Gel silicone elastomer and production process thereof

Abstract

The invention relates to the technical field of gel silicon, in particular to a gel silicon elastomer and a production process thereof. The gel silicon produced by the invention overcomes the problems of poor thixotropy and poor oxidation resistance of the gel silicon. Components a, b, c and d are obtained through production, a gel silicone elastomer intermediate is produced, and finally the gel silicone elastomer intermediate is dissolved in a carrier fluid to obtain the gel silicone elastomer. By changing the production raw materials of the component b, the dosage and the reaction material conditions, adjusting the dosage of the raw materials in the component c, changing the production process of the component a, and adjusting the first heating temperature, the second heating temperature and the reaction time in the production process of the production raw materials of the component d and the gel silicone elastomer precursor, the gel silicone elastomer is obtained. Finally, the reaction temperature of the gel silicone elastomer precursor and other raw materials is changed, the component dosage of the added composite liquid and antioxidant liquid is controlled, and the adding sequence and the adding speed are reasonably controlled, so that the gel silicone elastomer has good thixotropy, and in addition, the gel silicone elastomer has good scavenging capacity on free radicals.

Description

Technical Field

[0001] The invention relates to the technical field of gel silicone, in particular to a gel silicone elastomer and a production process thereof. Background Art

[0002] Gel silicone elastomer is mainly an elastomer made of silicon-containing compounds, which is often used in daily chemical products, such as skin care products, cosmetics and shampoo products. Gel silicone elastomer is added to skin care products to give them a smooth and refreshing touch and a clear feeling, and has a moisturizing effect on human skin, preventing human skin from being damaged by foreign substances. With the increasing demand for the safety and skin care effects of skin care products, the research on gel silicone elastomer is becoming more and more extensive.

[0003] However, some gel silicones are harmful to the human body. For example, patent CN1177615A discloses an elastomer gel containing volatile low molecular weight siloxane, which has high volatility and poor stability during use, which is not conducive to the performance of effective components. In addition, the raw material D4 used in it has been proven to be toxic to the human body, and the estrogen effect produced by it on the human body interferes with the body.

[0004] Patent CN101432340B discloses a silicone polyether elastomer gel, which is prepared by using an organic hydrogen siloxane containing a cyclosiloxane ring of SiH and a compound containing an aliphatic unsaturated hydrocarbon group as raw materials, and using a hydrosilane compound as a catalyst, and adding a carrier solvent of the polyether compound to swell and form an elastomer gel. The obtained gel has good antibacterial properties and good silky feel, but low transparency. Patent CN101686901B discloses a silicone-organic gel with a polyalkyleneoxy cross-linked silicone elastomer, the gel structure contains dimethyl, methyl hydrogen polysiloxane and polyoxyalkylene, the catalyst is a hydrosilylation catalyst, the gel has good absorbency and spreadability, but poor wettability. Patent CN101809091B discloses a silicone elastomer emulsion and a silicone organic elastomer gel, the obtained silicone organic elastomer gel is an aqueous emulsion composition, but the silicone organic elastomer gel has poor stability and poor antioxidant effect.

[0005] CN1185314A discloses a polysiloxane thickened with elastic silicone polyether. The obtained gel has good hydrophilicity, but poor thixotropy of the gel. Poor thixotropy leads to poor skin experience, reduced refreshing and smooth skin feel, and a milky white appearance, which is not conducive to practical applications.

[0006] Therefore, there is a need to develop a gel silicone elastomer having both high thixotropy and good antioxidant effect in the art to meet the application needs of different types of care products or cosmetics.

[0007] Therefore, a gel silicone elastomer and a production process thereof are proposed. Summary of the invention

[0008] The object of the present invention is to provide a gel silicone elastomer and a production process thereof, wherein components a, b, c and d are obtained by production, and then a gel silicone elastomer intermediate is produced, and finally the gel silicone elastomer is dissolved in polysiloxane quaternary ammonium salt-17 to obtain the gel silicone elastomer. By changing the production raw materials, dosage and reaction material conditions of component b, adjusting the dosage of the raw materials in component c, changing the production process of component a, adjusting the production raw materials of component d and the first and second heating temperatures and reaction time in the production process of the gel silicone elastomer precursor, and finally changing the reaction temperature of the gel silicone elastomer precursor and other raw materials, controlling the dosage of the added composite liquid and antioxidant liquid, and reasonably controlling the addition order and the addition speed, the gel silicone elastomer has good thixotropy, lipophilicity, silicone oil affinity, hydrophilicity, skin feel, spreadability and transparency, and a lower glass transition temperature, and has good scavenging ability for DPPH free radicals and ABTS free radicals.

[0009] To achieve the above object, the present invention provides the following technical solutions:

[0010] In one aspect, the present invention provides a production process of a gel silicone elastomer, and the production process is as follows:

[0011] S1. Add 14.7-34.2 parts of carboxyl cage-type silsesquiane to a polyethylene glycol diacrylate emulsion containing 8.0-10.5 parts of polyethylene glycol diacrylate to react and obtain component a;

[0012] The structure of carboxyl cage silsesquiane is shown below:

[0013]

[0014] S2: 5.2-12.4 parts of epoxy silane, 0.2-0.6 parts of potassium hydroxide and 1.9-2.6 parts of deionized water are mixed and reacted at 60° C. for 6 hours to obtain component b;

