阅读说明：本技术 非渗透性的含聚硅氧烷的嵌段共聚物及其制备方法和应用 (Non-permeable block copolymer containing polysiloxane, preparation method and application thereof ) 是由 张安强 何诗琦 张德强 钟伟强 林雅铃 于 2020-11-24 设计创作，主要内容包括：本发明属于杀菌材料技术领域,公开了非渗透性的含聚硅氧烷的嵌段共聚物及其制备方法和应用。具有式(Ⅰ)结构的含聚硅氧烷的嵌段共聚物：其中,n的取值为1-280,m的取值为30-400；b表示两个括号里的长链之间是嵌段结构；*表示取代的位置。相对于现有市售的小分子季铵盐杀菌剂,本发明所提出的具有式(Ⅰ)结构的含聚硅氧烷的嵌段共聚物具有更大的分子量,由于其分子体积巨大,难以渗透通过皮肤表皮,且可在皮肤表面有效吸附,尤其适合作为表皮长效杀菌剂使用。(The invention belongs to the technical field of sterilization materials, and discloses an impermeable block copolymer containing polysiloxane, a preparation method and an application thereof. A polysiloxane-containing block copolymer having the structure of formula (i): wherein, the value of n is 1-280, and the value of m is 30-400; b represents a block structure between two long chains in brackets; indicates the position of the substitution. Compared with the existing commercial small molecular quaternary ammonium salt bactericideThe polysiloxane-containing block copolymer with the structure of the formula (I) has larger molecular weight, is difficult to permeate through the epidermis of the skin due to large molecular volume, can be effectively adsorbed on the surface of the skin, and is particularly suitable for being used as a long-acting bactericide of the epidermis.)

1. A polysiloxane-containing block copolymer having the structure of formula (i):

wherein, the value of n is 1-280, and the value of m is 30-400;

b represents a block structure between two long chains in brackets;

indicates the position of the substitution.

2. The polysiloxane-containing block copolymer of formula (i) according to claim 1, wherein n is 1 to 200 and m is 50 to 300.

3. The polysiloxane-containing block copolymer according to claim 1, wherein the substituted position is hydrogen, alkyl, hydrocarbyl or aryl.

4. The polysiloxane-containing block copolymer having the structure of formula (I) according to claim 1, wherein the molecular weight of the polysiloxane-containing block copolymer having the structure of formula (I) is 5000-30000.

5. A process for preparing a polysiloxane containing block copolymer having the structure of formula (I) as claimed in any one of claims 1 to 4, which comprises the steps of:

(1) synthesis of polydimethylsiloxane-polymethylvinylsiloxane Block copolymer:

under the protection of inert gas, adding a siloxane ring material containing vinyl into a solvent, adding an initiator, carrying out a first reaction, then adding a siloxane ring material containing no vinyl and/or a siloxane ring material containing vinyl, carrying out a second reaction, adding a terminator, stirring, carrying out a third reaction, and separating to obtain a polydimethylsiloxane-polymethylvinylsiloxane block copolymer;

(2) synthesis of a polysiloxane-containing Block copolymer:

and (2) mixing the polydimethylsiloxane-polymethylvinylsiloxane segmented copolymer synthesized in the step (1), a catalyst, cysteamine hydrochloride and a solvent, stirring, reacting under the condition of ultraviolet irradiation, and separating to obtain the polysiloxane-containing segmented copolymer with the structure of the formula (I).

6. The process according to claim 5, wherein in the step (1), the vinyl group-containing siloxane ring material is at least one selected from the group consisting of trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane and pentamethylpentavinylcyclopentasiloxane; the siloxane ring material without vinyl is at least one of hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane.

7. The process according to claim 5, wherein in the step (1), the molar ratio of the vinyl group-containing siloxane ring material added before the first reaction to the total amount of the non-vinyl group-containing siloxane ring material and the vinyl group-containing siloxane ring material added before the second reaction is (0.5 to 12): (1-10).

8. The preparation method according to claim 5, wherein in the step (2), the mass ratio of the polydimethylsiloxane-polymethylvinylsiloxane block copolymer to the catalyst to the cysteamine hydrochloride is 1: (0.01-0.025): (0.588-1.26).

9. A fungicidal composition comprising the polysiloxane-containing block copolymer having the structure of formula (I) according to any one of claims 1 to 4.

10. Use of a polysiloxane containing block copolymer having the structure of formula (i) as claimed in any one of claims 1 to 4 in the preparation of a fungicide.

Technical Field

The invention belongs to the technical field of sterilization materials, and particularly relates to an impermeable block copolymer containing polysiloxane, and a preparation method and application thereof.

