阅读说明：本技术 一种聚硅氧烷嵌段聚合物及其应用 (Polysiloxane block polymer and application thereof ) 是由 刘海峰 王柱 哈成勇 孙成军 于 2019-08-05 设计创作，主要内容包括：本发明公开了一种聚硅氧烷嵌段聚合物及其应用。该聚硅氧烷嵌段聚合物,由如下步骤制备得到：(1)将2,4,6-三乙烯基-2,4-6-三甲基环三硅氧烷、六甲基环三硅氧烷混合均匀后溶于第一溶剂中,再加入第一引发剂反应,加入封端剂反应封端,得到乙烯基聚硅氧烷；(2)将步骤(1)得到的乙烯基聚硅氧烷、巯基单体、第二溶剂和第二引发剂混合均匀,紫外光照反应,或将步骤(1)得到的乙烯基聚硅氧烷、硅氢基单体和催化剂混合均匀反应,得到含SR<Sub>1</Sub>基或R<Sub>2</Sub>基的聚硅氧烷嵌段聚合物。本发明利用聚硅氧烷分子链段柔性高的特点以及偶联剂固化交联后偏向于无机材料的特点,制备韧性好、硬度高,具有疏水和自清洁特性的防护涂层。(The invention discloses a polysiloxane block polymer and application thereof. The polysiloxane block polymer is prepared by the following steps: (1) uniformly mixing 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane and hexamethylcyclotrisiloxane, dissolving in a first solvent, adding a first initiator for reaction, adding an end capping agent for reaction and end capping to obtain vinyl polysiloxane(ii) a (2) Uniformly mixing the vinyl polysiloxane obtained in the step (1), a sulfhydryl monomer, a second solvent and a second initiator, and carrying out ultraviolet irradiation reaction, or uniformly mixing the vinyl polysiloxane obtained in the step (1), a hydrosilyl monomer and a catalyst for reaction to obtain a mixture containing SR 1 Radical or R 2 Polysiloxane block polymers of the group. The invention utilizes the characteristic that polysiloxane molecular chain segments have high flexibility and the characteristic that coupling agents are biased to inorganic materials after curing and crosslinking to prepare the protective coating with good toughness, high hardness and hydrophobic and self-cleaning properties.)

1. A polysiloxane block polymer, characterized by being prepared by the steps of:

(1) uniformly mixing 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane and hexamethylcyclotrisiloxane, dissolving in a first solvent, adding a first initiator, reacting at the temperature of-20-30 ℃ for 3-24 h, adding an end capping agent, and reacting for 0.5-3 h to cap to obtain vinyl polysiloxane with the vinyl content of 10-100%;

(2) uniformly mixing the vinyl polysiloxane obtained in the step (1), a mercapto monomer, a second solvent and a second initiator, and carrying out ultraviolet irradiation for 10-60 min to obtain the composition containing SR₁Polysiloxane Block Polymer of said group R₁Is selected from (CH)₂)₃SiCH₃(OCH₃)₂，(CH₂)₃Si(OCH₂CH₃)₃，(CH₂)₃Si(OCH₃)₃And (CH)₂)₃SiCH₃(OCH₂CH₃)₂One of (1); or uniformly mixing the vinyl polysiloxane obtained in the step (1), the hydrosilyl monomer and the catalyst, and reacting for 15-48 h to obtain the compound containing R₂Polysiloxane Block Polymer of said group R₂Selected from SiCH₃(OCH₃)₂，Si(OCH₂CH₃)₃，Si(OCH₃)₃And SiCH₃(OCH₂CH₃)₂One kind of (1).

2. The polysiloxane block polymer of claim 1, wherein step (1) comprises the specific steps of: uniformly mixing 10 parts by mass of 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane and 0-77.5 parts by mass of hexamethylcyclotrisiloxane, dissolving in 0-350 parts by mass of first solvent, adding 0.01-0.5 part by mass of first initiator, reacting for 3-24 hours at-20-30 ℃, adding 0.1-2 parts by mass of end-capping agent, and reacting for 0.5-3 hours to cap to obtain vinyl polysiloxane with the vinyl content of 10-100%.

