CN111154104A - MT-mercapto silicone resin and preparation method and application thereof - Google Patents

MT-mercapto silicone resin and preparation method and application thereof Download PDF

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CN111154104A
CN111154104A CN202010026049.XA CN202010026049A CN111154104A CN 111154104 A CN111154104 A CN 111154104A CN 202010026049 A CN202010026049 A CN 202010026049A CN 111154104 A CN111154104 A CN 111154104A
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sio
mercapto
mercapto silicone
resin
silicone
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黄振宏
戢欢
赖应祥
邓海燕
谢金连
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Guangdong Biomax Si&f New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
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    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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Abstract

The invention discloses MT-mercapto silicone resin which satisfies the general formula: (R)1SiO3/2)a(R2SiO3/2)b(SiO4/2)c(R3 3SiO1/2)d(R4 2SiO2/2)e(ii) a Wherein R is1Is a mercapto-containing hydrocarbyl, aryl, acyloxy or amino group, a>0.025. The MT-mercapto silicone resin can be applied to products for caring hair, and effectively improves smoothness and styling property of hair.

Description

MT-mercapto silicone resin and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic silicon resin, and particularly relates to MT-mercapto silicon resin and a preparation method and application thereof.
Background
Silicones are a class of materials with a variety of specific properties. Silicon, which is widely used in daily chemical products, is generally a polyoxosilane. After being added into daily chemicals, the organic silicon can bring smooth, fresh and non-greasy skin feeling, has no toxic or side effect, and is a widely used additive in cosmetics.
Various subclasses of silicones (dimethicone, dimethiconol, aminopolydimethylsiloxane, etc.) have found particular utility in personal care compositions (e.g., cosmetic formulations) based on the soft and smooth characteristics and hydrophobic functionality imparted by the silicone.
Silicones used in hair cleansing products include high viscosity dimethicone, aminosilicone emulsions, dimethicone emulsions, silicone elastomer emulsions, and the like. Silicones useful as hair care and styling products include volatile silicone oils, high viscosity silicone oil blends, amino silicone oils, silicone volatile silicone oil blends, amino silicone emulsions, dimethyl silicone emulsions, silicone elastomer emulsions, and the like.
Under the influence of the concept of 'silicone oil-free shampoo', the consumption of organic silicon products in the daily chemical industry is accelerated and slides down. However, most of the existing shampoo without silicone oil has a conditioning effect by replacing silicone oil with grease substitutes, cellulose and the like, the aspects of smoothness, moisture and the like are far inferior to the aspects of silicone oil, and partial substitutes also have risks of allergy, irritation and the like.
However, as for the public worry about the application of the organic silicon product in the hair washing and caring product, how to provide the organic silicon product with higher caring effect under a smaller adding amount is an effective means for solving the potential health threat of the organic silicon to human bodies and improving the efficacy and quality of the hair washing and caring product.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the MT-mercapto silicone resin which can exert larger efficacy in daily chemicals with lower addition amount.
The second object of the present invention is to provide a method for preparing the MT-mercapto silicone resin.
The invention also aims to provide application of the MT-mercapto silicone resin.
One of the purposes of the invention is realized by adopting the following technical scheme:
an MT-mercapto silicone, wherein the MT-mercapto silicone has the general formula:
(R1SiO3/2)a(R2SiO3/2)b(SiO4/2)c(R3 3SiO1/2)d(R4 2SiO2/2)e(ii) a Wherein a + b + c + d + e is 1, and c is more than or equal to 0 and less than 0.30;
R1is a mercapto group-containing hydrocarbyl, aryl, acyloxy or amino group, a > 0.025;
R2is a hydrocarbyl, aryl, acyloxy or amino group, 0. ltoreq. b, and 0.25<a+b＜0.90；
R3Is alkyl, aryl, acyloxy or amino group, d is more than 0.10 and less than or equal to 0.75;
R4is a hydrocarbon group, e is 0 or less<0.40。
I.e., the MT-mercapto silicone of the present application must contain (R)1SiO3/2) Unit and (R)3 3SiO1/2) A unit; or further comprises (R)2SiO3/2) Unit, (SiO)4/2) Unit or and (R)4 2SiO2/2) A unit;
as (R)1SiO3/2)aThe units being derived from mercapto groups, in particular R1A group with a sulfhydryl at the end; (R)3 3SiO1/2) The source of the units is an M-group capping agent.
Further, wherein R is1
Alkyl with a mercapto group at the end, such as: -CH2CH2SH、-CH2CH2CH2SH、-CH2(CH3) CHSH; or
Is phenyl substituted alkyl with sulfhydryl at the end, such as: -C6H4CH2CH2SH、-C6H4CH2CH2CH2SH、-C6H4CH2(CH3)CHSH、-CH2CH2C6H4CH2CH2SH、-CH2CH2C6H4CH2CH2CH2SH、-CH2CH2CH2C6H4CH2CH2SH、-CH2CH2CH2C6H4CH2CH2CH2SH、-CH2(CH3)CHC6H4CH2CH2SH、-CH2(CH3)CHC6H4CH2CH2CH2SH; or
Mercapto-substituted acyloxy groups such as:
Figure BDA0002362509030000031
or
Mercapto-substituted amide groups such as:
Figure BDA0002362509030000032
Figure BDA0002362509030000033
or
Mercapto-substituted amino groups, such as:
Figure BDA0002362509030000034
Figure BDA0002362509030000035
wherein f-q are respectively selected from integer values between 1 and 18. Further, (R)2SiO3/2) The source of the units, i.e. R2Can be selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, phenyl, naphthyl, benzyl, tolyl, xylyl, biphenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, CH2CH2CH2NH、CH2(CH3)CHCH2(H)NCH3、CH2CH2NHCH2CH2NH2、CH2CH2NH2、CH2CH2NHCH3、CH2CH2CH2CH2NH2And CH2CH2NHCH2CH2NHC4H9。
Preferably, R1is-CH2CH2CH2SH，R3Is methyl.
