阅读说明：本技术 含氟环体改性聚硅氧烷及其制备方法和应用 (Modified polysiloxane containing fluorine ring bodies, preparation method and application thereof ) 是由 冯威 顾廷海 刘健 史大阔 张永明 于 2020-12-17 设计创作，主要内容包括：本发明涉及含氟聚合物技术领域,具体涉及一种含氟环体改性聚硅氧烷及其制备方法和应用。所述含氟环体改性聚硅氧烷的制备方法,包括以下步骤：(1)将含氟二氯硅烷溶解于溶剂中,在40-100℃条件下水解,得到水解均聚物；(2)向水解均聚物中加入第一单体、第二单体、封端剂和催化剂,在60-120℃条件下反应2-10h,得到含氟环体改性聚硅氧烷。本发明的含氟环体改性聚硅氧烷,在聚硅氧烷主链中引入含氟链段,改善了亲水亲油性能,降低了表面张力,提高了硅油耐油、化学稳定性、耐溶剂性能；其制备方法简单,副产物少,后处理方便,得到的产物品质高,适用于润滑油添加剂、织物整理剂、离型剂、硬质涂层防污领域。(The invention relates to the technical field of fluorine-containing polymers, and particularly relates to fluorine-containing ring modified polysiloxane and a preparation method and application thereof. The preparation method of the fluorine-containing ring body modified polysiloxane comprises the following steps: (1) dissolving fluorine-containing dichlorosilane in a solvent, and hydrolyzing at 40-100 ℃ to obtain a hydrolyzed homopolymer; (2) adding a first monomer, a second monomer, a blocking agent and a catalyst into the hydrolysis homopolymer, and reacting for 2-10h at the temperature of 60-120 ℃ to obtain the fluorine-containing ring body modified polysiloxane. According to the fluorine-containing ring modified polysiloxane, the fluorine-containing chain segment is introduced into the main chain of the polysiloxane, so that the hydrophilic and oleophilic properties are improved, the surface tension is reduced, and the oil resistance, chemical stability and solvent resistance of silicone oil are improved; the preparation method is simple, few in byproducts, convenient in post-treatment, high in quality of the obtained product, and suitable for the fields of lubricating oil additives, fabric finishing agents, release agents and hard coating antifouling.)

1. A fluorine-containing cyclic modified polysiloxane, which is characterized in that: the chemical structural formula is as follows:

wherein x is an integer of 0 to 3500, y is an integer of 0 to 2000, and z is an integer of 1 to 3000;

r is H, CH₂＝CH-、CH₃-、CH₃CH₂-, allyl, methoxy, ethoxy or phenyl;

R₁and R₂Each or both of CH₃-、CH₃CH₂-, phenyl or cyanopropyl;

R₃is H, CH₂＝CH-、CH₃-, allyl, methoxy, ethoxy or phenyl, and R₃Not being H or CH together with R₂＝CH-；

R₄Is H or CH₂＝CH-；

R₅Is R₁、R₂、R₃、R₄One of the functional groups, but not H or CH₂＝CH-；

R_fHas the following structure:

in the formula, R₁₁、R₆、R₇、R₈is-F, -H, - (CF)₂)_nCF₃、-CH(CF(CF₃)₂)₂、-CF(CF₂)_nCF₂H、CF₃(CF₂O)_nX-or CF₃(CF₂CF₂O)_nX-, wherein n is an integer of 1 to 10, and X is a divalent hydrocarbon group of 0 to 6 carbons;

R₉、R₁₀is a perfluoroalkylene group of 2 to 20 carbon atoms or a-C-O-C-containing perfluoroalkylene group.

