and transparent polysilsesquioxane resin xylene solution.

[0051] (2) The colorless transparent polysilsesquioxane resin xylene solution obtained in step (1) was subjected to low pressure at 150° C. to remove the xylene solvent for 1 hour, and then 32 g of isododecane was added, stirred and dissolved, and then the xylene was further removed at 150° C. for 1 hour. After cooling, a colorless transparent block solid thermoplastic polysilsesquioxane resin was obtained. The melting point was 133° C., the volatile content was 0.1%, and no toluene remained. Example 3

[0052] This embodiment provides a thermoplastic polysilsesquioxane resin, including R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 80 mol% of R 2 is propyl, 20 mol% of R 2 The molar ratio between the M unit and the T unit is 0.1:1.2.

[0053] The preparation method of the thermoplastic polysilsesquioxane resin comprises the following steps: (1) 11.8 g of trimethylethoxysilane, 164.8 g of propyltriethoxysilane, 55.2 g of octyltriethoxysilane and 92.8 g of isododecane were added to a reaction kettle, stirred and heated to 78°C, and then 122.4 g of 0.8% sulfuric acid aqueous solution was slowly dripped in. After the dripping was completed, the temperature was raised to 88°C, and the temperature was kept at reflux for 4 hours. The lower layer of acid water was discharged, and 6 g of 0.03% sodium hydroxide solution was added. The temperature was raised to 120°C, and the water was distilled for 3 hours to remove water. The mixture was cooled, neutralized to neutrality with glacial acetic acid, and filtered to obtain a colorless and transparent polysilsesquioxane resin isododecane solution.

[0054] (2) The colorless transparent polysilsesquioxane resin isododecane solution obtained in step (1) was subjected to low pressure at 150° C. to remove the solvent for 2 hours, and after cooling, a colorless transparent block solid thermoplastic polysilsesquioxane resin was obtained. The melting point was 146° C. and the volatile content was 0.18%. Example 4

[0055] This embodiment provides a thermoplastic polysilsesquioxane resin, including R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 76.9 mol% of R 2 is propyl, 23.1 mol% of R 2 The molar ratio between the M unit and the T unit is 0.05:1.3.

[0056] The preparation method of the thermoplastic polysilsesquioxane resin comprises the following steps: (1) Take 5.9 g (0.05 mol) of trimethylethoxysilane, 206 g (1 mol) of propyltriethoxysilane, 82.8 g (0.3 mol) of octyltriethoxysilane and 84.2 g of isododecane and add them to a reaction kettle. Stir and heat to 70°C. Slowly drop 122.4 g of 0.4% trifluoromethanesulfonic acid aqueous solution. After the drop is complete, heat to 90°C and reflux for 4 hours. Let stand to release the lower layer of acid water, add 6 g of 0.03% potassium hydroxide solution, heat to 145°C, distill for 3 hours to remove water, cool and neutralize with glacial acetic acid until neutral, filter, and obtain a colorless and transparent polysilsesquioxane resin isododecane solution.

[0057] (2) The colorless transparent polysilsesquioxane resin isododecane solution obtained in step (1) was subjected to low pressure at 150° C. to remove the solvent for 2 hours, and after cooling, a colorless transparent block-like solid thermoplastic polysilsesquioxane resin was obtained. The melting point was 147° C. and the volatile content was 0.16%. Example 5

[0058] The difference between this embodiment and embodiment 1 is that the thermoplastic polysilsesquioxane resin provided in this embodiment includes R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 90.9 mol% of R 2 is propyl, 9.1 mol% of R 2 The molar ratio between the M unit and the T unit is 2:1.1.

[0059] The amount of hexamethyldisiloxane added in this example is 324.76 g (2 mol). Example 6

[0060] The difference between this embodiment and embodiment 1 is that the thermoplastic polysilsesquioxane resin provided in this embodiment includes R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 90.9 mol% of R 2 is propyl, 9.1 mol% of R 2 The molar ratio between the M unit and the T unit is 3:1.1.

[0061] The added amount of hexamethyldisiloxane in this example is 487.14 g (3 mol). Example 7

[0062] The difference between this embodiment and embodiment 1 is that the thermoplastic polysilsesquioxane resin provided in this embodiment includes R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 60 mol% of R 2 is propyl, 40 mol% of R 2 The molar ratio between the M unit and the T unit is 0.1:1.