(R1SiO3/2)aUnit and (R)2SiO3/2)bThe units are all T units, 0.25<a + b is less than 0.75, wherein, 0.025<a<0.50, or further, 0.20<a<0.50。
(R3 3SiO1/2)dThe units are M units, the molar fraction of M units is generally less than 0.75, i.e. the value of d may range from 0.10<d<0.70, or from 0.30<d<0.60。
(R4 2SiO2/2)eThe units are D units and the value of e (mole fraction of D units) typically ranges from 0 to 0.40, or 0 to 0.30, or 0 to 0.20.
(SiO4/2)cThe units are Q units, and the value of c typically ranges from 0 to 0.30, 0 to 0.20, or 0 to 0.10.
Further, several optimized MT-mercapto silicones are provided below:
the MT-mercapto silicone resin conforms to the following general formula: (HSC)3H6SiO3/2)a(Me3SiO1/2)dWherein, 0.35<a<0.70，a+d＝1。
Further, the MT-mercapto silicone resin corresponds to the general formula: (HSC)3H6SiO3/2)a(R2SiO3/2)b(Me3SiO1/2)dWherein R is2Is methyl, propyl or phenyl; 0.20<a<0.50，0.10<b<0.3，0.30<d<0.70；a+b+d＝1。
Further, the MT-mercapto silicone resin corresponds to the general formula: (HSC)3H6SiO3/2)a(SiO4/2)c(Me3SiO1/2)d(Et2SiO2/2)e；0.30<a<0.55，0≤c<0.30，0.30<d<0.60，0≤e<0.30；a+c+d+e＝1。
The second purpose of the invention is realized by adopting the following technical scheme:
a preparation method of MT-mercapto silicone resin comprises the following steps:
1) to R1SiX3Or it and R2Si X3Adding an M-group blocking agent and water, and hydrolyzing under the condition of Lewis acid;
wherein X is methoxy, ethoxy, isopropoxy or chlorine;
the M-group end-capping agent is trimethylchlorosilane or hexamethyldisiloxane;
2) and (3) carrying out split-phase extraction, neutralizing an organic phase with sodium carbonate, and carrying out reduced pressure distillation to obtain the MT-mercaptosiloxane resin.
The silicon-containing M-group blocking agent may include a monofunctional silane, siloxane or silazane suitable monofunctional silane includes a triorganosilane such as halo-, alkoxy-, carboxy-triorganosilane, more specifically, specific examples of the silicon-containing M-group blocking agent include trimethylchlorosilane or a hydrolysate thereof, vinyldimethylchlorosilane or a hydrolysate thereof, allyldimethylchlorosilane or a hydrolysate thereof, dimethylchlorosilane or a hydrolysate thereof, dimethylphenylchlorosilane or a hydrolysate thereof, diphenylmethylchlorosilane or a hydrolysate thereof, trimethylmethoxysilane or a hydrolysate thereof, vinyldimethylmethoxysilane or a hydrolysate thereof, allyldimethylmethoxysilane or a hydrolysate thereof, dimethylmethoxysilane or a hydrolysate thereof, dimethylphenylmethoxysilane or a hydrolysate thereof, diphenylmethylmethoxysilane or a hydrolysate thereof, trimethylethoxysilane or a hydrolysate thereof, vinyldimethylethoxysilane or a hydrolysate thereof, allyldimethylethoxysilane or a hydrolysate thereof, dimethylethoxysilane or a hydrolysate thereof, hexamethylethoxysilane, hexamethyldisiloxane or a hydrolysate thereof, hexamethyloxysilane, a hydrolysate thereof, a hexamethyloxysilane, a polysiloxane.
The silicon-containing M-group blocking agent may be added at various times during the formation of the MT-mercaptosiloxane resin, for example, during hydrolysis of R1SiX3Or it and R2SiX3Before, during or after the step. Thus, the silicon-containing M-group capping agent may be partially hydrolyzed prior to capping the T-mercaptosiloxane resin.
The amount of M-group capping agent may range from 0.01 to 0.90 moles of silicon-containing M-group capping agent per mole of silicon present in the silicone resin. Alternatively, in this embodiment, the amount of silicon-containing M-group capping agent may range from 0.10 to 0.80, or 0.25 to 0.75 moles of silicon-containing M-group capping agent per mole of silicon.
If in hydrolysis R1SiX3Or it and R2SiX3The step of (a) is followed by providing a silicon-containing M-group capping agent, then the amount of M-group capping agent may range from 0.01 to 0.75 moles of silicon-containing M-group capping agent per mole of silicon present in the siloxane resin. Alternatively, the amount of M-group capping agent may range from 0.01 to 0.50,Or from 0.01 to 0.40, or from 0.01 to 0.30, or from 0.01 to 0.20 moles of silicon-containing M-group capping agent per mole of silicon. In this example, the value of d (mole fraction of M units) is less than 0.30. Alternatively, the value of d in this embodiment may range from 0.05 to less than 0.20, or from 0.05 to 0.15, or from 0.10 to 0.15.
