CN119081125A

CN119081125A - A modified hair care silicone oil and its preparation method and application

Info

Publication number: CN119081125A
Application number: CN202411228664.3A
Authority: CN
Inventors: 常宽; 刘付冰; 王靖; 晏晓东
Original assignee: Jiangnan University
Current assignee: Jiangnan University
Priority date: 2024-09-03
Filing date: 2024-09-03
Publication date: 2024-12-06

Abstract

The invention discloses a modified hair care silicone oil and a preparation method and application thereof, and belongs to the field of daily chemical industry. The modified hair care silicone oil of the invention is obtained by mixing silicone oil, an organic base and a solvent, stirring and dissolving; then adding a polyacid solution, stirring and reacting, purifying, and spin drying. The invention molecularly modifies amino silicone oil with a specific structure, connects Michael acceptor reactive groups, and utilizes Michael acceptor reactive groups to react with thiol groups in hair, thereby connecting silicone oil molecules to keratin in the form of chemical covalent bonds, thereby increasing the amount of silicone oil deposited on hair, improving the repair ability of hair hydrophobicity, and achieving multiple effects such as hydrophobicity, softness, and glossiness on hair. At the same time, the covalent bond connection is more firm, and the hair treated with the modified hair care silicone oil prepared by the invention is resistant to water washing, and can still retain a high hydrophobicity after multiple washings.

Description

Modified hair care silicone oil and preparation method and application thereof

Technical Field

The invention belongs to the field of daily chemical industry, and particularly relates to modified hair care silicone oil and a preparation method and application thereof.

Background

Nowadays, people have increasingly growing demands for hairdressing, hair bleaching, ironing and dyeing and styling are quite common, and part of people have high frequency. Such treatments, such as bleach-scalding, often lead to excessive loss and degradation of hair lipids, and in addition to the cleavage of disulfide bonds and oxidation of cysteines, which in turn lead to the disappearance of the hydrophobic barrier on the hair surface. On the one hand, the damage causes the water locking capacity of the hair to be reduced, the water enters and exits from the hair rapidly, the mechanical property of the hair is greatly influenced by the environment, on the other hand, the surface property of the hair is changed, the hydrophobicity is greatly reduced, the luster is lost, the scales of the hair are lifted, and finally, various hair quality problems such as dryness, dullness, roughness, fragility and the like are caused.

In order to solve the problems, natural grease and silicone oil are commonly used in hair care products to restore the hydrophobic property of hair. The natural grease and the silicone oil can play a series of roles of increasing the luster of the hairline, preventing static electricity, smoothing the hair tips and the like by forming a layer of protective film on the surface of the hairline. However, natural oils and silicone oils have limited adsorption capacity in hair and are easy to lose under multiple washes, and generally the use level of the oils and silicone oils needs to be increased to 1% -4% in shampoo products to ensure hair care effects, but silicone oils and oils have risks of blocking hair follicles and affecting scalp microecology when the use level of the oils and silicone oils is large.

Disclosure of Invention

Aiming at the defects of the prior art, the application provides modified hair care silicone oil and a preparation method and application thereof. According to the application, the modified hair care silicone oil is obtained by carrying out molecular modification on amino silicone oil with a specific structure and connecting Michael acceptor reactive groups. The Michael acceptor reactive group in the obtained modified hair care silicone oil can react with sulfydryl and amine in hair, so that silicone oil molecules are connected to keratin in a chemical covalent bond mode, further the deposition amount of the silicone oil on hair can be improved, the repairing capability of the hydrophobic property of the hair is improved, and multiple effects of hydrophobicity, softness, brightness, smoothness and the like of the hair are realized. Meanwhile, the covalent bond connection is firmer, and the hairline treated by the hair care silicone oil provided by the application is water-resistant, and can still keep higher hydrophobic performance after washing for a plurality of times.

The technical scheme of the invention is as follows:

the first aspect of the invention provides modified hair care silicone oil, and the structure of the modified hair care silicone oil is shown as a general formula (I):

Wherein R is Hoogch=chc-, m is 1 or more, n is 1 or more.