[0063] The T structural unit silane used in this embodiment is a mixture of 123.6 g of propyltriethoxysilane and 110.6 g of octyltriethoxysilane. Example 8

[0064] The difference between this embodiment and embodiment 1 is that: the thermoplastic polysilsesquioxane resin provided in this embodiment includes R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 90.9 mol% of R 2 is propyl, 4.55 mol% of R 2 is octyl, 4.55 mol% of R 2 The molar ratio between the M unit and the T unit is 0.1:1.1.

[0065] The T structural unit silane used in this embodiment is a mixture of 185.7 g of propyltriethoxysilane (1 mol), 17.8 g of methyltriethoxysilane (0.05 mol), and 27.6 g of octyltriethoxysilane (0.05 mol). Example 9

[0066] The difference between this embodiment and embodiment 1 is that: this embodiment provides a thermoplastic polysilsesquioxane resin, including R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 95 mol% of R 2 is propyl, 5 mol% of R 2 The molar ratio between the M unit and the T unit is 0.1:1.1.

[0067] The T structural unit silane used in this embodiment is a mixture of 194 g of propyltriethoxysilane and 15.2 g of octyltriethoxysilane.

[0068] Comparative Example 1 The difference between this comparative example and Example 1 is that hexamethyldisiloxane is not added in this comparative example. The product has a gel insoluble substance.

[0069] Comparative Example 2 The difference between this comparative example and Example 1 is that the thermoplastic polysilsesquioxane resin provided in this comparative example includes R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R 1 is methyl, 90.9 mol% of R 2 is propyl, 9.1 mol% of R 2 The molar ratio between the M unit and the T unit is 3.67:1.1.

[0070] The added amount of hexamethyldisiloxane in this comparative example is 649.52 g.

[0071] The obtained product cannot form a film and is a liquid resin.

[0072] Comparative Example 3 The only difference between this comparative example and Example 1 is that octyltriethoxysilane is not added in this comparative example.

[0073] Comparative Example 4 The difference between this comparative example and Example 1 is that the thermoplastic polysilsesquioxane resin provided in this comparative example is R 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 Represents a T unit; where R1 is methyl, 50 mol% of R 2 is propyl, 50 mol% of R 2 is octyl, and the molar ratio between M unit and T unit is 0.1:1.1; Among them, the added amount of propyltriethoxysilane is 113.5g, and the added amount of octyltriethoxysilane is 152.1g.

[0074] Comparative Example 5 The preparation method of the polysilsesquioxane resin provided in this comparative example is as follows: 206 g of propyl polysilsesquioxane and 27.6 g of octyl polysilsesquioxane are uniformly mixed to obtain a polysilsesquioxane.

[0075] Application Example 1 This application example provides a non-stick lip glaze, and the specific raw materials and raw material ratios are shown in Table 1. The preparation method of the non-stick lip glaze is as follows: weigh the raw material phase A in a beaker, heat and melt it until it is transparent, add the raw material phase B and stir evenly, then add the raw material phase C, put it into a three-roll mill and grind it three times until the material is uniform and fine, and finally add the phase D and stir evenly to obtain the non-stick lip glaze.

[0076] Table 1

[0077] Application Examples 2~8 The difference between Application Examples 2 to 7 and Application Example 1 is that the film-forming agents used are the thermoplastic polysilsesquioxane resins obtained in Examples 2 to 8, respectively.

[0078] Comparative Application Examples 1~5 The only difference between Comparative Application Examples 1 to 5 and Application Example 1 is that the film-forming agents used are the thermoplastic polysilsesquioxane resins obtained in Comparative Examples 1 to 5, respectively.

[0079] Performance Test: 1. The thermoplastic polysilsesquioxane resins obtained in Examples 1 to 8 and Comparative Examples 1 to 5 were subjected to skin tightening phenomenon simulation tests. The specific test methods and evaluation methods are as follows: According to the characteristics of skin tightness, elastic rubber skin (15*30mm) was used to simulate the stretching movement of the skin. 50 parts of thermoplastic polysilsesquioxane resin were dissolved in 50 parts of cyclopentasiloxane, and then coated on the elastic rubber skin. After drying, the elastic rubber skin was repeatedly pulled 5 times to observe the state of the thermoplastic polysilsesquioxane resin on the surface of the elastic rubber skin. The degree of damage of the thermoplastic polysilsesquioxane resin on the surface of the elastic rubber skin was compared to analyze the degree of relieving the skin tightness phenomenon. The state of the elastic rubber skin surface after repeated pulling was divided into 5 levels, where 1-5 levels correspond to the state of the rubber skin surface film-forming agent: basically flat-slightly wrinkled-small area wrinkled-large area wrinkled-severely wrinkled and broken.