Background

Some microorganisms harmful to human bodies, such as bacteria, fungi, molds, etc., are inevitably encountered in daily life, and thus it is often necessary to inhibit or kill such microorganisms using an antibacterial agent to prevent contamination and invasion of the microorganisms such as bacteria.

Disinfection of human skin surfaces is clearly necessary. However, some small-molecule bactericides or disinfectants, such as quaternary ammonium salts, have strong permeability to the skin, penetrate through the skin epidermis barrier, enter the human body for circulation, have certain toxicity to the human body, and cause potential risks to be increased.

Therefore, it is desirable to provide an impermeable bactericide which is safe without permeating the skin and has good bactericidal properties.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides an impermeable block copolymer containing polysiloxane, a preparation method and application thereof, wherein the block copolymer containing polysiloxane contains primary amine hydrochloride groups, has no permeability to skin, has good bactericidal effect and is a very safe bactericidal agent.

In a first aspect of the invention, an impermeable polysiloxane-containing block copolymer is provided.

Specifically, an impermeable, polysiloxane-containing block copolymer having the structure of formula (I):

wherein, the value of n is 1-280, and the value of m is 30-400;

b represents a block structure between two long chains in brackets;

indicates the position of the substitution.

Preferably, the value of n is 1-200, and the value of m is 50-300; further preferably, the value of n is 50-180, and the value of m is 80-280; more preferably, the value of n is 50-150, and the value of m is 80-260.

Preferably, the substituted position may be hydrogen, alkyl, hydrocarbyl or aryl.

Further preferably, the alkyl group is C₁-C₈For example selected from methyl, ethyl or propyl.

Further preferably, the hydrocarbyl group is C₂-C₁₀For example, an ethenyl, propenyl, or butenyl group.

Preferably, the number average molecular weight of the impermeable polysiloxane-containing block copolymer of formula (I) is 5000-30000; further preferred number average molecular weight is 8000-.

Another aspect of the present invention provides a method for preparing an impermeable polysiloxane-containing block copolymer.

Specifically, the preparation method of the impermeable polysiloxane-containing block copolymer comprises the following steps:

(1) synthesis of polydimethylsiloxane-polymethylvinylsiloxane Block copolymer:

under the protection of inert gas, adding a vinyl-containing siloxane ring material into a solvent, adding an initiator, carrying out a first reaction, then adding a vinyl-free siloxane ring material and/or a vinyl-containing siloxane ring material, carrying out a second reaction, adding a terminator, stirring, carrying out a third reaction, and separating to obtain a polydimethylsiloxane-polymethylvinylsiloxane block copolymer, which is marked as PDMS-b-PVMS;

(2) synthesis of a polysiloxane-containing Block copolymer:

and (2) mixing the polydimethylsiloxane-polymethylvinylsiloxane block copolymer (PDMS-b-PVMS) synthesized in the step (1), a catalyst (the catalyst is represented by DMAP), cysteamine hydrochloride (AH) and a solvent, stirring, reacting under the condition of ultraviolet irradiation, and separating to obtain the polysiloxane-containing block copolymer (marked as PDMS-b- (PDMS-g-AH)) with the structure of the formula (I).

Preferably, in step (1), the inert gas is nitrogen or argon.

Preferably, in step (1), the solvent is tetrahydrofuran.

Preferably, in step (1), the vinyl-containing siloxane ring material is selected from trimethyltrivinylcyclotrisiloxane (labeled D)₃ ^v) Tetramethyltetravinylcyclotetrasiloxane (labeled as D)₄ ^v) Or pentamethylpentavinylcyclopentasiloxane (labeled D)₅ ^v) At least one of (1).

Preferably, in step (1), the non-vinyl-containing siloxane ring material is selected from hexamethylcyclotrisiloxane (labeled as D)₃) Or octamethylcyclotetrasiloxane (labeled D)₄) Or decamethylcyclopentasiloxane (labeled as D)₅) At least one of (1).

Preferably, in step (1), the molar ratio of the vinyl-containing siloxane ring material added before the first reaction to the total amount of the non-vinyl-containing siloxane ring material and/or vinyl-containing siloxane ring material added before the second reaction is (0.5 to 12): (1-10); further preferably, the molar ratio is (1-10): (1-10).

Further preferably, in step (1), the molar ratio of the vinyl-free siloxane ring material to the vinyl-containing siloxane ring material added before the second reaction is (0 to 3.5): (0.8-3.2); further preferably, the molar ratio is (0.1-3): (1-3).

Preferably, in step (1), the initiator is an anionic polymerization initiator; further preferably, the initiator is n-butyllithium (n-BuLi). The initiator functions as a ring-opening polymerization.

The amount of the initiator added is adjusted according to the molecular weight of the final product to be obtained.