The second aspect of the invention provides a preparation method of hair care silicone oil, which comprises the following steps of mixing silicone oil, at least one organic base and a solvent, stirring and dissolving, then adding a polybasic acid solution, continuing stirring and reacting, purifying, and spin-drying to obtain the hair care silicone oil.

Preferably, the unit mole ratio of the silicone oil, the polybasic acid, the pyridine and the dicyclohexylcarbodiimide is 1 (1.6-2.4): 3.2-4.8.

Preferably, the unit mole ratio of the silicone oil, the polybasic acid, the pyridine and the dicyclohexylcarbodiimide is 1 (1.8-2.2): 3.6-4.4, and preferably, the unit mole ratio of the silicone oil, the polybasic acid, the pyridine and the dicyclohexylcarbodiimide is 1:2:4.

Preferably, the silicone oil is an amino silicone oil.

Preferably, the aminosilicone is poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ].

Preferably, the solvent is selected from at least one of dichloromethane, dichloroethane, chloroform and tetrahydrofuran, and the mass volume ratio g/mL of the silicone oil to the solvent is 5-30:100, preferably 8-15:100, and most preferably 11:100.

Preferably, the polyacid is a polyacid of an alpha, beta-unsaturated double bond.

Preferably, the polyacid solution is dimethyl sulfoxide solution of polyacid, and the concentration of the polyacid solution is 2% -8%, preferably 4% -6%, and more preferably 5.8%.

Preferably, the temperature of the stirring dissolution is from 0 ℃ to 20 ℃, preferably from 0 ℃ to 10 ℃, most preferably 4 ℃.

Preferably, the temperature of the stirring reaction is 0-20 ℃ and the time is 6-10h.

In a third aspect, the present invention provides the use of a hair care silicone oil as described in the first aspect or a hair care silicone oil prepared by the method of preparation as described in the second aspect, for hair care.

The beneficial technical effects of the invention are as follows:

According to the invention, the modified hair care silicone oil is obtained by carrying out molecular modification on amino silicone oil with a specific structure and connecting Michael acceptor reactive groups. The Michael acceptor reactive group in the obtained modified hair care silicone oil can react with sulfydryl and amine in hair, so that silicone oil molecules are connected to keratin in a chemical covalent bond mode, further the deposition amount of the silicone oil on hair can be improved, the repairing capability of the hydrophobic property of the hair is improved, and multiple effects of hydrophobicity, softness, brightness, smoothness and the like of the hair are realized. Meanwhile, the covalent bond connection is firmer, and the hairline treated by the hair care silicone oil provided by the invention is water-resistant, and can still keep higher hydrophobic performance after washing for a plurality of times.

Drawings

FIG. 1 is an infrared spectrum of the product molecule of example 1 of the present invention.

FIG. 2 is a comparison of the friction coefficients of hair care silicone oil, oleic acid, amino silicone oil prepared in examples 1-3 of the present invention applied to healthy hair and damaged hair.

FIG. 3 is a graph showing the contact angle comparison of hair care silicone oil, oleic acid, amino silicone oil prepared in examples 1-3 of the present invention applied to healthy hair and damaged hair.

FIG. 4 shows the friction coefficient of the hair care silicone oil, oleic acid, amino silicone oil prepared in examples 1 to 3 of the present invention after the application to healthy hair and damaged hair, after the elution test.

FIG. 5 shows contact angles before and after elution of the hair care silicone oil, oleic acid, and amino silicone oil prepared in examples 1 to 3 of the present invention after application to healthy hair and damaged hair.

FIG. 6 is a thermogravimetric curve of different hairs of the present invention.

Detailed Description

The present invention will be described in detail below with reference to the drawings and examples.

In order to achieve the above object, the first aspect of the present invention provides a modified hair care silicone oil, wherein the structure of the modified hair care silicone oil is shown as a general formula (I):

Wherein R is Hoogch=chc-, m is 1 or more, n is 1 or more.