[0015] S3: 1.4-2.3 parts of isotridecyl alcohol and 30 parts of the deionized water are mixed, and then 1.4-3.5 parts of ethylene oxide and 0.02 parts of potassium hydroxide are added, and the mixture is reacted at 160° C. for 3 hours to obtain component c;

[0016] S4: 14.0-16.0 parts of carboxyl-polyethylene glycol-silane and 80 parts of the deionized water are mixed, and then 7.0-8.3 parts of a 30% hydrochloric acid aqueous solution are added, and the mixture is reacted at 60° C. for 5 hours to obtain component d;

[0017] S5: mixing the component b and the component c, heating them for the first time at 55-90° C., adding the component d for reaction, adding the component a, heating them for the second time at 85-95° C., and reacting for 40-80 minutes to obtain a gel silicone elastomer precursor;

[0018] S6: Mix the gel silicone elastomer precursor with 1 part of hexadecyltrimethylammonium bromide, 3 parts of lauryl polyoxyethylene ether and 10 parts of jojoba oil, heat to 45-80°C and stir, then quickly cool to 25-50°C to obtain a mixed gel silicone elastomer precursor; slowly add a composite liquid containing 1.3-2.0 parts of acetyl hexapeptide-3 to the mixed gel silicone elastomer precursor at a stirring speed of 80-800rpm, and continue stirring to obtain a uniform phase; slowly add 0.5 parts of an antioxidant to the uniform phase, and stir to obtain a gel silicone elastomer intermediate;

[0019] S7: adding 6-12 parts of polysiloxane quaternary ammonium salt-17 to the gel silicone elastomer intermediate, and reacting to obtain the gel silicone elastomer.

[0020] Preferably, the epoxysilane in S2 is one of octamethylcyclononasiloxane, hexamethylcyclooctasiloxane, tetradecamethylcycloheptasiloxane, eicosylcyclodecasiloxane and tetracosylcyclododecylsiloxane.

[0021] Preferably, the antioxidant in S6 is two of catechin, epigallocatechin gallate, epigallocatechin gallate and epigallocatechin gallate; and the dosage ratio of the two antioxidants is 1-4:1-4.

[0022] Preferably, the production process of component a in S1 is as follows: dissolving 10.0-10.5 parts of the polyethylene glycol diacrylate in 100 parts of the deionized water and 2 parts of Tween 20 at 70°C to obtain the polyethylene glycol diacrylate emulsion; transferring the polyethylene glycol diacrylate emulsion to a reactor 1, adding 25.0-34.2 parts of the carboxyl cage-type silsesquiane thereto, stirring evenly and heating to 73-85°C, stirring and reacting for 3 hours to obtain a component a precursor; removing the liquid from the component a precursor, washing and drying to obtain the component a.

[0023] The structure of polyethylene glycol diacrylate is shown in Formula II: wherein n2 is 10.

[0024]

[0025] Preferably, the production process of component b in S2 is as follows: adding the epoxy silane to reactor 2, and then adding the potassium hydroxide and the deionized water to obtain a mixed solution; heating the mixed solution to 60°C, stirring and reacting for 6 hours, during which the hydroxyl value in the mixed solution is measured until the hydroxyl value no longer changes, to obtain a hydrolyzate; filtering the hydrolyzate, washing it with the deionized water, and drying it to obtain component b.

[0026] Preferably, the epoxy silane is one of icosylcyclodecasiloxane and tetracosylcyclododecylsiloxane.

[0027] Preferably, the production process of the gel silicone elastomer precursor in S5 is as follows: add the component b and the component c into the reaction kettle five and stir evenly, carry out the first heating to 55-70°C, then add the component d and 0.1 parts of concentrated sulfuric acid thereto, stir and react for 5 hours, then continue to add the component a thereto, carry out the second heating, continue to stir and react for 40-65 minutes, cool down and dry to obtain the gel silicone elastomer precursor.

[0028] Preferably, the production process of the gel silicone elastomer intermediate in S6 is as follows: the gel silicone elastomer precursor is mixed with the hexadecyltrimethylammonium bromide, the lauryl polyoxyethylene ether and the jojoba oil, heated to 45-65°C and stirred for 20 minutes, and then quickly cooled to 40-50°C to obtain the mixed gel silicone elastomer precursor; 4.5 parts of glycerol, 1.5 parts of deionized water, 1.2 parts of betaine, 0.2 parts of disodium EDTA and the acetyl hexapeptide-3 are mixed to obtain the composite liquid; the antioxidant is dissolved in 15 parts of deionized water to obtain an antioxidant liquid; under slow stirring at 80-200rpm, the composite liquid is slowly added to the mixed gel silicone elastomer precursor, and stirring is continued to obtain the homogeneous phase; the antioxidant liquid is added to the homogeneous phase under slow stirring, and stirring is continued until the system is completely fused to obtain the gel silicone elastomer intermediate; the stirring speed when the antioxidant liquid is added is consistent with the stirring speed when the composite liquid is added.