[0080] The evaluation results obtained from the above skin tightening phenomenon simulation test are shown in Table 2.

[0081] Table 2

[0082] According to the data in Table 2, we can see that: The thermoplastic polysilsesquioxane resin obtained in the embodiment of the present invention is minimally damaged on the surface of the elastic rubber skin and exhibits excellent flexibility, indicating that the thermoplastic polysilsesquioxane resin obtained in the embodiment of the present invention will not cause skin tightness when applied to the skin as a film-forming agent.

[0083] It can be seen from Comparative Examples 1 and 2 that when no M unit is added or the amount of M unit added is too high, no product that can be used in subsequent applications can be obtained.

[0084] It can be seen from the comparison between Comparative Example 3 and Example 1 that when the thermoplastic polysilsesquioxane resin does not contain an octyl structure, the performance of relieving skin tightness is poor.

[0085] It can be seen from the comparison between Comparative Example 4 and Example 1 that when the molar ratio of the propyl group to the octyl group in the thermoplastic polysilsesquioxane resin is not within the specified range of the present invention, the skin tension relieving performance is reduced.

[0086] It can be seen from the comparison between Comparative Example 5 and Example 1 that the performance of relieving skin tightness is not ideal when only propyl polysilsesquioxane and octyl polysilsesquioxane are physically blended.

[0087] 2. The non-stick lip glazes obtained in Application Examples 1 to 8 and Comparative Application Examples 1 to 5 were tested for their moisturizing, color fixation, makeup durability, and tightness relief properties. The specific testing methods are as follows: The non-stick lip glaze was applied to the lips of 20 young women respectively. After 12 hours, four items including moisturizing, color fixing, makeup lasting property and tightness relief were evaluated respectively according to the survey. The evaluation standard z of each item was set to 5 points at most. The better the effect, the higher the score was given. The average score of the 20 young women was listed in Table 3 as the result.

[0088] Table 3

[0089] The data in Table 3 above show that the thermoplastic polysilsesquioxane resin provided by Examples 1 to 8 of the present invention can greatly alleviate the tightness of the non-stick lip glaze on the lips. It also proves that the thermoplastic polysilsesquioxane has excellent properties such as excellent moisturizing, color fixing and makeup lasting properties.

[0090] It can be seen from the comparison between Comparative Application Example 3 and Example 1 that when the thermoplastic polysilsesquioxane resin does not have an octyl structure, the obtained product containing the thermoplastic polysilsesquioxane resin has reduced effects on relieving skin tightness, moisturizing, color fixing and makeup durability.

[0091] It can be seen from the comparison between Comparative Application Example 4 and Example 1 that the molar ratio of propyl and octyl in the thermoplastic polysilsesquioxane resin added in this comparative application example is not within the limited range of the present invention, and the obtained product containing the thermoplastic polysilsesquioxane resin has reduced effects on relieving skin tightness, moisturizing, color fixing and makeup durability.

[0092] It can be seen from the comparison between Comparative Application Example 5 and Example 1 that the polysilsesquioxane resin mixture obtained by physically blending propyl polysilsesquioxane and octyl polysilsesquioxane is not as good as the thermoplastic polysilsesquioxane resin obtained in Example 1 in terms of skin tightness relief effect, moisturizing, color fixation and makeup durability.

[0093] The applicant declares that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A thermoplastic polysilsesquioxane resin, characterized in that: The thermoplastic polysilsesquioxane resin comprises 1 3SiO 1 / 2 The M unit and the R 2 SiO 3 / 2 The molar ratio between the M unit and the T unit is (0.01-3):1; The R 1 are independently selected from substituted or unsubstituted C1-C8 straight or branched alkyl groups, R 2 are independently selected from substituted or unsubstituted C1-C30 alkane groups, wherein more than 60 mol% of R 2 is propyl, 1 mol% or more of R 2 is octyl; the substituted substituent is selected from any one of aryl, alkyl and alkenyl.

2. The thermoplastic polysilsesquioxane resin according to claim 1, characterized in that The molar ratio between the M unit and the T unit is (0.03-2):1; Preferably, the R 1 Selected from methyl and ethyl; Preferably, the R 2 The octyl content is 9mol%~40mol%; Preferably, the R 2 The content of propyl group is 60mol%~91mol%.