The second aspect of the invention provides a preparation method of hair care silicone oil, which comprises the following steps:

and accurately weighing the silicone oil, the organic base and the solvent by a balance, adding the silicone oil, the organic base and the solvent into a beaker together, stirring for dissolution, adding the polybasic acid, and continuing stirring for reaction for 6-10h. After the reaction is finished, purifying and spin-drying to obtain the product, namely the hair care silicone oil.

It will be appreciated that the method of the present invention provides molecular modification of amino silicone oils of specific structure to attach michael acceptor reactive groups. The Michael acceptor reactive group can react with sulfhydryl and amine in hair, so that silicone oil molecules are connected to keratin in a chemical covalent bond mode, further, the deposition amount of silicone oil on hair can be increased, the repairing capability of the hair hydrophobic property is improved, and multiple effects of hydrophobicity, softness, brightness, smoothness and the like of the hair are reflected. Meanwhile, the covalent bond connection is firmer, and the hairline treated by the hair care silicone oil provided by the invention is water-resistant, and can still keep higher hydrophobic performance after washing for a plurality of times.

In some embodiments, the unit molar ratio of silicone oil, polyacid, organic base is 1 (1.6-2.4): 3.6-4.4.

In some embodiments, the unit molar ratio of silicone oil, polyacid, organic base is more preferably 1 (2-2.2): 4-4.4, preferably the unit molar ratio of silicone oil, polyacid, organic base is 1:2:4.

In some embodiments, the organic base comprises at least one of pyridine, dicyclohexylcarbodiimide, ethanol, sodium ethoxide.

Preferably, the organic base is pyridine or dicyclohexylcarbodiimide. The unit mole ratio of the silicone oil, the polybasic acid, the pyridine and the dicyclohexylcarbodiimide is 1 (1.6-2.4): 1.6-2.4. Preferably, the unit mole ratio of the silicone oil, the polybasic acid, the pyridine and the dicyclohexylcarbodiimide is 1 (1.8-2.2): (1.8-2.2): (1.8-2.2), and more preferably, the unit mole ratio of the silicone oil, the polybasic acid, the pyridine and the dicyclohexylcarbodiimide is 1:2:2:2.

In some embodiments, the silicone oil is an amino silicone oil, preferably the silicone oil is a non-terminal amino silicone oil, and further preferably the amino silicone oil is poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ].

In some embodiments, the solvent is selected from at least one of dichloromethane, dichloroethane, chloroform, tetrahydrofuran. The mass volume ratio g/mL of the silicone oil to the solvent is 5-30:100, preferably 8-15:100, and most preferably 11:100.

In some embodiments, the polyacid is a polyacid of an alpha, beta-unsaturated double bond, preferably the polyacid of an alpha, beta-unsaturated double bond is selected from at least one of maleic acid, fumaric acid, shikimic acid. According to the invention, by expanding molecules and selecting fumaric acid and shikimic acid, fumaryl silicone oil and shikimic acid amide silicone oil can be prepared respectively, and lubrication and hydrophobic property tests show that the synthetic molecules can improve hair smoothness and hydrophobicity, and the reaction has general applicability.

In some embodiments, the polyacid solution refers to a dimethylsulfoxide solution of a polyacid having a concentration of 2% to 8%, preferably 4% to 6%, more preferably 5.8%.

In some embodiments, the temperature of the stirring dissolution is from 0 ℃ to 20 ℃, preferably from 0 ℃ to 10 ℃, most preferably 4 ℃. The temperature of the stirring reaction is 0-20 ℃ and the time is 6-10h.

In some embodiments, the purification comprises, after the reaction is completed, adding distilled water for liquid separation purification until the aqueous phase ph=6-7, preferably ph=7, and the remaining solvent is subjected to spin-drying to obtain the product.

It is understood that the preparation method is to react polybasic acid with amino silicone oil to obtain the modified hair care silicone oil containing Michael acceptor reactive groups. Taking maleic acid and poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ] as examples, the route during the reaction is shown in the following formula (1):

Wherein m is greater than or equal to 1, and n is greater than or equal to 1.