[0029] On the other hand, the present invention provides a gel silicone elastomer, wherein the raw materials for preparing the gel silicone elastomer include a gel silicone elastomer precursor obtained from component a, component b, component c and component d, and 1 part of hexadecyltrimethylammonium bromide, 3 parts of lauryl alcohol polyoxyethylene ether, 10 parts of jojoba oil, 1.3-2.0 parts of acetyl hexapeptide-3, 0.5 parts of antioxidant and 6-12 parts of polysiloxane quaternary ammonium salt-17;

[0030] The structure of the gel silicone elastomer precursor includes formula I and formula II:

[0031]

[0032] The structure of A in Formula II is shown in Formula III:

[0033]

[0034] Preferably, n1 in Formula I is one of 5, 6, 7, 8 and 10; n2 in Formula II is 10; n3 in Formula I and Formula II is the same; and n3 is one of 2, 3, 4, 5 and 7.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] 1. By using cyclic siloxane as a reaction raw material, under alkaline conditions, epoxy siloxane is hydrolyzed and undergoes a ring-opening process, and linear polydimethylsiloxane is formed through chain initiation, chain growth, chain termination and chain transfer processes. After component b is produced, it is reacted with component a, component c and component d as well as other raw materials to obtain a gel silicone elastomer. By changing the type of cyclic siloxane and the amount of the ring-opening raw material, the obtained gel silicone elastomer has high viscosity and good thixotropy, and has good refreshing and smooth skin feel.

[0037] 2. By adjusting the amount of tetramethylcyclododecylsiloxane, isotridecyl alcohol and ethylene oxide, the thixotropy of the gel silicone elastomer is further improved. The amount of isotridecyl alcohol and ethylene oxide is adjusted, and the ethylene oxide is ring-opened and polymerized under the action of potassium hydroxide to form a polyether compound, namely component C. The amount of ethylene oxide is adjusted so that the amount of alkyl groups and ethers in component C is within a reasonable range, and the amount of tetramethylcyclododecylsiloxane is adjusted so that the ring-opened polydimethylsiloxane and the polyether in component C are within a suitable range, thereby gradually improving the refreshing feeling and smooth skin feel.

[0038] 3. By changing the production process of component a, the dosage of polyethylene glycol diacrylate and carboxyl cage silsesquiane is adjusted, and the reaction temperature is adaptively adjusted. Under heating conditions, the carboxyl group of carboxyl cage silsesquiane undergoes an esterification reaction with the hydroxyl group of polyethylene glycol diacrylate, thereby introducing the cage silane structure into the polyethylene glycol diacrylate. Component a is used as a crosslinking agent, and its production process is adjusted to reduce the glass transition temperature of the gel silicone elastomer. When it is used as a cosmetic raw material, the liquid ingredients in the cosmetics are not easily frozen under low temperature conditions.

[0039] 4. After mixing components b and c, heating for the first time and then adding component d, component d is formed by removing the alkoxy group in carboxyl-polyethylene glycol-silane, and the three elements connected to silicon become hydrogen. The carboxyl group in component d reacts with the hydroxyl group in component b and component c respectively, thereby introducing the silicon hydrogen structure into component b and component c respectively, and then adding component a for a second heating, and the unsaturated double bond in component a reacts with the silicon hydrogen structure to obtain a gel silicone elastomer intermediate with a network cross-linking structure. After human body evaluation, it was concluded that it has high lipophilicity, silicone oil affinity, hydrophilicity, skin feel, spreadability and transparency.

[0040] 5. A gel silicone elastomer intermediate is obtained by mixing a gel silicone elastomer precursor with other components, heating and stirring, and then rapidly cooling the mixture to a fixed temperature; the composite liquid is added to the intermediate under slow stirring, and then an antioxidant liquid is added; the heating and cooling speeds are controlled and the dosage of the substances is changed, so that the gel silicone elastomer intermediate is an emulsion-like gel with uniform particle size, and the nano-scale gel silicone elastomer precursor is more evenly integrated with the system; in addition, polysiloxane quaternary ammonium salt-17 is added as a carrier fluid, so that the gel silicone elastomer has a good antioxidant effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 It is a graph showing the viscosity test results of Examples 13, 16-25 of the present invention and Comparative Examples 3-6. DETAILED DESCRIPTION

[0042] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] See also Figure 1 The present invention provides a gel silicone elastomer and a production process thereof, and the technical scheme is as follows:

[0044] The substance information involved in the present invention is as follows: tetramethylcyclododecylsiloxane CAS: 18919-94-3; icosylcyclodecasiloxane CAS: 18772-36-6; octadecylcyclononasiloxane CAS: 556-71-8; hexadecylcyclooctasiloxane CAS: 556-68-3; tetradecamethylcycloheptasiloxane CAS: 107-50-6; isomeric tridecanol CAS: 68526-86-3; ethylene oxide CAS: 75-21-8; polyethylene glycol diacrylate CAS: 9051-31-4; polysiloxane quaternary ammonium salt-17 CAS: 519142-86-0 ; Polyoxyethylene lauryl ether CAS: 9002-92-0; Jojoba oil CAS: 61789-91-1; Betaine CAS: 107-43-7; Catechin (EC) CAS: 18829-70-4; Epigallocatechin gallate (EGC) CAS: 3371-27-5; Epigallocatechin gallate (ECG) CAS: 130405-40-2; Epigallocatechin gallate (EGCG) CAS: 4233-96-9; Cetyltrimethylammonium bromide (CTAB) CAS: 57-09-0; Disodium EDTA CAS: 6381-92-6.