Further, in step 1), when R is1SiX3Or it and R2SiX3When X in (1) contains chlorine, the hydrolysis can be carried out without adding a Lewis acid, or further, when the Lewis acid is from the hydrolysis of the X group or is hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid or acetic acid; the hydrolysis is carried out in a solvent such as isopropanol, ethanol or dodecane.
In step 1), in hydrolysis R1SiX3Or it and R2SiX3The reaction temperature is generally maintained between 0 ℃ and 100 ℃ or between 20 ℃ and 80 ℃ during the step (a). However, as one of ordinary skill in the art will appreciate, other reaction temperatures that enable hydrolysis to occur are also contemplated.
Typically, sufficient water is used in this step to provide greater than 1.0 mole of water per mole of silicon in the resin, or sufficient water is used in this step to provide in the range of 1.0 to 20 moles of water per mole of silicon on the T-mercaptosiloxane resin.
The third purpose of the invention is realized by adopting the following technical scheme:
an MT-mercapto silicone as described above for use in a hair care product.
Compared with the prior art, the invention has the beneficial effects that:
the MT-mercapto silicone resin provided by the invention can play a large role in daily chemicals with a low addition amount. The MT-mercapto silicone resin is applied to hairdressing products, and can effectively improve the smoothness and the styling property of hair; the hair is soft, so that the hair can be conveniently straightened and curled, meanwhile, the hair can be brightened, and the moisture balance of the hair is protected.
The invention also provides a preparation method of the MT-mercapto silicone resin and application of the MT-mercapto silicone resin in hairdressing products.
Detailed Description
The following examples are included to illustrate preferred embodiments of the invention. It should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventor to function well in the practice of the invention, and thus can be considered to constitute preferred modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and equivalents can be substituted for elements thereof to adapt a particular situation or material to the teachings of the invention and still obtain a like or similar result without departing from the spirit and scope of the invention. It is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
In this application, the M, D, T and Q elements and nomenclature based on these elements are known in the art. For example, the MT-mercaptosiloxane resin of the present invention is a siloxane resin having at least M units and T units.
The general structural formulas of the MT-mercapto silicone resins obtained in examples 1 to 4 satisfy: (HSC)3H6SiO3/2)a(Me3SiO1/2)dWherein as (HSC)3H6SiO3/2) The unit is derived from alkyl with sulfhydryl at the terminal, such as gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl trichlorosilane or gamma-mercaptopropyl triethoxysilane; as (Me)3SiO1/2) The unit is derived from one or more than two of trimethylchlorosilane, trimethylethoxysilane and hexamethyldisiloxane; (HSC)3H6SiO3/2) Units and (Me)3SiO1/2) The unit feeding molar ratio is 1.00: (1.00-5.00), in view of (HSC)3H6SiO3/2) Units and (Me)3SiO1/2) The polymerization ratio of the units is present at the theoretical lower limit of 1.00: 3.00 actual preparation in MT-mercapto Silicone (HSC)3H6SiO3/2) Units and (Me)3SiO1/2) Molar ratio of units 1.00: (1.00-3.00); i.e. the value range of aThe circumference is 0.25-0.50, and the value range of d is 0.50-0.75; the content of the mercapto group in the obtained MT-mercapto silicone resin is 2.02-5.90 mmol/g.
Example 1
Mixing gamma-mercaptopropyl trichlorosilane (419.00 g, 2.00mol), trimethylchlorosilane (108.50 g, 1.00mol) and isopropanol (52.80 g, 0.88mol), controlling the temperature to be 0-10 ℃, and adding water (264.00 g, 14.67mol) within 30 min. Keeping the temperature of 0-10 ℃ for reaction for 60 min. The reaction mixture was heated to 30 ℃ for 60min and then heated to 60 ℃ for 180 min. After cooling, isododecane (211.20 g, 1.24mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The filtrate was heated to 150 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 1-a.
Viscosity of MT-Mercaptosiloxane resin 1-a: 14500 mPas, refractive index: 1.4892, mercapto content: 5.90 mmol/g.
Example 2
Gamma-mercaptopropyltrimethoxysilane (392.00 g, 2.00mol), trimethylethoxysilane (236.00 g, 2.00mol), isopropanol (62.80 g, 1.047mol) were mixed, the temperature was controlled at 0-10 ℃, a mixture of concentrated sulfuric acid (98% wt, 6.30 g, 0,06mol) and water (14.00 g, 0.77mol) was added over 10min, and then water (300.00 g, 16.67mol) was added over 20 min. Keeping the temperature of 0-10 ℃ for reaction for 60 min. The reaction mixture was heated to 30 ℃ for 120min and then to 60 ℃ for 180 min. After cooling, isododecane (251.20 g, 1.48mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The filtrate was heated to 150 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 1-b.
Viscosity of MT-Mercaptosiloxane resin 1-b: 2300mPa · s, refractive index: 1.4812, mercapto content: 4.78 mmol/g.
Example 3
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), hexamethyldisiloxane (243.00 g, 1.50mol) were mixed and the temperature was controlled at 30 ℃ and a mixture of trifluoromethanesulfonic acid (1.50 g, 0.01mol) and isopropanol (71.50 g, 1.192mol) was added over a period of 5 min. Water (357.50 g, 19.86mol) was added over 15min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, isododecane (286.00 g, 1.68mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The filtrate was heated to 150 ℃ and maintained under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 1-c.