When shikimic acid reacts with poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ], the route during the reaction is shown in the following formula (3):

In a third aspect, the present invention provides a hair care silicone oil prepared by the preparation method of the first aspect or the use of the hair care silicone oil of the second aspect, wherein the hair care silicone oil is used for hair care.

It can be understood that the hair care silicone oil prepared by the invention is obtained through amidation reaction, and can be in click reaction with sulfhydryl groups, so that free sulfhydryl protection of hair and improvement of hydrophobicity and smoothness of hair are realized. In addition, since it belongs to modified silicone oil, it has simultaneously good film forming property of conventional silicone oil. Therefore, the hair care silicone oil prepared by the invention can cooperate with each other to promote the repair of hair through the action of thiol clicking reaction and hair surface film forming for damaged hair containing free thiol, and the action of the hair care silicone oil for bleaching damaged hair bundles is similar to that of common silicone oil, and the hair care silicone oil can repair the damaged hair bundles through the film forming effect on the hair surface.

The mercapto impact principle (for example, maleimido silicone oil) is shown in formula (2).

Wherein m is greater than or equal to 1, and n is greater than or equal to 1.

The invention also provides a method for repairing hair by using the hair care silicone oil in the first aspect, which comprises the following steps of repairing damaged hair in a1, 3-propylene glycol solution of the hair care silicone oil at 30-45 ℃, most preferably at 40 ℃ for 5-30 min, preferably 10-20 min, wherein the 1, 3-propylene glycol solution of the hair care silicone oil is obtained by adding modified hair care silicone oil into the 1, 3-propylene glycol solution, and the mass fraction of the modified hair care silicone oil is 0.2% -0.6%, most preferably 0.5%. The repair bag dips damaged hair into the hair care silicone oil solution, or other method by which hair can be contacted with the hair care silicone oil. The invention does not limit the specific repairing method, and any method capable of realizing the effect of the invention is within the protection scope of the invention.

It will be appreciated that the maleimido silicone oils of the present invention prepared by acylation of amino silicone oils with maleic acid are useful in the technical field of hair products. In addition, the C-S bond newly generated in the sulfhydryl reaction can well solve the problems of dry, dull and rough hair caused by S-S bond fracture, thereby effectively improving the problems of hair performance damage caused by disulfide bond damage caused by hair smoothness and hydrophobicity (including bleaching, scalding, dyeing, ultraviolet irradiation, repeated washing, high temperature and the like).

The present invention will be further illustrated by examples and the like.

Example 1

The preparation method of the hair care silicone oil comprises the steps of accurately weighing silicone oil, pyridine, dicyclohexylcarbodiimide and maleic acid according to the mol ratio of 1:2:2:2 of silicone oil to pyridine to dicyclohexylcarbodiimide to polybasic acid, and simultaneously weighing dichloromethane according to the mass volume ratio g/mL of the silicone oil to dichloromethane of 5-30:100. Wherein, maleic acid is dissolved in dimethyl sulfoxide solution to prepare maleic acid solution with mass concentration of 5.8 percent for standby.

The silicone oil, pyridine, dicyclohexylcarbodiimide agent dichloromethane were added together into a beaker, stirred at 4 ℃ to dissolve, then maleic acid was added, and the stirring reaction was continued for 8h. After the reaction is finished, distilled water is added for liquid separation and purification until the pH value of the water phase is=7, and the residual solvent is dried by spin to obtain the product, namely the hair care silicone oil.

For the reacted system, assuming that the reaction is thorough, calculating the mass m ₁ of the product theory according to the stoichiometric coefficient, and finally obtaining the mass m ₂ of the product through experiments, wherein the yield is wt, and the calculation formula is as follows:

wt=(m₂/m₁)*100%

The yields of example 1 are shown in table 1.

Example 2

Example 2 was essentially the same as example 1, except that the type of organic acid was changed as shown in Table 1, in that fumaric acid was used as the organic acid in example 2. The yields of example 2 are shown in table 1.

Example 3

Example 3 is essentially the same as example 1, except that the type of organic acid is changed as shown in Table 1, and the organic acid used in example 3 is shikimic acid. The yields of example 3 are shown in table 1.