[0045] Example 1

[0046] S1: Production process of component a: dissolving 9.4 parts of polyethylene glycol diacrylate in 100 parts of water and 2 parts of Tween 20 at 70°C to obtain polyethylene glycol diacrylate emulsion; transferring the polyethylene glycol diacrylate emulsion to a reactor 1, adding 25.0 parts of carboxyl cage-type silsesquiane thereto, stirring evenly, heating to 80°C, stirring and reacting for 3 hours to obtain component a precursor; removing liquid from the component a precursor, washing, and drying to obtain component a;

[0047] Production process of S2 component b: 6.7 parts of octamethylcyclononasiloxane are added to the second reaction kettle, and then 0.2 parts of potassium hydroxide and 1.9 parts of deionized water are added to obtain a mixed solution; the mixed solution is heated to 60°C and stirred for reaction for 6 hours, during which the hydroxyl value in the mixed solution is measured until the hydroxyl value no longer changes, to obtain a hydrolyzate; the hydrolyzate is filtered, washed with deionized water, and dried to obtain component b;

[0048] Production process of S3 component c: 2.0 parts of isotridecyl alcohol and 30 parts of deionized water are added to the reactor 3, and 2.2 parts of ethylene oxide and 0.02 parts of potassium hydroxide are added thereto after stirring evenly. After fully mixing, the temperature is raised to 160°C, and the reaction is stirred for 3 hours, and then filtered, washed with water and dried to obtain component c;

[0049] Production process of S4 component d: 15.6 parts of carboxyl-polyethylene glycol-silane and 80 parts of water are added to a reactor 4, followed by adding 7.4 parts of a 30% by mass aqueous solution of hydrochloric acid, stirring and reacting at 60°C for 5 hours, filtering and drying to obtain component d;

[0050] Production process of S5 gel silicone elastomer precursor: add component b and component c into reactor 5, heat it up for the first time, heat it up to 60°C and stir it evenly, then add component d and 0.1 parts of concentrated sulfuric acid, stir and react for 5 hours, then continue to add component a, heat it up for the second time, heat it up to 90°C, continue to stir and react for 50 minutes, cool it down and dry it to obtain the gel silicone elastomer precursor;

[0051] Production process of S6 gel silicone elastomer intermediate: Mix gel silicone elastomer precursor with 1 part of CTAB, 3 parts of lauryl polyoxyethylene ether and 10 parts of jojoba oil, heat to 50°C and stir for 20 minutes, then quickly cool to 40°C to obtain a mixed gel silicone elastomer precursor; mix 4.5 parts of glycerol with 1.5 parts of deionized water, 1.2 parts of betaine, 0.2 parts of EDTA disodium and 1.3 parts of acetyl hexapeptide-3 to obtain a composite liquid; dissolve 0.2 parts of EC and 0.3 parts of EGC in 15 parts of deionized water to obtain an antioxidant liquid; slowly add the composite liquid to the mixed gel silicone elastomer precursor under slow stirring (200rpm), and continue stirring to obtain a uniform phase; add the antioxidant liquid to the uniform phase under slow stirring (keep the same stirring speed as the slow addition of the composite liquid), and continue stirring until the system is completely fused to obtain a gel silicone elastomer intermediate;

[0052] Production process of S7 gel silicone elastomer: add gel silicone elastomer intermediate and 10 parts of polysiloxane quaternary ammonium salt-17 into reactor six, stir at 60°C for 1 hour to obtain gel silicone elastomer.

[0053] Example 2-14

[0054] Different from Example 1, the following production process conditions are changed, as shown in Table 1.

[0055] Comparative Example 1

[0056] Different from Example 1, no epoxy silane was added.

[0057] Comparative Example 2

[0058] Different from Example 1, no potassium hydroxide was added.

[0059] Table 1 Production process conditions of component b

[0060]

[0061] Embodiment 15

[0062] The gel silicone elastomers produced in Examples 1-14 and Comparative Examples 1 and 2 were tested for viscosity and thixotropy. The specific test method is as follows: a Brookfield plate viscometer is used to test the viscosity of the silicone gel at 1 rpm and 0.1 rpm at 25°C. The thixotropy is calculated as follows: The final test results are shown in Table 2.

[0063] Table 2 Thixotropy test results of Examples 1-14 and Comparative Examples 1 and 2

[0064]

[0065]

[0066] The gel silicone elastomer produced by the present invention has a viscosity of 332806-398094cps at 25°C and 0.1rpm, a viscosity of 75902-84760cps at 1rpm, and a thixotropy of 4.38-4.71. The higher the thixotropy value, the higher the viscosity drop after external shearing, and has a good smooth skin feel and refreshing feeling after contact with the skin. By using cyclic silane as a raw material, a linear polydimethylsiloxane containing terminal hydroxyl groups is prepared after ring opening, and the produced component b is reacted with a, c and d and other components, and cross-linked and polymerized to obtain a gel silicone elastomer. The results of Examples 1 and 2 show that as the amount of 18methylcyclononasiloxane increases, the viscosity at 25°C at 0.1rpm, the viscosity at 25°C at 1rpm and the thixotropy are all improved. The results of Examples 1, 3, 5, 7 and 9 show that as the type and dosage of epoxy silane change, the thixotropy tends to increase as a whole. This is because at the same friction, as the length of the molecular chain segment increases, the length of the linear polydimethylsiloxane formed also increases, and the viscosity and thixotropy increase accordingly. However, the thixotropy does not increase infinitely with the increase of the molecular chain length. As shown in the results of Examples 9 and 10, the viscosity at 25°C at 0.1rpm and the viscosity at 25°C at 1rpm increase, but the thixotropy decreases. The results of Examples 10-12 show that as the dosage of potassium hydroxide increases, the thixotropy and the viscosity at 25°C at 0.1rpm and the viscosity at 25°C at 1rpm first increase and then decrease. If the dosage of potassium hydroxide is too high, the cyclic siloxane is excessively opened, which has a greater destructive effect on the molecular structure. Comparative Example 1 does not add epoxy silane, lacks a linear polydimethylsiloxane structure in the molecule, and the viscosity and thixotropy decrease significantly. In Comparative Example 2, potassium hydroxide is not added, the ring-opening process cannot proceed smoothly, and it is impossible to react and cross-link with other components, and the component fusion is poor. The gel silicone elastomers of the embodiment and comparative example 1 are both clear and transparent, while the comparative example 2 is slightly turbid, and at the same time, the thixotropy is also reduced.