Viscosity of MT-Mercaptosiloxane resin 1-c: 20 mPas, refractive index: 1.4450, mercapto content: 4.01 mmol/g.
Example 4
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), hexamethyldisiloxane (1620.00 g, 10.00mol) were mixed and a mixture of trifluoromethanesulfonic acid (4.20 g, 0.03mol) and isopropanol (209.20 g, 3.49mol) was added over a period of 5min at a controlled temperature of 30 ℃. Water (357.50 g, 19.86mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The obtained filtrate was heated to 80 ℃ and kept under a pressure of 1.3kPa for 30min, and excess hexamethyldisiloxane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 1-d.
Viscosity of MT-Mercaptosiloxane resin 1-d: 7 mPas, refractive index: 1.4432, mercapto content: 2.02 mmol/g.
The general structural formulas of the MT-mercapto silicone resins obtained in examples 5 to 8 satisfy: (HSC)3H6SiO3/2)a(R2SiO3/2)b(Me3SiO1/2)dWherein as (HSC)3H6SiO3/2) The source of the unit is gamma-mercaptopropyltrimethoxysilane or gamma-mercaptopropyltriethoxysilane; as (Me)3SiO1/2) The source of the units is hexamethyldisiloxane; as (R)2SiO3/2) The unit is derived from one or more than two of propyl trimethoxy silane, propyl triethoxy silane or phenyl trimethoxy silane; namely R2Is propyl or phenyl;
(HSC3H6SiO3/2) Unit, (R)2SiO3/2) Unit (Me)3SiO1/2) The unit feed molar ratio was (1.00): (0.43-0.78): (0.86-2.67); namely, the value range of a is 0.22 to 0.44, the value range of b is 0.10 to 0.30, and the value range of d is 0.33 to 0.65; the obtained MT-mercapto silicone resin has a mercapto content of 2.40-3.80 mmol/g.
Example 5
Gamma-mercaptopropyltrimethoxysilane (392.00 g, 2.00mol), phenyltrimethoxysilane (118.8 g, 0.86mol), hexamethyldisiloxane (169.71 g, 0.86mol) were mixed and a mixture of trifluoromethanesulfonic acid (1.50 g, 0.01mol) and isopropanol (70.00 g, 1.17mol) was added over a period of 5min at a controlled temperature of 30 ℃. The temperature was controlled at 30 ℃ and water (350.00 g, 19.44mol) was added over 30 min. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, hexaisododecane (280.00 g, 1.65mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. Heating the obtained filtrate to 80 ℃, keeping the temperature for 30min under the pressure of 1.3kPa, and distilling isododecane under reduced pressure to obtain colorless and transparent liquid, namely the phenyl MT-mercaptosiloxane resin 2-a.
Viscosity of phenyl-containing MT-mercaptosiloxane resin 2-a: 12800 mPas, refractive index: 1.4945, mercapto content: 3.92 mmol/g.
Example 6
Gamma-mercaptopropyltrimethoxysilane (392.00 g, 2.00mol), propyltrimethoxysilane (140.50 g, 0.86mol), hexamethyldisiloxane (185.20 g, 1.14mol) were mixed and a mixture of trifluoromethanesulfonic acid (1.50 g, 0.01mol) and isopropanol (71.71 g, 1.20mol) was added over a period of 5min at a temperature of 30 ℃. Water (358.60 g, 19.92mol) was added over 15min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, isododecane (286.86 g, 1.69mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The filtrate was heated to 150 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless and transparent liquid, i.e., propyl-containing MT-mercaptosiloxane resin 3-a.
Viscosity of propyl-containing MT-mercaptosiloxane resin 3-a: 3400mPa · s, refractive index: 1.4793, mercapto content: 3.80 mmol/g.
Example 7
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), propyltriethoxysilane (319.90 g, 1.55mol), hexamethyldisiloxane (323.00 g, 2.00mol) were mixed and the temperature was controlled at 30 ℃ and a mixture of trifluoromethanesulfonic acid (1.5 g, 0.01mol) and isopropanol (112.00 g, 1.87mol) was added over a period of 5 min. Water (560.00 g, 31.11mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, isododecane (448.00 g, 2.64mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The filtrate was heated to 80 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless and transparent liquid, i.e., propyl-containing MT-mercaptosiloxane resin 3-b.
Viscosity of propyl-containing MT-Mercaptosiloxane resin 3-b: 1200 mPas, refractive index: 1.4636, mercapto content: 2.61 mmol/g.
Example 8
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), propyltriethoxysilane (274.60 g, 1.33mol), hexamethyldisiloxane (432.10 g, 2.67mol) were mixed and the temperature was controlled at 30 ℃ and a mixture of trifluoromethanesulfonic acid (3.00 g, 0.02mol) and isopropanol (71.00 g, 1.18mol) was added over a period of 5 min. Water (591.67 g, 32.87mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, isododecane (473.33 g, 2.78mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. Heating the obtained filtrate to 80 ℃, keeping the temperature for 30min under the pressure of 1.3kPa, and distilling isododecane under reduced pressure to obtain colorless and transparent liquid, namely the propyl-containing MT-mercaptosiloxane resin 3-c.