2. The fluorine-containing ring body-modified polysiloxane according to claim 1, characterized in that: x is-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CHCH₃CH₂-、-CH₂CHCH₃CH₂CH₂-or-CH₂CHCH₃CHCH₃CH₂-。

3. The fluorine-containing ring body-modified polysiloxane according to claim 1, characterized in that: r₉、R₁₀is-CF₂CF₂-、-CF₂CF₂CF₂-、-CF₂CFCF₃-、-C₈F₁₆-、-CF₂OCF₂-or-CF₂CF₂C(CF₃)₂O(CF₃)₂CCF₂CF₂-。

4. The fluorine-containing ring body-modified polysiloxane according to claim 1, characterized in that: when R is₃Or R₄Is CH₂When the fluorine-containing ring body modified polysiloxane is CH-, the fluorine-containing ring body modified polysiloxane is vinyl fluorosilicone oil, the fluorine content of the vinyl fluorosilicone oil is 10-80%, the vinyl content of the vinyl fluorosilicone oil is 0.2-40%, the polymerization degree DP is 100-²/s。

5. The fluorine-containing ring body-modified polysiloxane according to claim 1, characterized in that: when R is₃、R₄Is H, and R₃When R is not H simultaneously, the fluorine-containing ring modified polysiloxane is hydrogen-based fluorosilicone oil, the fluorine content of the fluorine-containing ring modified polysiloxane is 10-85%, the hydrogen content of the fluorine-containing ring modified polysiloxane is 5-70%, the polymerization degree DP is 15-500, and the viscosity of the fluorine-containing ring modified polysiloxane at 25 ℃ is 30-2000mm²/s。

6. A method for producing a fluorocyclo-modified polysiloxane according to any one of claims 1 to 5, which comprises: the method comprises the following steps:

(1) dissolving fluorine-containing dichlorosilane in a solvent, and hydrolyzing at 40-100 ℃ to obtain a hydrolyzed homopolymer;

(2) adding a first monomer, a second monomer, a blocking agent and a catalyst into the hydrolysis homopolymer, and reacting for 2-10h at the temperature of 60-120 ℃ to obtain fluorine-containing ring body modified polysiloxane;

the fluorine-containing dichlorosilane has the following structure:

the first monomer is one or more of tetramethyl tetravinylcyclotetrasiloxane, trimethyl trivinylcyclotrisiloxane, methyl vinyl siloxane mixed ring body, tetramethylcyclotetrasiloxane, heptamethylcyclotetrasiloxane and methyl hydrogen cyclosiloxane mixed ring body;

the second monomer is one or more of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octaphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, 1,3,5, 7-tetramethyl-2, 4,6, 8-tetracyanopropylcyclotetrasiloxane and 1,3,5, 7-tetraphenyl-2, 4,6, 8-tetracyanopropylcyclotetrasiloxane.

7. The method for producing a fluorocyclo-modified polysiloxane according to claim 6, wherein: in the step (1), the solvent is one of trifluoromethylbenzene, methyl pentafluorobenzene, pentafluorodichloropropane, trifluorotrichloroethane, FCH-101, 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, fluoromethyl-1, 1,1,3,3, 3-hexafluoroisopropyl ether, cyclohexane, n-heptane, n-pentane, xylene, toluene, dichloromethane, chloroform and carbon tetrachloride; the dosage of the solvent is 0.8 to 1.5 times of the total mass of the reactants.

8. The method for producing a fluorocyclo-modified polysiloxane according to claim 6, wherein: in the step (2), the catalyst is styrene-divinylbenzene type strong acid cation exchange resin, acid clay, trifluoromethanesulfonic acid and H₂SO₄One of chloroplatinic acid, sulfonated coal and zirconium solid acid catalyst; the amount of the catalyst is 0.1-1.5% of the total mass of the reactants.

9. The method for producing a fluorocyclo-modified polysiloxane according to claim 6, wherein: in the step (2), the end-capping reagent is one of tetramethyldiphenyl disiloxane, tetramethoxydimethyl disiloxane, tetraethoxydimethyl disiloxane, tetramethyldivinyldisiloxane, tetraethoxydivinyl disiloxane, tetramethyldiallyl disiloxane, tetramethyldisiloxane, methylvinyldimethoxysilane, hexamethoxydisiloxane, hexaethyldisiloxane and triethyldimethyl disiloxane.

10. Use of the fluorine-containing cyclic body-modified polysiloxane according to any one of claims 1 to 5, characterized in that: is used in the fields of lubricating oil, additives, fabric finishing agents, release agents and hard coating antifouling.