[0067] Examples 16-25

[0068] The difference from Example 13 is that the production process of component c and the amount of tetramethylcyclododecylsiloxane in component b are changed, as shown in Table 3.

[0069] Table 3 Production process of component c and the amount of tetramethylcyclododecylsiloxane in component b

[0070] Amount of isotridecyl alcohol (parts) Ethylene oxide dosage (parts) Dosage of tetramethylcyclododecylsiloxane (parts) Embodiment 13 2.0 2.2(n3＝5) 8.8 Example 16 1.4 2.2(n3＝5) 8.8 Embodiment 17 2.3 2.2(n3＝5) 8.8 Embodiment 18 2.0 1.4(n3＝3) 8.8 Embodiment 19 2.0 1.8(n3＝4) 8.8 Embodiment 20 2.0 2.6(n3＝5) 8.8 Embodiment 21 2.0 3.5(n3＝7) 8.8 Embodiment 22 2.0 1.8(n3＝4) 8.0 Embodiment 23 2.0 1.8(n3＝4) 7.1 Embodiment 24 2.0 1.8(n3＝4) 10.6 Embodiment 25 2.0 1.8(n3＝4) 12.4

[0071] Comparative Example 3

[0072] The difference from Example 13 is that the amount of ethylene oxide used is 1.5 parts.

[0073] Comparative Example 4

[0074] The difference from Example 13 is that the amount of ethylene oxide used is 4.0 parts.

[0075] Comparative Example 5

[0076] The difference from Example 13 is that the amount of tetracosylcyclododecylsiloxane used is 6.0 parts.

[0077] Comparative Example 6

[0078] The difference from Example 13 is that the amount of tetracosylcyclododecylsiloxane used is 14.2 parts.

[0079] Embodiment 26

[0080] The gel silicone elastomers produced in Examples 13, 16-25 and Comparative Examples 3-6 were subjected to thixotropy tests. The specific test method was carried out with reference to the method in Example 15. The final test results are shown in Tables 4 and Figure 1 shown.

[0081] Table 4 Thixotropy test results of Examples 13, 16-25 and Comparative Examples 3-6

[0082]

[0083]

[0084] like Figure 1As shown, the viscosity of the gel silicone elastomer produced by the present invention at 0.1rpm is 367595-402603cps at 25℃, and the viscosity at 1rpm is 79912-85306cps at 25℃. The results in Table 4 show that the thixotropy is 4.60-4.77. Under the action of potassium hydroxide, isomeric tridecanol and ethylene oxide ring-opening product are polymerized to form a polyether compound, namely component c. One end of component c is isomeric tridecanol, the middle is a polyether structure, and the other end is a hydroxyl structure. The results of Examples 13, 16 and 17 show that as the amount of isomeric tridecanol increases, the thixotropy gradually decreases. The alkyl component and the polyether component have moderate viscosity and high thixotropy under the conditions of Example 13. The results of Examples 13, 18-21 show that as the amount of ethylene oxide increases, the thixotropy increases and then decreases, and tends to remain unchanged. The amount of ethylene oxide increases, the proportion of polyether in component c gradually increases, and the viscosity at 25℃ at 1rpm gradually increases, but the thixotropy decreases. The results of Examples 19, 22-25 show that as the amount of tetramethylcyclododecylsiloxane increases, the thixotropy reaches the highest under the conditions of Example 24, and the viscosity of the gel silicone elastomer of Example 25 at 1rpm is the highest. In Comparative Examples 3 and 4, the amount of ethylene oxide is too high or too low, and the thixotropy decreases. In Comparative Examples 5 and 6, the amount of tetramethylcyclododecylsiloxane is too low or too high, and the thixotropy further decreases. In summary, the amount of alkyl and polyether in component c is controlled within a reasonable range, and the amount of tetramethylcyclododecylsiloxane is controlled within a reasonable range, so that the ratio of open-ring polydimethylsiloxane and polyether is within a reasonable range, the thixotropy of the obtained gel silicone elastomer is improved, and the refreshing feeling and smooth skin feel are further improved.

[0085] Examples 27-34

[0086] Different from Example 24, the production process of component a is changed, as shown in Table 5.

[0087] Comparative Example 7

[0088] Different from Example 24, polyethylene glycol diacrylate was not added.

[0089] Comparative Example 8

[0090] Different from Example 24, no carboxyl cage-type silsesquiane was added.

[0091] Embodiment 35

[0092] The gel silicone elastomers produced in Examples 27-34 and Comparative Examples 7 and 8 were tested for thixotropy and glass transition temperature. The test results are shown in Table 5.