Viscosity of propyl-containing MT-Mercaptosiloxane resin 3-c: 17 mPas, refractive index: 1.4432, mercapto content: 2.42 mmol/g.
The general structural formulas of the MT-mercapto silicone resins obtained in examples 9 to 10 satisfy: (HSC)3H6SiO3/2)a(SiO4/2)c(Me3SiO1/2)d；
Wherein as (HSC)3H6SiO3/2) The source of the unit is gamma-mercaptopropyltrimethoxysilane or gamma-mercaptopropyltriethoxysilane; as (Me)3SiO1/2) The source of the units is hexamethyldisiloxane; as (SiO)4/2) The source of the units is tetramethoxysilane or tetraethoxysilane; (HSC)3H6SiO3/2) Unit (Me)3SiO1/2) Unit and (SiO)4/2) The feed ratio of (1.00): (0.43-0.67): (0.57-2.00);
namely, the value range of a is 0.27 to 0.50, the value range of c is 0.13 to 0.30, and the value range of d is 0.25 to 0.58; the obtained MT-mercapto silicone resin has a mercapto content of 3.05-4.98 mmol/g.
Example 9
Gamma-mercaptopropyltrimethoxysilane (392.00 g, 2.00mol), tetramethoxysilane (130.29 g, 0.86mol), isododecane (104.43 g, 0.61mol) were mixed and a mixture of concentrated hydrochloric acid (36% wt, 15.71 g) and ethanol (52.29 g, 1.14mol) was added over a period of 5min at a temperature of 30 ℃. Water (260.86 g, 14.49mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 180min, and then heating to 80 ℃ for reaction for 120 min. After cooling, isododecane (104.43 g, 0.61mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. Hexamethyldisilazane (92.00 g, 0.57mol) was added to the filtrate, and the mixture was heated to 60 ℃ to react for 120 min. The mixture was heated to 150 ℃ and maintained under a pressure of 1.3kPa for 60 minutes, and isododecane was distilled off under reduced pressure to obtain a white solid powder, i.e., MT-mercaptosiloxane resin 4-a containing Q units.
Mercapto content of MT-mercaptosiloxane resin containing Q Unit 4-a: 4.98 mmol/g.
Example 10
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), tetraethoxysilane (277.30 g, 1.33mol), hexamethyldisiloxane (324.00 g, 2.00mol) were mixed and a mixture of concentrated hydrochloric acid (36% wt, 27.33 g) and ethanol (91.00 g, 1.98mol) was added over 5min at 30 ℃. Water (455.00 g, 25.28mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 180min, and then heating to 80 ℃ for reaction for 120 min. After cooling, isododecane (364.00 g, 2.14mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was separated, and a mixture of potassium hydroxide (1.83 g, 0.03mol) and methanol (15.00 g, 0.47mol) was added to the lower organic phase, which was heated to 80 ℃ and reacted for 120 min. After cooling, it is neutralized to neutrality with concentrated hydrochloric acid, then dried with anhydrous sodium sulphate and filtered. The filtrate was heated to 80 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 4-b containing Q units.
Viscosity of MT-mercaptosiloxane resin containing Q Unit 4-b: 4300 mPas, refractive index: 1.4720, mercapto content: 3.05 mmol/g.
The general structural formula of the MT-mercapto silicone resin obtained in example 11 satisfies: (HSC)3H6SiO3/2)a(Me3SiO1/2)d(Me2SiO2/2)e(ii) a As (HSC)3H6SiO3/2) The source of the unit is gamma-mercaptopropyltriethoxysilane; as (Me)2SiO2/2) The source of the units is dimethyldiethoxysilane as (Me)3SiO1/2) The source of the units is hexamethyldisiloxane; (HSC)3H6SiO3/2) Unit (Me)3SiO1/2) Unit (Me)2SiO2/2) The unit feeding molar ratio is 1.00: 1.00: 0.57. namely, the value of a is 0.39, the value of d is 0.39, the value of e is 0.22: the resulting MT-mercaptosilicone resin had a mercapto content of 2.87 mmol/g.
Example 11
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), dimethyldiethoxysilane (169.90 g, 1.15mol), hexamethyldisiloxane (324.00 g, 2.00mol) were mixed and a mixture of trifluoromethanesulfonic acid (1.5 g, 0.01mol) and isopropanol (97.50 g, 1.63mol) was added over a period of 5min at a controlled temperature of 30 ℃. Water (505.00 g, 28.06mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, isododecane (374.33 g, 2.20mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The filtrate was heated to 80 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 5-a containing D units.
Viscosity of MT-mercaptosiloxane resin containing D units 5-a: 780 mPas, refractive index: 1.4696, mercapto content: 2.87 mmol/g.
The general structural formula of the MT-mercapto silicone resin obtained in example 12 satisfies: (HSC)3H6SiO3/2)a(SiO4/2)c(Me3SiO1/2)d(Me2SiO2/2)e(ii) a As (HSC)3H6SiO3/2) The source of the unit is gamma-mercaptopropyltriethoxysilane; as(Me2SiO2/2) The source of the units is dimethyldiethoxysilane as (Me)3SiO1/2) The source of the units is hexamethyldisiloxane; as (SiO)4/2)cThe source of the units is tetraethoxysilane; (HSC)3H6SiO3/2) Unit, (SiO)4/2) Unit (Me)3SiO1/2) Unit (Me)2SiO2/2) The feeding molar ratio of the unit is 1: 0.40: 1.85: 0.96. namely, the value range of a is 0.31, the value range of c is 0.12, the value range of d is 0.57, and the value range of e is 0.30: the resulting MT-mercaptosilicone resin had a mercapto content of 2.69 mmol/g.