Examples 1'-3'

Examples 1'-3' were substantially the same as example 1, except that they were as shown in Table 1. Example 1' only changed the molar ratio of silicone oil, pyridine, dicyclohexylcarbodiimide and polyacid, example 2' changed the reaction temperature, and example 3' only changed the reaction time. The yields are shown in table 1.

Examples 4'-6'

Examples 4'-6' were substantially the same as example 2, except that they were as shown in Table 1. Example 4' only changed the molar ratio of silicone oil, pyridine, dicyclohexylcarbodiimide and polyacid, example 5' changed the reaction temperature, and example 6' only changed the reaction time. The yields are shown in table 1.

Examples 7'-9'

Examples 7'-9' were substantially the same as example 3, except that they were as shown in Table 1. Example 7' only changed the molar ratio of silicone oil, pyridine, dicyclohexylcarbodiimide and polyacid, example 8' changed the reaction temperature, and example 9' only changed the reaction time. The yields are shown in table 1.

Table 1 composition and yield of examples

As can be seen from the above table, the yields of the products were highest in examples 1-3 compared to the other conditions, so that the optimal reaction conditions were n silicone oil: n maleic acid: n pyridine: n dicyclohexylcarbodiimide=1:2:2, reaction time 8h, reaction temperature 4 ℃.

Therefore, the invention further examines the influence of different types of silicone oil on the preparation of the hair care silicone oil according to the condition.

Comparative example 10

Substantially the same as in example 1, except that the silicone oil raw material used was a common silicone oil, 0.1 ammonia value. The yields are shown in Table 2.

Comparative example 11

Substantially the same as in example 1, except that the silicone oil raw material used was a common silicone oil, namely, a Dow Corning amino silicone oil, having an ammonia value of 0.2. The yields are shown in Table 2.

Comparative example 12

Substantially the same as in example 1, except that the silicone oil raw material used was a common silicone oil having an ammonia value of 0.3. The yields are shown in Table 2.

TABLE 2 reaction conditions and yields for example 1 and comparative examples 10-12

As can be seen from Table 2, the product could not be obtained from the conventional aminosilicone, and the final reaction conditions were n poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ]: n maleic acid: n pyridine: n dicyclohexylcarbodiimide

=1:2:2:2, Reaction time 8h, reaction temperature 4 ℃.

After the reaction is finished, distilled water is used for liquid separation and purification, after the pH value of the water phase is neutral, the residual solution is spin-dried, and finally white emulsion is obtained, namely the molecule provided by the invention, and the maleimido silicone oil synthesized by maleic acid and silicone oil is taken as an example, and the infrared spectra of the molecule and the two main raw materials are shown in figure 3.

Application example

In view of the fact that hair is broken by disulfide bonds during ultraviolet irradiation or perming, free sulfhydryl groups are generated, so that the hydrophobic and smooth performances of the hair are reduced. Thus, the reactants impart the effect of protecting free sulfhydryl groups and protecting hair from uv damage.

In order to explore the optimal conditions of the modified hair care silicone oil prepared in the examples and the comparative examples for protecting free sulfhydryl groups, different experiments are designed to repair damaged hair bundles, wherein the damaged hair bundles are healthy Asian black hair, and the damaged hair bundles are obtained by incubating the healthy Asian black hair for 30min through 5% thioglycollic acid with the pH value of=9. And (3) dissolving the hair-care silicone oil in 1, 3-propylene glycol to obtain a repairing liquid, and researching the optimal repairing concentration, repairing corresponding temperature and repairing time of the hair-care silicone oil in the repairing liquid. Precisely weighing 0.5g of damaged hair bundles, respectively soaking the damaged hair bundles in the repairing solutions prepared in different examples or comparative examples, setting a certain reaction temperature and a certain reaction time, and taking out and airing the damaged hair bundles to obtain the repairing hair bundles. See in particular table 3.

Application examples 1 to 3

The use of the hair care silicone oils prepared in examples 1 to 3, respectively.