[0093] Table 5 Production process conditions of component a

[0094]

[0095] The gel silicone elastomer produced by the present invention has a thixotropy of 4.69-4.74 and a glass transition temperature of -55 to -65°C. By adjusting the production process of component a, under heating conditions, the carboxyl group of the carboxyl cage-type silsesquiane and the hydroxyl group of the polyethylene glycol diacrylate undergo an esterification reaction, and the formed component c structure contains both a cage-type silane structure and a polymerizable unsaturated double bond. The results of Examples 24, 27-29 show that as the amount of polyethylene glycol diacrylate increases, the thixotropy remains substantially unchanged, and the glass transition temperature shows a trend of first decreasing and then increasing. The amount has little effect on the thixotropy, but has a greater effect on the temperature resistance. The unsaturated double bond content increases, and the degree of crosslinking with components b, c and d increases, and the temperature resistance is improved. However, if the polyethylene glycol content is too high, the temperature resistance is affected, and its original existing form cannot be maintained at a lower temperature. The results of Examples 28 and 30-32 show that as the amount of carboxyl cage silsesquiane increases, the thixotropy does not change much, and the glass transition temperature gradually decreases. The introduced carboxyl cage silsesquiane presents a three-dimensional structure, the bond energy of the silicon oxygen bond is high, and the bond length is long, and the temperature resistance is good, so the amount is increased, and the glass transition temperature is reduced. The results of Examples 32-34 show that the reaction temperature is controlled in a suitable range, and the glass transition temperature is low. Comparative Example 7 does not add polyethylene glycol diacrylate, and it is impossible to crosslink with components b, c and d and other components, and the gel interpenetrating network structure is not formed, so the thixotropy is reduced, and the temperature resistance is reduced. Comparative Example 8 does not add carboxyl cage silsesquiane, and the thixotropy is reduced, and the temperature resistance is significantly reduced.

[0096] Examples 36-46

[0097] Different from Example 32, the production process of component d and the gel silicone elastomer precursor is changed, as shown in Table 6.

[0098] Table 6 Production process conditions of component d and gel silicone elastomer precursor

[0099]

[0100] Embodiment 47

[0101] The difference from Example 32 is that the amount of tetracosylcyclododecylsiloxane used is 12.4 parts.

[0102] Comparative Example 9

[0103] In contrast to Example 32, no carboxyl-polyethylene glycol-silane was added.

[0104] Comparative Example 10

[0105] The difference from Example 32 is that the temperature is increased only once, and the temperature is 90°C.

[0106] Comparative Example 11

[0107] Different from Example 32, the reaction time is 80 min.

[0108] Embodiment 48

[0109] The gel silicone elastomers obtained in Examples 32, 36-47 and Comparative Examples 9-11 were subjected to performance tests, and 30 testers were selected to conduct evaluations. The lipophilicity, silicone oil affinity, hydrophilicity, skin feel, spreadability and transparency were evaluated, and the individual score was set to 10 points, with 10 points being the best. The evaluation results are shown in Table 7 below.

[0110] Table 7 Evaluation results of Examples 32, 36-47 and Comparative Examples 9-11

[0111]

[0112] The gel silicone elastomer produced by the present invention has an oleophilicity of 7.5-10 points, an affinity for silicone oiliness of 7.5-10 points, a skin feel of 8.5-9 points, a spreadability of 10 points, a transparency of 9.5-10 points, a hydrophilicity of 8-9.5 points, and a total score of 52.0-58.0 points. The results of Examples 32, 36 and 37 show that as the amount of carboxyl-polyethylene glycol-silane increases, the total score shows an overall increasing trend. This is because under the action of hydrochloric acid, the silicon-alkoxy group in the carboxyl-polyethylene glycol-silane is converted into a silicon-hydrogen bond, and the carboxyl group therein is esterified with the terminal hydroxyl groups in component b and component c, and finally a cross-linking reaction is carried out, and the properties such as oleophilicity, affinity for silicone oiliness and hydrophilicity are improved. The results of Examples 37-40 show that as the amount of hydrochloric acid aqueous solution increases, the total score shows a trend of first increasing and then decreasing. The amount of hydrochloric acid added is controlled within a reasonable range, and the overall performance of the gel silicone elastomer is improved. The total score under the conditions of Example 39 is the highest. The results of Examples 39, 41 and 42 show that the total score is the highest when the first heating temperature is 70°C. This is because the temperature of the first heating is conducive to the reaction of component d with component b and component c, respectively, thereby bonding component d to component b and component c, respectively, and improving the overall score. The results of Examples 42-44 show that setting the secondary heating temperature to 90°C promotes the addition reaction of olefin bonds in component a with silicon hydrogen. Under the conditions of Example 42, the lipophilicity, silicone oil affinity, hydrophilicity, skin feel, spreadability and transparency are high. The results of Examples 42, 45 and 46 show that the overall performance of the gel silicone elastomer is improved by reasonably adjusting the reaction time. Compared with Example 32, Example 47 has an improved total score, in which the lipophilicity and silicone oil affinity are improved, the compatibility of the open-ring polydimethylsiloxane component with grease and silicone oil is increased, and the score is improved. In Comparative Example 9, carboxyl-polyethylene glycol-silane is not added, and component a cannot undergo a cross-linking reaction with component b and component c, and the overall performance of the gel silicone elastomer decreases. In comparative example 10, the temperature was too high, and component d did not react completely with component b and component c, which ultimately reduced the overall performance of the gel silicone elastomer. In comparative example 11, the reaction time was too long, and the total score was reduced.

[0113] Examples 49-63

[0114] Different from Example 46, the production process of the gel silicone elastomer intermediate and the gel silicone elastomer in S6 and S7 is changed, as shown in Table 8.

[0115] Table 8 Production process conditions of gel silicone elastomer intermediates and gel silicone elastomer

[0116]

[0117] Comparative Example 12

[0118] Different from Example 46, the heating temperature is 80°C.