3. The polysiloxane block polymer of claim 2, wherein step (1) comprises the specific steps of: uniformly mixing 10 parts by mass of 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane and 0-50 parts by mass of hexamethylcyclotrisiloxane, dissolving the mixture in 0-350 parts by mass of a first solvent, adding 0.01-0.5 part by mass of a first initiator, reacting for 3-24 hours at the temperature of-20-30 ℃, adding 0.1-2 parts by mass of an end-capping agent, and reacting for 0.5-3 hours to cap to obtain vinyl polysiloxane with the vinyl content of 15-100%.

4. The polysiloxane block polymer of claim 2 or 3, wherein the first solvent is tetrahydrofuran or xylene, the first initiator is selected from one of tetramethylammonium hydroxide, dodecyltrimethylammonium hydroxide, cesium hydroxide, potassium hydroxide, sodium hydroxide, butyllithium, lithium trimethylsilanolate, sodium trimethylsilanolate, potassium trimethylsilanolate, cesium methanolate, potassium methanolate, sodium methanolate, lithium bistrimethylsilyl amine, and an alkali gum, and the blocking agent is selected from one of formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, trimethylchlorosilane, and vinyldimethylchlorosilane.

5. The polysiloxane block polymer of claim 1, wherein the preparation of step (2) comprises SR₁The specific steps of the polysiloxane block polymer are as follows: sequentially adding 10 parts by mass of vinyl polysiloxane, mercapto monomer with the same molar weight as vinyl, 0-90 parts by mass of second solvent and 0.001-0.1 part by mass of second initiator, uniformly mixing, and performing ultraviolet irradiation for 10-60 min to obtain the SR-containing material₁The polysiloxane block polymer comprises a mercapto monomer, a second solvent and a second initiator, wherein the mercapto monomer is selected from one of mercaptopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropylmethyldimethoxysilane and mercaptopropylmethyldiethoxysilane, the second solvent is selected from one of dichloromethane, tetrahydrofuran, ethyl acetate, xylene, toluene, acetonitrile, dioxane and cyclohexane, and the second initiator is selected from one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether.

6. The polysiloxane block polymer of claim 1, wherein the preparation of step (2) comprises SR₂The specific steps of the polysiloxane block polymer are as follows: sequentially adding 10 parts by mass of vinyl polysiloxane, a hydrosilyl monomer with the same molar weight as the vinyl and 0.001-0.1 part by mass of a catalyst, uniformly mixing, and reacting for 15-48 h to obtain the material containing SR₁The polysiloxane block polymer is a polysiloxane block polymer, the hydrosilyl monomer is one of triethoxysilane, trimethoxysilane, methyldimethoxysilane and methyldiethoxysilane, and the catalyst is a hydrosilylation catalyst.

7. Use of the polysiloxane block polymer according to claim 1 as a protective coating for metal, concrete, cloth or wood furniture.

8. Use of a polysiloxane block polymer according to claim 7 as a protective coating, characterized in that said protective coating is prepared by the steps of: 10 parts by mass of a mixture containing SR₁Polysiloxane block polymers containing radicals or containing SR₂The protective coating is prepared by dissolving a polysiloxane block polymer, 40-100 parts by mass of a third solvent, 1-5 parts by mass of water and 0.1-2 parts by mass of a second catalyst, stirring for 24-48 h to prepare a coating treatment liquid, and curing the coating treatment liquid.

9. The use of the polysiloxane block polymer of claim 8 as a protective coating, wherein said third solvent is selected from the group consisting of tetrahydrofuran, ethanol, toluene, xylene, trimethylbenzene, ethylbenzene and dioxane; the second catalyst is selected from one of hydrochloric acid, acetic acid, tetrabutyltin, tetraisobutyltin, dioctyltin oxide, dibutyltin dilaurate and dibutyltin diacetate.

10. The use of the polysiloxane block polymer as a protective coating according to claim 8, wherein the curing is carried out at 100-250 ℃ for 5-300 min or at room temperature for 7-20 days.

The technical field is as follows:

the invention relates to the technical field of high molecular materials and the technical field of fine chemical engineering, in particular to a polysiloxane block polymer and application thereof.

Background art:

common commercially available vinylpolysiloxanes having a vinyl content of up to 10% (i.e.10% of the silicon atoms are bonded to vinyl groups) are prepared by ring-opening copolymerization of octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane and are used as starting materials for silicone rubbers. In fact, the raw materials for preparing the silicone rubber do not need too high vinyl content, the common silicone rubber needs to mix polyvinyl polysiloxane with vinyl-terminated polysiloxane to achieve the optimal strength and toughness, and the higher content of vinyl polysiloxane is not reported due to no application requirement.