The specific application method comprises the steps of respectively mixing the hair care silicone oil prepared in the examples 1-3 with a1, 3-propylene glycol solution to obtain a repairing solution, wherein the mass concentration of the modified hair care silicone oil in the repairing solution is shown in the table 3 (the mass fraction in the table 3), respectively soaking 0.5g of damaged hair bundles in the repairing solution prepared by the hair care silicone oil prepared in the examples 1-3 to repair the damaged hair bundles, and obtaining a repaired hair sample, wherein the specific soaking temperature and time are shown in the table 3, namely the repairing temperature and repairing time in the table 3.

Comparative application examples 1 to 9

The modified hair care silicone oils of examples 1 to 3 were used for hair restoration, respectively, and differ from application examples 1 to 3 in specific restoration conditions, as shown in Table 3.

The specific application method comprises the steps of respectively mixing the hair care silicone oil prepared in the examples 1-3 with 1, 3-propylene glycol solution to obtain repair solutions with different modified silicone oils and different mass fractions as shown in the comparative application examples 1-9 in table 3, respectively soaking 0.5g of damaged hair bundles in the prepared repair solutions to finish repair of the damaged hair bundles, and using the repaired hair samples for subsequent tests, wherein the specific soaking temperature and time are shown in table 3, namely the repair temperature and repair time in table 3.

Comparative application examples 10 to 13

The hair care silicone oil prepared in comparative examples 10 to 12 was used directly for hair care using poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ].

The specific application method comprises the steps of mixing the hair care silicone oil or poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ] prepared in the comparative examples 10-12 with 1, 3-propylene glycol solution to obtain a repairing solution, wherein the mass concentration of the modified hair care silicone oil in the repairing solution is shown in the table 3 ("mass fraction" in the table 3), immersing 0.5g of damaged hair bundles in the repairing solution prepared in the comparative examples 10-12 to repair the damaged hair bundles, wherein the repairing temperature and the repairing time of the repaired hair bundles are shown in the table 3, and the repairing temperature and the repairing time of the repaired hair samples are shown in the table 3.

Test example:

The thiol content, the protection rate and the like of the hair treated by the application example are measured, and the method is concretely as follows:

(1) Determination of free thiol content:

The free mercapto group is reacted with excess DNTB at normal temperature to form a coloured substance which absorbs in ultraviolet light at 412nm, wherein E _mol =13600, A=according to the Lamber-Beer law

E _mol C L, and l=1, and the actual thiol concentration can be obtained by measuring the absorbance (a). This method is an Ellman method and allows quantification of free thiol groups in different hair strands.

The specific procedure was as follows, taking precisely 20mg of the hair samples treated in the application examples and comparative application examples, immersing in 1.0ml of a reaction buffer consisting of 8M urea, 10mM DTNB, 3mM ethylenediamine tetraacetic acid (EDTA) and 0.2M Tris-HCl, pH 8.0. The samples were incubated under N ₂ for 15min. After centrifugation at 8000rpm for 10min, the supernatant was taken and its absorbance was read at 412nm in the test results of the ultraviolet spectrophotometer. 3 replicates were run for each group and the final results averaged. The thiol content was calculated using the following equation:

Thiol content (mmol) g ^-1) =a×v/(13600×m) ×100%.

Wherein A is absorbance, mmol/L, V is volume of the clear liquid, L, m is mass of the clear liquid, g.

The thiol content of the damaged hair strand was a, the thiol content of the hair strand after the repair of the above application example was b, and the protection ratio (%) was calculated by the following formula,

Protection ratio = (a-b)/a x 100%

The content of free mercapto groups in the hair tresses obtained in the application examples, i.e., the protection ratio, is shown in Table 3.

TABLE 3 Effect of the products prepared in examples and comparative examples for thiol repair

As is clear from Table 3, the modified silicone oils of application examples 1 to 3 all have good restoration effects, and the unmodified amino silicone oils of comparative application examples 10 to 13 are theoretically incapable of restoring reduced hair, and the result of the experiment has a restoration rate of about 1%, which is attributed to the experimental error.