[0119] Comparative Example 13

[0120] Different from Example 46, the cooling temperature is 25°C.

[0121] Comparative Example 14

[0122] Different from Example 46, the heating temperature and the cooling temperature are both 40°C.

[0123] Comparative Example 15

[0124] Different from Example 46, no antioxidant liquid was added.

[0125] Comparative Example 16

[0126] Different from Example 46, no silane quaternary ammonium salt was added.

[0127] Comparative Example 17

[0128] Different from Example 46, the rotation speed is 800 rpm.

[0129] Embodiment 64

[0130] The gel silicone elastomers produced in Examples 46, 49-63 and Comparative Examples 12-17 were tested for their antioxidant properties, wherein the gel silicone elastomers were diluted 100 times and 25 times, respectively, i.e., the gel silicone elastomers were mixed with water in a ratio of 1:99 and 4:96. The test results are shown in Table 9.

[0131] Table 9 Antioxidant test results of Examples 46, 49-63 and Comparative Examples 12-17

[0132]

[0133]

[0134] After dilution, the gel silicone elastomer produced by the present invention has a scavenging rate of 73.7%-85.0% for DPPH after dilution 100 times, a scavenging rate of 90.5%-98.2% for DPPH after dilution 25 times, a scavenging rate of 72.6%-83.1% for ABTS after dilution 100 times, and a scavenging rate of 45.6%-64.5% for ABTS after dilution 25 times. The scavenging rate of free radicals after dilution 25 times and dilution 100 times shows an overall increasing trend. The results of Examples 46, 49-51 show that with the increase of heating temperature, the scavenging rate of DPPH and ABTS shows a trend of first increasing and then decreasing, and the antioxidant capacity is the strongest under the conditions of Example 50. The results of Examples 50, 52 and 53 show that when the temperature of rapid cooling is 45°C, the obtained gel silicone elastomer has the highest scavenging rate for DPPH and ABTS. By adding lauryl alcohol polyoxyethylene ether and jojoba oil as emulsified phase, adjusting the mixed temperature and the temperature of rapid cooling at the same time, then slowly adding the composite liquid containing water phase, finally adding antioxidant liquid, this kind of process production mode makes the main component of gel silicon elasticity form a nanoemulsion with uniform particle size, otherwise the main component particle size is different and the poor dispersion effect will cause the antioxidant performance to decline. As shown in the results of comparative examples 12, 13 and 14, the heating temperature is too high or too low, and the heating temperature and the cooling temperature are kept consistent, then the scavenging ability of DPPH and ABTS is greatly reduced. The results of embodiment 52, 54 and 55 show that the amount of acetyl hexapeptide-3 is controlled within a reasonable range, and the antioxidant effect is further improved, although this is due to its use as a neurotransmitter release inhibitor, it can promote the gel silicon elastomer to provide electrons to free radicals, further improving the antioxidant effect. The results of Examples 54, 56-58 show that the antioxidant effect is improved by reasonably adjusting the type and amount of antioxidant liquid components, among which the antioxidant effect is best under the conditions of Example 58; ECG, EGCG and EC in the antioxidant liquid have rich phenolic hydroxyl structures and have good scavenging ability for DPPH and ABTS. The results of Examples 58-60 show that the stirring speed is controlled in the range of 80-250rpm, so that the gel silicone elastomer can form a uniform nanoemulsion structure while ensuring the uniformity and transparency of the system. The speed of Comparative Example 17 is too high, and the antioxidant effect is reduced compared with the results of Examples 46, 49-63. The results of Examples 58 and 61-63 show that as the amount of silane quaternary ammonium salt increases, the antioxidant effect gradually improves. Lauryl alcohol polyoxyethylene ether reduces the interfacial tension between the aqueous phase and the oil phase in the process of producing gel silicone elastomer to obtain small-sized droplets. Polysiloxane quaternary ammonium salt-17, as a carrier solvent, has a maintaining effect on the droplets in the emulsion. At the same time, it provides a spatial barrier for macromolecular groups, reduces the aggregation of droplet particles in the gel silicone elastomer, improves the stability of the gel silicone elastomer, and thus improves the antioxidant performance.In Comparative Example 16, no silane quaternary ammonium salt was added, and the scavenging ability of the gel silicone elastomer to DPPH and ABTS decreased.

[0135] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A production process for a gel silicone elastomer, characterized in that: The production process is as follows: S1. Add 14.7-34.2 parts of carboxyl cage-type silsesquiane to a polyethylene glycol diacrylate emulsion containing 8.0-10.5 parts of polyethylene glycol diacrylate to react and obtain component a; S2: 5.2-12.4 parts of epoxy silane, 0.2-0.6 parts of potassium hydroxide and 1.9-2.6 parts of deionized water are mixed and reacted at 60° C. for 6 hours to obtain component b; S3: 1.4-2.3 parts of isotridecyl alcohol and 30 parts of the deionized water are mixed, and then 1.4-3.5 parts of ethylene oxide and 0.02 parts of potassium hydroxide are added, and the mixture is reacted at 160° C. for 3 hours to obtain component c; S4: 14.0-16.0 parts of carboxyl-polyethylene glycol-silane and 80 parts of the deionized water are mixed, and then 7.0-8.3 parts of a 30% hydrochloric acid aqueous solution are added, and the mixture is reacted at 60° C. for 5 hours to obtain component d; S5: mixing the component b and the component c, heating them for the first time at 55-90° C., adding the component d for reaction, adding the component a, heating them for the second time at 85-95° C., and reacting for 40-80 minutes to obtain a gel silicone elastomer precursor; S6: Mix the gel silicone elastomer precursor with 1 part of hexadecyltrimethylammonium bromide, 3 parts of lauryl polyoxyethylene ether and 10 parts of jojoba oil, heat to 45-80°C and stir, then quickly cool to 25-50°C to obtain a mixed gel silicone elastomer precursor; slowly add a composite liquid containing 1.3-2.0 parts of acetyl hexapeptide-3 to the mixed gel silicone elastomer precursor at a stirring speed of 80-800rpm, and continue stirring to obtain a uniform phase; slowly add 0.5 parts of an antioxidant to the uniform phase, and stir to obtain a gel silicone elastomer intermediate; S7: adding 6-12 parts of polysiloxane quaternary ammonium salt-17 to the gel silicone elastomer intermediate, and reacting to obtain the gel silicone elastomer.