Preferably, in the step (1), the temperature of the first reaction is below 1 ℃, and the time of the first reaction is 8-20 hours; further preferably, the temperature of the first reaction is 0 ℃ or lower, and the time of the first reaction is 10 to 14 hours.

Preferably, in the step (1), the temperature of the second reaction is below 1 ℃, and the time of the second reaction is 8-20 hours; further preferably, the temperature of the second reaction is 0 ℃ or lower, and the time of the second reaction is 10 to 14 hours.

Preferably, in the step (1), the terminating agent is chlorosilane containing vinyl; further preferably, the terminating agent is dimethylvinylchlorosilane (THF) or methylphenylvinylchlorosilane. The terminator functions as a terminator for polymerization and introduces a vinyl group at the end of a polymer chain.

Preferably, in the step (1), the mass ratio of the terminating agent to the vinyl-containing siloxane ring material is 1 (30-50).

Preferably, in the step (1), the time of the third reaction is 0.5-2 hours; further preferably 1 to 1.5 hours.

Preferably, in the step (1), the separation process is implemented by rotary evaporation at the temperature of 120-130 ℃ and filtration, and the filtrate is taken.

Preferably, in the step (2), the mass ratio of the polydimethylsiloxane-polymethylvinylsiloxane block copolymer to the catalyst to the cysteamine hydrochloride is 1: (0.01-0.025): (0.588-1.26); molar ratio [ AH ]]/[-NH₂]1.0-1.2/1. The amount of cysteamine hydrochloride added is generally calculated according to the vinyl content in PDMS-b-PVMS.

Preferably, in step (2), the solvent is an alcohol; methanol or ethanol is more preferable.

Preferably, in the step (2), the catalyst is ether or 2, 2-dimethylolpropionic acid; more preferably, the catalyst is benzoin diethyl ether.

Preferably, in the step (2), the wavelength of the ultraviolet light is 300-400 nm; further preferably 350-370 nm.

Preferably, in the step (2), the specific process of the separation is as follows: and (2) carrying out rotary evaporation on the mixture obtained after the reaction under the ultraviolet irradiation condition at the temperature of 60-70 ℃, removing most of solvent, adding a large amount of diethyl ether, separating out the product, and drying to obtain the product, namely the polysiloxane-containing block copolymer with the structure of the formula (I).

The catalyst in step (2) is a mercapto group (-SH) and a vinyl group (-CH ═ CH)₂) Catalysts for click addition. Cysteamine hydrochloride (AH) is also known as: 2-aminoethanethiol hydrochloride, the purpose of which is to react with the vinyl (-CH ═ CH) groups of polysiloxanes via the mercapto groups in the molecule₂) And click addition is carried out on the side group, and a primary amine hydrochloride group with bacteriostatic activity is introduced.

Preferably, the polysiloxane-containing block copolymer having the structure of formula (I) is synthesized by the following route (hv represents UV):

another aspect of the invention provides the use of an impermeable polysiloxane-containing block copolymer.

A germicidal composition comprising the aforementioned non-permeable polysiloxane-containing block copolymer.

The use of the aforementioned impermeable polysiloxane-containing block copolymers for the preparation of fungicides.

Compared with the prior art, the invention has the following beneficial effects:

compared with the existing commercial micromolecular quaternary ammonium salt bactericide, the PDMS-b- (PDMS-g-AH) provided by the invention has larger molecular weight, is difficult to permeate through the skin epidermis due to huge molecular volume, can be effectively adsorbed on the skin surface, and is particularly suitable for being used as an epidermis long-acting bactericide.

Drawings

FIG. 1 is an FTIR (Fourier Infrared Spectroscopy) spectrum of the polysiloxane-containing block copolymer obtained in example 1.

Detailed Description

In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.

The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.

Example 1: preparation of impermeable polysiloxane-containing Block copolymers

The synthetic route is as follows:

(1) synthesis of polydimethylsiloxane-polymethylvinylsiloxane Block copolymer:

20g of trimethyltrivinylcyclotetrasiloxane (D) are introduced under nitrogen into an eggplant-shaped reaction flask₃ ^v) 40g of tetrahydrofuran was added thereto, 4mL of n-butyllithium (n-BuLi) was added, and the mixture was subjected to a first reaction at a temperature of 0 ℃ for 12 hours, followed by addition of 20g of hexamethylcyclotrisiloxane (D)₃) Performing a second reaction at 0 ℃ for 12 hours, adding dimethylvinylchlorosilane (THF), stirring, performing a third reaction at 0 ℃ for 1 hour, separating, performing rotary evaporation at 130 ℃ and filtering to obtain a polydimethylsiloxane-polymethylvinylsiloxane segmented copolymer, wherein the label is PDMS-b-PVMS; number average molecular weight (M) of PDMS-b-PVMS_n) Weight average molecular weight (M)_w) And molecular weight distribution index (M)_w/M_n) Respectively as follows: 4900. 6200 and 1.26;