And under the optimal application condition, testing the performance of the hair after the hair care silicone oil is repaired. Specifically, 0.5g of damaged hair bundles are precisely weighed and soaked in blank, oleic acid, amino silicone oil and repairing solution (the mass fraction of modified hair care silicone oil in the repairing solution is 0.5%) in application examples 1-3 under the experimental conditions in application examples 1-3, the reaction temperature is set to be 40 ℃, the reaction time is 15min, and the damaged hair bundles are taken out and dried to obtain the repaired hair bundles. The following performance tests were performed using healthy hair tresses and hair tresses, respectively.

(2) Coefficient of friction test

The test method was as follows, according to the application examples, healthy hair tresses and reduced hair tresses were prepared, respectively, by treatment with 1, 3-propanediol, treatment with 1, 3-propanediol solution of 0.5% oleic acid, treatment with 1, 3-propanediol solution of 0.5% poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ], treatment with 1, 3-propanediol solution of 0.5% maleimido silicone oil (application example 1), treatment with 1, 3-propanediol solution of 0.5% fumaramido silicone oil (application example 2), and treatment with 1, 3-propanediol solution of 0.5% shikimamido silicone oil (application example 3), and hair tresses were obtained as test hair tresses, wherein the treatment temperature was 40 ℃ and the time was 15min. And randomly selecting 40 hairs from each group of hair bundles, testing 20 hairs by using an XCF-1A fiber friction coefficient tester, and calculating the average value of each group according to the dynamic friction coefficient obtained by the test to obtain the average value as the expression of the smoothness performance of each group of hairs. The specific results are shown in FIG. 2. In the figure, the blank represents 1, 3-propanediol treatment, oleic acid represents 0.5% oleic acid in 1, 3-propanediol solution treatment, aminosilicone represents 0.5% poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ] in 1, 3-propanediol solution treatment, maleimidosilane represents 0.5% maleimidosilane in 1, 3-propanediol solution treatment, fumaramidosilane represents 0.5% fumaramidosilane in 1, 3-propanediol solution treatment, shikimamido silicone represents 0.5% shikimamido silicone in 1, 3-propanediol solution treatment, and it is seen from the figure that the smooth lifting of aminosilicone, whether for healthy hair or for damaged hair, is more pronounced due to its extremely low surface tension, thereby making it easier to form a protective film on the hair surface, thereby achieving a smooth effect, compared to oleic acid. From the viewpoint of improving the smoothness of damaged hair, the repairing effect of modified silicone oil such as maleimido silicone oil, fumaryl silicone oil and shikimamide silicone oil is definitely the most excellent, because the nature of the modified silicone oil is the modified silicone oil, and the modified silicone oil has the active site of Michael addition while having low surface tension and good film forming property, and the repairing effect is the best due to the cooperation of the two factors.

(3) Hydrophobic Property test

The test method comprises the steps of preparing and treating hair bundles, testing friction coefficient, randomly selecting 20 hair bundles in each group, measuring contact angle of the hair bundles by using an OCA 40 optical contact angle measuring instrument, averaging, and taking average degree as the hydrophobic property. The specific results are shown in FIG. 3.

As can be seen from fig. 3, the improvement of the hydrophobic properties of the aminosilicone, both for healthy hair and for damaged hair, is more pronounced compared to oleic acid, due to its extremely low surface tension, which makes it easier to form a protective film on the hair surface, thus achieving a hydrophobic effect. From the viewpoint of improving the hydrophobicity of damaged hair, the repairing effect of modified silicone oil such as maleimido silicone oil, fumaryl silicone oil and shikimamide silicone oil is definitely the most excellent, because the nature of the modified silicone oil is the modified silicone oil, the modified silicone oil has the active site of Michael addition while having low surface tension and good film forming property, and the repairing effect is the best due to the cooperation of the two factors.

(4) Elution resistance test

And (3) performing an elution resistance test by using the reduced hair tress and the hair tress obtained after the reduced hair tress is repaired, repeatedly washing 7 times at room temperature by using shampoo, and simulating 7 times of shampoo in daily life. The hair before and after elution was tested for hydrophobicity and smoothness using the method described above. The results are shown in fig. 4 and 5.