The invention content is as follows:

the invention aims to solve the problems in the prior art and provides a polysiloxane block polymer and application thereof. The invention fully utilizes the characteristic that polysiloxane molecular chain segments have high flexibility and the characteristic that coupling agents are biased to inorganic materials after curing and crosslinking to prepare the protective coating with good toughness, high hardness and hydrophobic and self-cleaning properties.

The invention provides a polysiloxane block polymer, which is characterized by being prepared by the following steps:

(1) uniformly mixing 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane (CAS number: 3901-77-7) and hexamethylcyclotrisiloxane (CAS number: 541-05-9), dissolving in a first solvent, adding a first initiator, reacting for 3-24 hours at the temperature of-20-30 ℃, adding a capping agent, and reacting for 0.5-3 hours to cap to obtain vinyl polysiloxane with the vinyl content of 10-100%;

(2) uniformly mixing the vinyl polysiloxane obtained in the step (1), a mercapto monomer, a second solvent and a second initiator, and carrying out ultraviolet irradiation for 10-60 min to obtain the composition containing SR₁Polysiloxane Block Polymer of said group R₁Is selected from (CH)₂)₃SiCH₃(OCH₃)₂，(CH₂)₃Si(OCH₂CH₃)₃，(CH₂)₃Si(OCH₃)₃And (CH)₂)₃SiCH₃(OCH₂CH₃)₂One of (1);

or uniformly mixing the vinyl polysiloxane obtained in the step (1), the hydrosilyl monomer and the catalyst, and reacting for 15-48 h to obtain the compound containing R₂Polysiloxane Block Polymer of said group R₂Selected from SiCH₃(OCH₃)₂，Si(OCH₂CH₃)₃，Si(OCH₃)₃And SiCH₃(OCH₂CH₃)₂One kind of (1).

The vinyl content mentioned above refers to the percentage of the molar amount of vinyl groups in the polysiloxane molecule to the molar amount of silicon. The polysiloxane block polymer is vinyl polysiloxane, a functional group of a coupling agent is introduced by a mercapto click chemistry/olefin hydrosilylation method, the cross-linking characteristic is endowed, and the polysiloxane block polymer has the effects of low surface energy characteristic, hydrophobicity and easiness in cleaning when being applied to metal, concrete and cloth furniture protection.

The reaction of 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane (ViD3) and hexamethylcyclotrisiloxane (D3) to produce vinyl polysiloxanes is shown in formula I:

wherein: initiator means a first initiator, Terminator means a terminating agent, and m/m + n is 0 to 0.1.

Containing SR₁The reaction equation for the polysiloxane block polymer is shown in formula II:

wherein R is₁Is selected from (CH)₂)₃SiCH₃(OCH₃)₂，(CH₂)₃Si(OCH₂CH₃)₃，(CH₂)₃Si(OCH₃)₃And (CH)₂)₃SiCH₃(OCH₂CH₃)₂One kind of (1).

Containing SR₂The reaction equation for the polysiloxane block polymer is shown in formula III:

wherein R in formula III₂Selected from SiCH₃(OCH₃)₂，Si(OCH₂CH₃)₃，Si(OCH₃)₃And SiCH₃(OCH₂CH₃)₂One kind of (1).

Preferably, the specific steps of step (1) are: uniformly mixing 10 parts by mass of 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane and 0-77.5 parts by mass of hexamethylcyclotrisiloxane, dissolving in 0-350 parts by mass of first solvent, adding 0.01-0.5 part by mass of first initiator, reacting for 3-24 hours at-20-30 ℃, adding 0.1-2 parts by mass of end-capping agent, and reacting for 0.5-3 hours to cap to obtain vinyl polysiloxane with the vinyl content of 10-100%.

Further, the specific steps of the step (1) are as follows: uniformly mixing 10 parts by mass of 2,4, 6-trivinyl-2, 4-6-trimethylcyclotrisiloxane and 0-50 parts by mass of hexamethylcyclotrisiloxane, dissolving the mixture in 0-350 parts by mass of a first solvent, adding 0.01-0.5 part by mass of a first initiator, reacting for 3-24 hours at the temperature of-20-30 ℃, adding 0.1-2 parts by mass of an end-capping agent, and reacting for 0.5-3 hours to cap to obtain vinyl polysiloxane with the vinyl content of 15-100%.