3. The thermoplastic polysilsesquioxane resin according to claim 1, characterized in that The raw materials for preparing the thermoplastic polysilsesquioxane resin include the following components: (A) a silane having a T structural unit, wherein the silane having a T structural unit is used to form a T unit; The silane having T structural units includes propyl T structural unit silane, octyl T structural unit silane and optionally other T structural unit silanes; (B) silane having M structural unit; The silane having an M structural unit is used to form an M unit; (C) a catalyst; (D) organic solvents; The molar ratio between the silane having the T structural unit and the silane having the M structural unit is 1:(0.01-3); Preferably, the molar ratio between the silane having the M structural unit and the silane having the T structural unit is (0.03-2):1; Preferably, the molar ratio between the propyl T structural unit silane and the octyl T structural unit silane is (0.6-1): (0.05-0.4).

4. The thermoplastic polysilsesquioxane resin according to claim 3, characterized in that The propyl T structural unit silane includes propyl trimethyloxysilane and / or propyl triethoxysilane; Preferably, the silane of the octyl T structural unit includes octyltrimethoxysilane and / or octyltriethoxysilane; Preferably, the silane of the other T structural unit includes one or more of methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethyloxysilane, phenyltriethoxysilane, hexyltrimethoxysilane and hexyltriethoxysilane; Preferably, the silane having the M structural unit includes one or more of hexamethyldisiloxane, trimethylethoxysilane, tetramethyldivinyldisiloxane, dimethylvinylethoxysilane and tetramethyldisiloxane.

5. The thermoplastic polysilsesquioxane resin according to claim 3, characterized in that The organic solvent is one or more of toluene, xylene, heptane, octane, isododecane, isohexadecane, D40 solvent oil, D60 solvent oil, ethanol, isopropanol, butanol and isopentyl glycol.

6. The thermoplastic polysilsesquioxane resin according to claim 3, characterized in that The catalyst is an acid catalyst aqueous solution and / or an alkaline catalyst aqueous solution; Preferably, the acid catalyst is any one or more of glacial acetic acid, hydrochloric acid, sulfuric acid, methanesulfonic acid, and trifluoromethanesulfonic acid; Preferably, the base catalyst is any one or more of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylphosphonium hydroxide; Preferably, the concentration of the acid catalyst aqueous solution is 0.1wt%-5wt%; Preferably, the concentration of the acid catalyst aqueous solution is 0.5 wt %-3 wt %; Preferably, the concentration of the aqueous base catalyst solution is 0.01 wt %-0.1 wt %; Preferably, the concentration of the aqueous base catalyst solution is 0.02 wt %-0.06 wt %.

7. A method for preparing a thermoplastic polysilsesquioxane resin according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: A composition formed by a silane having a T structural unit, a silane having an M structural unit, a catalyst and an organic solvent is subjected to a hydrolysis condensation reaction to obtain the thermoplastic polysilsesquioxane resin; Preferably, the preparation method comprises the following steps: S1. A silane having a T structural unit, a silane having an M structural unit and an organic solvent are mixed and heated to a first set temperature, an acidic catalyst is added, and the temperature is continued to rise to a second set temperature and then kept warm for reaction, and then the lower layer of acid water is allowed to stand and discharged, an alkaline catalyst is added, and the temperature is continued to rise to a third set temperature, and after reflux reaction, the mixture is cooled and neutralized to obtain a thermoplastic polysilsesquioxane resin solution; S2. removing the solvent from the thermoplastic polysilsesquioxane resin solution at a fourth set temperature to obtain the thermoplastic polysilsesquioxane resin.

8. The preparation method according to claim 7, characterized in that: The temperature of the hydrolysis condensation reaction is 70-160°C; the time of the hydrolysis condensation reaction is 3-12h; Preferably, the first set temperature is 70-80°C; the second set temperature is 80-90°C; the third set temperature is 115-145°C; the fourth set temperature is 120-150°C; Preferably, the insulation reaction time is 2 to 5 hours; the reflux reaction time is 1 to 5 hours; and the solvent removal time is 1 to 5 hours.

9. Use of the thermoplastic polysilsesquioxane resin according to any one of claims 1 to 6 or the thermoplastic polysilsesquioxane resin prepared by the preparation method according to claim 7 or 8 as a cosmetic film-forming agent.

10. Use of the thermoplastic polysilsesquioxane resin according to any one of claims 1 to 6 or the thermoplastic polysilsesquioxane resin prepared by the preparation method according to claim 7 or 8 in cosmetics and personal care products.

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