From the figure, the restoration effect of the amino silicone oil is disappeared after elution, and the restoration of the maleic (fumare and shikima) amido silicone oil is slightly weakened relative to the restoration of the maleic (fumare and shikima) amido silicone oil before elution, which shows that the restoration of the maleic (fumare and shikima) amido silicone oil has the advantage of eluting resistance. In addition, the Michael addition plays a dominant role in the repair process of the maleimido silicone oil relative to the film-forming property of the silicone oil itself, and the use amount of the maleimido silicone oil is very low (0.5%), so that the factors greatly improve the risk of blocking hair follicles and affecting scalp microecology.

(5) Water-locking performance test

Healthy hair, reduced hair, and healed hair (maleimido silicone oil treated hair of application example 1, fumaramidyl silicone oil treated hair of application example 2, shikimamido silicone oil healed hair of application example 3) air-dried under the same environment with higher humidity were selected and cut into 1mm long and short hair pieces, and the moisture content was measured using a TGA/DSC1/1100SF thermogravimetric analyzer. See in particular fig. 6.

As can be seen from fig. 6, the total moisture content of the restored hair (15.28%) is significantly higher than that of the healthy hair (12.04%) because the surface barrier is destroyed and the external environment humidity is high, the moisture entry is more convenient, and the total moisture content of the restored hair (12.72%, 13.28%, 13.71%) is significantly reduced relative to that of the damaged hair and is very close to that of the healthy hair, so that the water-locking barrier of the damaged hair is significantly recovered after the maleimido silicone oil is restored.

The above is only a preferred embodiment of the present invention, and the present invention is not limited to the above examples. It is to be understood that other modifications and variations which may be directly derived or contemplated by those skilled in the art without departing from the spirit and concepts of the present invention are deemed to be included within the scope of the present invention.

Claims

1. The modified hair care silicone oil is characterized by having a structure shown in a general formula (I):

Wherein R is Hoogch=chc-, m is 1 or more, n is 1 or more.

2. A method for preparing the modified hair care silicone oil according to claim 1, comprising the steps of:

mixing silicone oil, organic base and solvent, stirring and dissolving;

then adding the polybasic acid solution, continuing stirring reaction, purifying, and spin-drying to obtain the modified hair care silicone oil.

3. The preparation method according to claim 2, wherein the unit molar ratio of the silicone oil, the polybasic acid and the organic base is 1 (1.6-2.4): 3.6-4.4.

4. The preparation method according to claim 2, wherein the unit molar ratio of the silicone oil, the polybasic acid and the organic base is more preferably 1 (2-2.2): (4-4.4), and preferably the unit molar ratio of the silicone oil, the polybasic acid and the organic base is 1:2:4;

The organic base comprises at least one of pyridine, dicyclohexylcarbodiimide, ethanolamine and sodium ethoxide.

5. The method of claim 2, wherein the silicone oil is an amino silicone oil.

6. The preparation method according to claim 2, wherein the aminosilicone is poly [ dimethylsiloxane-CO- (3-aminopropyl) methylsiloxane ].

7. The preparation method according to claim 2, wherein the solvent is at least one selected from dichloromethane, dichloroethane, chloroform and tetrahydrofuran, and the mass-to-volume ratio g/mL of the silicone oil to the solvent is 5-30:100, preferably 8-15:100, and most preferably 11:100.

8. The method according to claim 2, wherein the polybasic acid is a polybasic acid having an α, β -unsaturated double bond.

9. The method of claim 2, wherein the polyacid solution is dimethylsulfoxide solution of polyacid, and the concentration of the polyacid solution is 2% -8%, preferably 4% -6%, more preferably 5.8%;

The temperature of the stirring dissolution is 0 ℃ to 20 ℃, preferably 0 ℃ to 10 ℃, most preferably 4 ℃;

The temperature of the stirring reaction is 0-20 ℃ and the time is 6-10h.

10. Use of a hair care silicone oil according to claim 1 or a hair care silicone oil prepared by the method of any one of claims 2 to 9, wherein the hair care silicone oil is used for hair care.