2. The production process of a gel silicone elastomer according to claim 1, characterized in that: The epoxysilane in S2 is one of octamethylcyclononasiloxane, hexadecylcyclooctasiloxane, tetradecamethylcycloheptasiloxane, eicosylcyclodecasiloxane and tetracosylcyclododecylsiloxane.

3. The production process of a gel silicone elastomer according to claim 1, characterized in that: The antioxidants in S6 are two of catechin, epigallocatechin gallate, epigallocatechin gallate and epigallocatechin gallate; the dosage ratio of the two antioxidants is 1-4:1-4.

4. The production process of a gel silicone elastomer according to claim 1, characterized in that: The production process of component a in S1 is as follows: dissolving 10.0-10.5 parts of the polyethylene glycol diacrylate in 100 parts of the deionized water and 2 parts of Tween 20 at 70°C to obtain the polyethylene glycol diacrylate emulsion; transferring the polyethylene glycol diacrylate emulsion to a reactor 1, adding 25.0-34.2 parts of the carboxyl cage-type silsesquiane thereto, stirring evenly and heating to 73-85°C, stirring and reacting for 3 hours to obtain a component a precursor; removing the liquid from the component a precursor, washing and drying to obtain the component a.

5. The production process of a gel silicone elastomer according to claim 1, characterized in that: The production process of component b in S2 is as follows: add the epoxy silane into reactor 2, and then add the potassium hydroxide and the deionized water to obtain a mixed solution; heat the mixed solution to 60°C, stir and react for 6 hours, during which the hydroxyl value in the mixed solution is measured until the hydroxyl value no longer changes, to obtain a hydrolyzate; filter the hydrolyzate, wash it with the deionized water, and dry it to obtain component b.

6. The production process of a gel silicone elastomer according to claim 2, characterized in that: The epoxy silane is one of icosylcyclodecasiloxane and tetracosylcyclododecylsiloxane.

7. The production process of a gel silicone elastomer according to claim 1, characterized in that: The production process of the gel silicone elastomer precursor in S5 is as follows: add the component b and the component c into the reactor five and stir evenly, carry out the first heating to 55-70°C, then add the component d and 0.1 parts of concentrated sulfuric acid thereto, stir and react for 5 hours, then continue to add the component a thereto, carry out the second heating, continue to stir and react for 40-65 minutes, cool down and dry to obtain the gel silicone elastomer precursor.

8. The production process of a gel silicone elastomer according to claim 1, characterized in that: The production process of the gel silicone elastomer intermediate in S6 is as follows: the gel silicone elastomer precursor is mixed with the hexadecyl trimethyl ammonium bromide, the lauryl alcohol polyoxyethylene ether and the jojoba oil, heated to 45-65°C and stirred for 20 minutes, and then rapidly cooled to 40-50°C to obtain the mixed gel silicone elastomer precursor; 4.5 parts of glycerol, 1.5 parts of deionized water, 1.2 parts of betaine, 0.2 parts of disodium EDTA and the acetyl hexapeptide-3 are mixed to obtain the composite liquid; the antioxidant is dissolved in 15 parts of deionized water to obtain an antioxidant liquid; under slow stirring at 80-200rpm, the composite liquid is slowly added to the mixed gel silicone elastomer precursor, and stirring is continued to obtain the homogeneous phase; The antioxidant liquid is added to the homogeneous phase under slow stirring, and stirring is continued until the system is completely fused to obtain the gel silicone elastomer intermediate; the stirring speed when the antioxidant liquid is added is consistent with the stirring speed when the composite liquid is added.

9. A gel silicone elastomer obtained by the production process according to any one of claims 1 to 8, characterized in that: The raw materials for preparing the gel silicone elastomer include a gel silicone elastomer precursor obtained from component a, component b, component c and component d, as well as 1 part of hexadecyltrimethylammonium bromide, 3 parts of lauryl alcohol polyoxyethylene ether, 10 parts of jojoba oil, 1.3-2.0 parts of acetyl hexapeptide-3, 0.5 parts of antioxidant and 6-12 parts of polysiloxane quaternary ammonium salt-17; The structure of the gel silicone elastomer precursor includes formula I and formula II: The structure of A in Formula II is shown in Formula III:

10. The gel silicone elastomer according to claim 9, characterized in that: n1 in formula I is one of 5, 6, 7, 8 and 10; n2 in formula II is 10; n3 in formula I and formula II is the same; n3 is one of 2, 3, 4, 5 and 7.

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