Example 12
Gamma-mercaptopropyltriethoxysilane (476.00 g, 2.00mol), tetraethoxysilane (168.10 g, 0.81mol), dimethyldiethoxysilane (142.70 g, 0.96mol), hexamethyldisiloxane (300.30 g, 1.85mol) were mixed, and a mixture of concentrated hydrochloric acid (36% wt, 33.00 g) and ethanol (132.00 g, 2.87mol) was added over a period of 5min at a temperature of 30 ℃. Water (426.67 g, 23.70mol) was added over 30min at 30 ℃. Controlling the temperature to 30 ℃ for reaction for 180min, and then heating to 80 ℃ for reaction for 120 min. After cooling, isododecane (440.00 g, 2.59mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was separated, and a mixture of potassium hydroxide (2.24 g, 0.04mol) and methanol (17.67 g, 0.55mol) was added to the lower organic phase, which was heated to 80 ℃ and reacted for 120 min. After cooling, it is neutralized to neutrality with concentrated hydrochloric acid, then dried with anhydrous sodium sulphate and filtered. The filtrate was heated to 80 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-mercaptosiloxane resin 6-a containing Q units and D units.
Viscosity of MT-mercaptosiloxane resin 6-a containing Q units and D units: 2900 mPas, refractive index: 1.4706, mercapto content: 2.69 mmol/g.
Comparative example 1
Methyltriethoxysilane (168.00 g, 0.94mol), hexamethyldisiloxane (810.0 g, 5.00mol) were mixed and a mixture of triflic acid (1.50 g, 0.01mol) and isopropanol (100.00 g, 1.67mol) was added over a period of 5min with temperature controlled at 30 ℃. The temperature was controlled at 30 ℃ and water (178.00 g) was added over 30 min. Controlling the temperature to 30 ℃ for reaction for 240min, and then heating to 60 ℃ for reaction for 120 min. After cooling, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was removed separately, and the resulting lower organic phase was neutralized with sodium carbonate, then dried with anhydrous sodium sulfate, and filtered. The obtained filtrate was heated to 80 ℃ and kept under a pressure of 1.3kPa for 30 minutes, and hexamethyldisiloxane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-methylsiloxane resin 7-a.
Viscosity of MT-methylsiloxane resin 7-a: 2 mPas, refractive index: 1.3856, mercapto content: 0 mmol/g.
Comparative example 2
N-propyltriethoxysilane (206.00 g, 1.00mol), dimethyldiethoxysilane (102.00 g, 0.82mol), hexamethyldisiloxane (121.50 g, 0.75mol) were mixed and a mixture of concentrated hydrochloric acid (36% wt, 12.90 g) and ethanol (51.60 g, 1.12mol) was added over 5min at 30 ℃. Water (281.00 g, 15.61mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 180min, and then heating to 80 ℃ for reaction for 120 min. After cooling, isododecane (172.00 g, 1.01mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was separated, and a mixture of potassium hydroxide (1.12 g, 0.02mol) and methanol (6.90 g, 0.22mol) was added to the lower organic phase, which was heated to 80 ℃ and reacted for 120 min. After cooling, it is neutralized to neutrality with concentrated hydrochloric acid, then dried with anhydrous sodium sulphate and filtered. The filtrate obtained was heated to 80 ℃ and maintained under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-propylsiloxane resin 7-b containing D units.
Viscosity of MT-propyl siloxane resin containing D units 7-b: 2100mPa · s, refractive index: 1.4265, mercapto content: 0 mmol/g.
Comparative example 3
N-propyltriethoxysilane (206.00 g, 1.00mol), tetraethoxysilane (100.40 g, 0.48mol), dimethyldiethoxysilane (89.60 g, 0.61mol), hexamethyldisiloxane (196.00 g, 1.21mol) were mixed, and a mixture of concentrated hydrochloric acid (36% wt, 17.70 g) and ethanol (70.80 g, 1.54mol) was added over a period of 5min at a temperature of 30 ℃. Water (284.00 g, 15.78mol) was added over 30min at a controlled temperature of 30 ℃. Controlling the temperature to 30 ℃ for reaction for 180min, and then heating to 80 ℃ for reaction for 120 min. After cooling, isododecane (238.20 g, 1.40mol) was added and extracted for 60min, the mixture was transferred to a separatory funnel and allowed to stand for phase separation. The upper aqueous phase was separated, and a mixture of potassium hydroxide (1.12 g, 0.02mol) and methanol (9.6 g, 0.30mol) was added to the lower organic phase, which was heated to 80 ℃ and reacted for 120 min. After cooling, it is neutralized to neutrality with concentrated hydrochloric acid, then dried with anhydrous sodium sulphate and filtered. The filtrate obtained was heated to 80 ℃ and maintained under a pressure of 1.3kPa for 30 minutes, and isododecane was distilled off under reduced pressure to obtain a colorless transparent liquid, i.e., MT-propylsiloxane resin 7-c containing Q units and D units.
Viscosity of MT-propyl siloxane resin 7-c containing Q units and D units: 4450 mPas, refractive index: 4216, mercapto content: 0 mmol/g.