(2) synthesis of a polysiloxane-containing Block copolymer:

mixing the polydimethylsiloxane-polymethylvinylsiloxane block copolymer (PDMS-b-PVMS) synthesized in the step (1), benzoin diethyl ether, cysteamine hydrochloride (AH) (the mass ratio of the polydimethylsiloxane-polymethylvinylsiloxane block copolymer to the benzoin diethyl ether to the cysteamine hydrochloride is 1: 0.025: 1) and ethanol, stirring in a quartz reaction bottle, reacting for 1 hour under the 365nm ultraviolet irradiation condition, and separating: the mixture obtained after the reaction under the ultraviolet irradiation condition is subjected to rotary evaporation at 70 ℃, most of ethanol is removed, a large amount of ether is added, the product is separated out, and the product is dried in vacuum at 70 ℃ for 12 hours, so that the polysiloxane-containing block copolymer (marked as PDMS-b- (PDMS-g-AH)) is prepared, wherein the molecular weight of both blocks of PDMS and PDMS-g-AH in the PDMS-b- (PDMS-g-AH) is about 2500.

The hydrogen nuclear magnetic resonance spectrum of the polysiloxane-containing block copolymer obtained in example 1 was characterized as follows:¹H-NMR(600MHz,D₂O,ppm)δ:3.09(s,2H,SiCH₂CH₂SCH₂CH₂),2.83(s,2H,SiCH₂CH₂SCH₂),2.65(s,2H,SiCH₂CH₂),0.93(s,2H,SiCH₂),0-0.16(m,3H,SiCH₃)。

FIG. 1 is an FTIR (Fourier Infrared Spectroscopy) spectrum (wavenumber on the abscissa) of the polysiloxane-containing block copolymer obtained in example 1; as can be seen from the figure, at a wave number of 3410cm^-1(corresponding to the NH group), 2966cm^-1，1616cm^-1(corresponding to the NH group), 1268cm^-1，1110cm^-1，1040cm^-1，814cm^-1Has stronger absorption.

Example 2: preparation of impermeable polysiloxane-containing Block copolymers

Example 2 differs from example 1 only in the number average molecular weight (M) of the polydimethylsiloxane-polymethylvinylsiloxane block copolymer obtained by changing 20g of hexamethylcyclotrisiloxane in example 1 to 5g of hexamethylcyclotrisiloxane_n) Weight average molecular weight (M)_w) And molecular weight distribution index (M)_w/M_n) Respectively as follows: 5000. 6200, and 1.24.

Product effectiveness testing

Characterization of bacteriostatic properties

Taking dodecyl dimethyl benzyl ammonium chloride (benzalkonium chloride, BC) as a reference, respectively selecting escherichia coli (E.coli) and staphylococcus albus (S.albus) as representatives of gram-negative bacteria and gram-positive bacteria, and candida albicans (C.albicans) as representatives of fungi. The products synthesized in the examples were evaluated for their inhibitory effect on the three bacteria/fungi mentioned above.

The bacteriostatic experiment is briefly described as follows:

bacterial or fungal suspensions cultured in culture medium and diluted to 10⁵CFU/mL, then 100. mu.L of the bacterial or fungal suspension and 100. mu.L of a quaternary ammonium salt solution at various concentrations were mixed and transferred to a 96-well plate. Medium was used as a control instead of quaternary ammonium salt solution. Then, the 96-well plate was incubated at 28 ℃ (fungi) or 37 ℃ (bacteria) for an appropriate number of days, and then 10 μ L of 2,3, 5-triphenyltetrazolium chloride (TTC) solution with a mass concentration of 5% was added to each well of the 96-well plate, and incubated at an appropriate temperature for 2h in the dark. The Minimum Inhibitory Concentration (MIC) value is the lowest concentration at which no visible bacterial or fungal growth occurs, i.e. the concentration that is not stained red by TTC. Then 100 μ L of the mixture in 96-well plates at or above MIC values was transferred to culture medium for 48 hours. The Minimum Fungicidal Concentration (MFC) or Minimum Bactericidal Concentration (MBC) value is the lowest concentration at which less than 5 colonies formation is observed, and the results are shown in table 1.

Table 1: bacteriostatic effect of block copolymers containing polysiloxanes

As can be seen from table 1, the block copolymer containing polysiloxane prepared in examples 1-2 of the present invention has certain bacteriostatic effect on escherichia coli (e.coli), staphylococcus albus (s.albus) and candida albicans (c.albicans).