Further, the first solvent is tetrahydrofuran or xylene, the first initiator is selected from one of tetramethylammonium hydroxide, dodecyltrimethylammonium hydroxide, cesium hydroxide, potassium hydroxide, sodium hydroxide, butyllithium, lithium trimethylsilanolate, sodium trimethylsilanolate, potassium trimethylsilanolate, cesium methanolate, potassium methanolate, sodium methanolate, lithium bistrimethylsilyl amide, and an alkali glue having an initiating effect, and the blocking agent is selected from one of formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, trimethylchlorosilane, and vinyldimethylchlorosilane.

Preferably, the preparation described in step (2) comprises SR₁The specific steps of the polysiloxane block polymer are as follows: sequentially adding 10 parts by mass of vinyl polysiloxane, mercapto monomer with the same molar weight as vinyl, 0-50 parts by mass of second solvent and 0.001-0.1 part by mass of second initiator, uniformly mixing, and performing ultraviolet irradiation for 10-60 min to obtain the SR-containing material₁The polysiloxane block polymer comprises a mercapto monomer, a second solvent and a second initiator, wherein the mercapto monomer is selected from one of mercaptopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropylmethyldimethoxysilane and mercaptopropylmethyldiethoxysilane, the second solvent is selected from one of dichloromethane, tetrahydrofuran, ethyl acetate, xylene, toluene, acetonitrile, dioxane and cyclohexane, and the second initiator is selected from one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether.

Preferably, the preparation described in step (2) comprises SR₂The specific steps of the polysiloxane block polymer are as follows: sequentially adding 10 parts by mass of vinyl polysiloxane, a hydrosilyl monomer with the same molar weight as the vinyl and 0.001-0.1 part by mass of a catalyst, uniformly mixing, reacting for 15-48 h,to obtain a mixture containing SR₁The polysiloxane block polymer is a polysiloxane block polymer, the hydrosilyl monomer is one of triethoxysilane, trimethoxysilane, methyldimethoxysilane and methyldiethoxysilane, and the catalyst is a hydrosilylation catalyst. Hydrosilylation catalysts include karstedt hydrosilylation, speier and other catalysts commercially available that have a hydrosilylation catalytic effect.

The invention also provides the application of the polysiloxane block polymer as a protective coating, and the protective coating is used on metal, concrete, cloth or wooden furniture. Application methods include, but are not limited to, dipping, brushing, spraying, and the like.

Vinyl polysiloxane with 10-30% of vinyl content is used for water repellent treatment of textiles; vinyl polysiloxane with 10-100% of vinyl content is used for water repellent treatment of concrete; vinyl polysiloxane with vinyl content of 50-100% is used for metal anticorrosion treatment; the vinyl polysiloxane with the vinyl content of 40-100% is used for furniture protection treatment.

Preferably, the protective coating is prepared by the following steps: 10 parts by mass of a mixture containing SR₁Polysiloxane block polymers containing radicals or containing SR₂The protective coating is prepared by dissolving a polysiloxane block polymer, 40-100 parts by mass of a third solvent, 1-5 parts by mass of water and 0.1-2 parts by mass of a second catalyst, stirring for 24-48 h to prepare a coating treatment liquid, and curing the coating treatment liquid.

Further, the third solvent is one selected from tetrahydrofuran, ethanol, toluene, xylene, trimethylbenzene, ethylbenzene and dioxane; the second catalyst is selected from one of hydrochloric acid, acetic acid, tetrabutyltin, tetraisobutyltin, dioctyltin oxide, dibutyltin dilaurate and dibutyltin diacetate.

Further, the curing mode is curing for 5-300 min at the temperature of 100-250 ℃, or standing for 7-20 d at room temperature for curing.

The invention has the beneficial effects that: the vinyl polysiloxane disclosed by the invention is used as a raw material to graft a coupling agent to form an active monomer with high crosslinking degree, has a flexible chain segment and high crosslinking degree, has remarkable corrosion resistance and hydrophobic property and strong weather resistance, and is suitable for being used as a protective coating of structural parts and decorative parts under severe outdoor conditions.

The specific implementation mode is as follows:

the present invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.

The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art. In the following examples, the hydrosilylation catalyst is Sibao ACS-Pt-50.