Performance detection
The MT-mercapto silicone resins obtained in examples 1 to 12 and the MT silicone resins obtained in comparative examples 1 to 3 were subjected to a hair curling effect test with deionized water as a blank.
The formula of the hair curling product comprises an agent A and an agent B, wherein the agent A is prepared from 6 wt% of MT-mercapto silicone resin or MT silicone resin, 4 wt% of isohexadecane, 2 wt% of Sepigel 305 emulsifier, 3 wt% of glycerol, 5 wt% of ammonia water (28 wt%) and the balance of deionized water; the agent B consists of 3 wt% of hydrogen peroxide and the balance of deionized water.
The treatment method is as follows:
1) preparation of Hair sample
Taking a proper amount of hair (healthy hair without perm or hair dyeing treatment, length of about 20cm, 100 + -5 hair) of young female, cleaning with standard shampoo, washing with clear water for three times, rinsing with hair conditioner for one time, washing with clear water for three times, air drying, measuring from one end of hair root, cutting to 15cm length, fastening with nylon thread, making into hair bundle (1 g per bundle), spreading and coiling on hair curler (diameter of D)00.80cm) is fixed.
2) Hair curling treatment
And (3) immersing the fixed hair bundle into the prepared agent A, keeping the fixed hair bundle for half a minute, fishing up and placing the hair bundle on a net for one minute, naturally draining, wrapping the hair bundle with a PE plastic film, placing the hair bundle into a 60 ℃ oven, keeping the temperature for 15 minutes, taking out the hair bundle, cooling the hair bundle to room temperature, immersing the hair bundle in the agent B for 5 minutes, taking out the hair bundle, washing the hair bundle with deionized water for three times (50 milliliters of water per time), placing the hair bundle into the 60 ℃ oven, keeping the temperature for 10 minutes, taking out the hair bundle.
3) Measuring crimp radius
Putting curled hair on white paper, copying an arc with a pencil, taking two points on the arc, respectively making tangent lines, making the perpendicular lines of the two tangent lines, and making the intersection point of the two perpendicular lines to obtain the curling radius R of the hair0Thereby obtaining the curl diameter L of the hair0＝2R0。
4) Determination of curl Retention
The hair with the measured curl radius was suspended in a constant temperature and humidity apparatus having a relative humidity of 80% and a temperature of 25 ℃ for 24 hours, allowed to deform under its own weight, and then the deformed curl radius R was measuredt. And obtaining a deformed curl diameter L thereoft。
Curl retention was calculated as follows:
Figure BDA0002362509030000181
l is 15(cm) of original length of hair
LtCurl diameter (cm) of hair after 24 hours constant temperature suspension
L0Curl diameter (cm) of hair 24 hours before hanging it at constant temperature
5) Hair curling treatment results
TABLE 1 Hair curling treatment Effect
Figure BDA0002362509030000191
In the above table, curl diameter L0The hair waving agent shows initial waving performance, and the smaller the waving diameter, the better the initial waving effect.
In the above table, the curl diameter L after deformationtIt means that the hair curling agent has the property of resisting gravity and curling hair, and the smaller the curling diameter after deformation, the better the effect of resisting gravity and curling hair.
In the above table, the curl retention rate indicates the anti-fading capability of the curling agent, and the larger the curl retention rate, the better the anti-fading capability of the curling agent.
6) Comparative analysis of curl results
The MT-mercapto silicone resins obtained in examples 1 to 4 had a mercapto group content of 2 to 6 mmol. multidot.g-1The curl diameter L gradually increases with the viscosity0And a post-deformation curl diameter LtBoth decrease and then increase, indicating that both the initial curl performance and the gravity-resistant curl performance are better and then gradually worse, while the curl retention is higher and then gradually lower, indicating that the curl performance is better and then gradually worse in terms of anti-decay ability.
The MT-mercapto silicone resin obtained in examples 1 to 4 had a mercapto group content of 4 to 6 mmol. multidot.g-1Has higher curl retention rate, i.e. better anti-attenuation capability of curling performance.
The MT-mercapto silicone resins obtained in examples 1 to 4 had smaller curl diameters L at viscosities of 3000 mPas or less0And a post-deformation curl diameter LtNamely better initial hair curling performance and gravity-resistant hair curling performance.
MT-mercapto silicone resins from examples 5 to 8, in which some of the mercapto T-blocks were replaced by phenyl T-blocks or propyl T-blocks and the mercapto content was 2 to 4mmol g-1At the same time, the curl diameter L gradually increases with the viscosity0And a post-deformation curl diameter LtBoth increase gradually, indicating that the initial curling properties and the gravity-resistant curling properties are gradually deteriorated, while the curl retention rate increases first and then decreases gradually, indicating that the anti-fading capability of the curling properties is first improved and then gradually deteriorated.
The MT-mercapto silicone resins obtained in examples 5 to 8 had a mercapto group content of 2 to 3 mmol. multidot.g-1Has higher curl retention, i.e., better anti-fading capability of curling performance。
The MT-mercapto silicone resins obtained in examples 5 to 8 had smaller curl diameters L at viscosities of 3000 mPas or less0And a post-deformation curl diameter LtNamely better initial hair curling performance and gravity-resistant hair curling performance.
MT-mercapto silicone resins obtained in examples 9 to 10, to which a certain amount of Q-mer was introduced, had a mercapto group content of 3 to 4 mmol. multidot.g-1At the same time, the curl diameter L gradually increases with the viscosity0And a post-deformation curl diameter LtBoth gradually increase, indicating that the initial curling properties and the gravity-resistant curling properties are gradually deteriorated, while the curl retention rate is gradually decreased.
In the MT-mercapto silicone resins obtained in examples 9 to 10, the liquid mercapto silicone resin has a lower content of real mercapto groups than the solid mercapto silicone resin, but has a higher curl retention rate, i.e., a better curl performance with respect to damping, and a smaller curl diameter L0And a post-deformation curl diameter LtThe hair curling agent has the minimum, namely the initial hair curling performance and the gravity-resistant hair curling performance are better.
The MT-mercapto silicone resin obtained in example 11 has a certain amount of methyl D-mer introduced therein, and the mercapto group content is 2 to 3 mmol. multidot.g-1Crimp diameter L0Diameter L of crimp after deformationtAnd curl retention are preferably similar to those of example 8.
The MT-mercapto silicone resin obtained in example 12, which has incorporated therein both Q-mer and methyl D-mer in a certain amount, has a curl diameter L in comparison with that of example 80Diameter L of crimp after deformationtLarger, lower curl retention, i.e., both perform poorly.
Comparing the examples and comparative examples in the table together, none of the MT-silicone resins containing no mercapto group showed significant curling properties, while the MT-mercapto silicone resins of the various types showed significant curling properties with a mercapto group content of 2 mmol. g-1The above MT-mercapto silicone resin with viscosity of 3000 mPas or less has small crimp diameter L0Diameter L of crimp after deformationtAnd higher curl retention, i.e., better initial curl performance, gravity curl resistance, and curl decay resistanceForce.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.

Claims (10)

1. An MT-mercapto silicone, wherein the MT-mercapto silicone has the general formula:
(R1SiO3/2)a(R2SiO3/2)b(SiO4/2)c(R3 3SiO1/2)d(R4 2SiO2/2)e(ii) a Wherein a + b + c + d + e is 1, and c is more than or equal to 0 and less than 0.30;
R1is a mercapto-containing alkyl, aryl, acyloxy or amino group, a is more than or equal to 0.025;
R2is a hydrocarbyl, aryl, acyloxy or amino group, 0. ltoreq. b, and 0.25<a+b＜0.90；
R3Is alkyl, aryl, acyloxy or amino group, d is more than 0.10 and less than or equal to 0.75;
R4is a hydrocarbon group, e is 0 or less<0.40。
2. The MT-mercapto silicone of claim 1, wherein R is1
Comprises the following steps: -CH2CH2SH、-CH2CH2CH2SH、-CH2(CH3) CHSH; or
Comprises the following steps: -C6H4CH2CH2SH、-C6H4CH2CH2CH2SH、-C6H4CH2(CH3)CHSH、-CH2CH2C6H4CH2CH2SH、-CH2CH2C6H4CH2CH2CH2SH、-CH2CH2CH2C6H4CH2CH2SH、-CH2CH2CH2C6H4CH2CH2CH2SH、-CH2(CH3)CHC6H4CH2CH2SH、-CH2(CH3)CHC6H4CH2CH2CH2SH; or
Comprises the following steps:
Figure FDA0002362509020000011
Figure FDA0002362509020000012
Figure FDA0002362509020000013
wherein f-q are respectively selected from integer values between 1 and 18.
3. The MT-mercapto silicone of claim 1, wherein R is1is-CH2CH2CH2SH，R3Is methyl.
4. The MT-mercaptosilicone of claim 1 wherein 0.20< a < 0.50.
5. The MT-mercapto silicone according to claim 1, wherein said MT-mercapto silicone corresponds to the general formula: (HSC)3H6SiO3/2)a(Me3SiO1/2)dWherein, 0.35<a<0.70，a+d＝1。
6. The MT-mercapto silicone according to claim 1, wherein said MT-mercapto silicone corresponds to the general formula: (HSC)3H6SiO3/2)a(R2SiO3/2)b(Me3SiO1/2)dWherein R is2Is methyl, propyl or phenyl; 0.20<a<0.50，0.10<b<0.3，0.30<d<0.70；a+b+d＝1。
7. The MT-mercapto silicone according to claim 1, wherein said MT-mercapto silicone corresponds to the general formula: (HSC)3H6SiO3/2)a(SiO4/2)c(Me3SiO1/2)d(Et2SiO2/2)e；0.30<a<0.55，0≤c<0.30，0.30<d<0.60，0≤e<0.30；a+c+d+e＝1。
8. A preparation method of MT-mercapto silicone resin is characterized by comprising the following steps:
1) to R1SiX3Or it and R2SiX3Adding an M-group blocking agent and water, and hydrolyzing under the condition of Lewis acid;
wherein X is methoxy, ethoxy, isopropoxy or chlorine;
the M-group end-capping agent is trimethylchlorosilane or hexamethyldisiloxane;
2) and (3) carrying out split-phase extraction, neutralizing an organic phase with sodium carbonate, and carrying out reduced pressure distillation to obtain the MT-mercaptosiloxane resin.
9. The process according to claim 8, wherein in step 1) the Lewis acid is derived from the hydrolysis of the X group or is hydrochloric acid, sulfuric acid, trifluoromethanesulfonic acid or acetic acid; the hydrolysis is carried out in isopropanol, ethanol or isododecane.
10. An MT-mercapto silicone as described in any one of claims 1 to 7 for use in a hair care product.
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