Technical Field

The invention relates to the technical field of fluorine-containing polymers, and particularly relates to fluorine-containing ring modified polysiloxane and a preparation method and application thereof.

Background

The organic silicon is a polymer with excellent high and low temperature resistance, weather resistance and aging resistance, and has wide application range. The fluorine-containing polysiloxane is polysiloxane with a side chain containing fluorine atoms, has excellent performances of high temperature resistance, chemical corrosion resistance, oil resistance, solvent resistance, low surface tension, low dielectric constant and the like of organic fluorine and organosilicon materials, is widely applied to the fields of automobiles, electronics, daily chemicals, medicines, aerospace and aviation and the like, and is an important direction for research of people.

Disclosure of Invention

The invention aims to provide fluorine-containing ring modified polysiloxane, wherein a fluorine-containing chain segment is introduced into a polysiloxane main chain, so that the hydrophilic and oleophilic properties are improved, the surface tension is reduced, and the oil resistance, chemical stability and solvent resistance of silicone oil are improved; the invention also provides a preparation method and application thereof, the preparation method is simple, the byproducts are few, the post-treatment is convenient, the obtained product has high quality, and the preparation method is suitable for the fields of lubricating oil additives, fabric finishing agents, release agents and hard coating antifouling.

The fluorine-containing ring modified polysiloxane has the following chemical structural formula:

wherein x is an integer of 0 to 3500, y is an integer of 0 to 2000, and z is an integer of 1 to 3000;

r is H, CH₂＝CH-、CH₃-、CH₃CH₂-, allyl, methoxyPhenyl, ethoxy or phenyl;

R₁and R₂Each or both of CH₃-、CH₃CH₂-, phenyl or cyanopropyl;

R₃is H, CH₂＝CH-、CH₃-, allyl, methoxy, ethoxy or phenyl, and R₃Not being H or CH together with R₂＝CH-；

R₄Is H or CH₂＝CH-；

R₅Is R₁、R₂、R₃、R₄One of the functional groups, but not H or CH₂＝CH-；

R_fHas the following structure:

in the formula, R₁₁、R₆、R₇、R₈is-F, -H, - (CF)₂)_nCF₃、-CH(CF(CF₃)₂)₂、-CF(CF₂)_nCF₂H、CF₃(CF₂O)_nX-or CF₃(CF₂CF₂O)_nX-wherein n is an integer of 1 to 10 and X is a divalent hydrocarbon group of 0 to 6 carbons, preferably-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂CHCH₃CH₂-、-CH₂CHCH₃CH₂CH₂-or-CH₂CHCH₃CHCH₃CH₂-CH is more preferable₂-、-CH₂CH₂-。

R₉、R₁₀Is a perfluoroalkylene group of 2 to 20 carbon atoms or a-C-O-C-containing perfluoroalkylene group, preferably-CF₂CF₂-、-CF₂CF₂CF₂-、-CF₂CFCF₃-、-C₈F₁₆-、-CF₂OCF₂-or-CF₂CF₂C(CF₃)₂O(CF₃)₂CCF₂CF₂-。

When R is₃Or R₄Is CH₂When the fluorine-containing ring body modified polysiloxane is CH-, the fluorine-containing ring body modified polysiloxane is vinyl fluorosilicone oil, the fluorine content of the vinyl fluorosilicone oil is 10-80%, the vinyl content of the vinyl fluorosilicone oil is 0.2-40%, the polymerization degree DP is 100-²/s。

When R is₃Or R₄Is H, and R₃When R is not H simultaneously, the fluorine-containing ring modified polysiloxane is hydrogen-based fluorosilicone oil, the fluorine content of the fluorine-containing ring modified polysiloxane is 10-85%, the hydrogen content of the fluorine-containing ring modified polysiloxane is 5-70%, the polymerization degree DP is 15-500, and the viscosity of the fluorine-containing ring modified polysiloxane at 25 ℃ is 30-2000mm²/s。

The preparation method of the fluorine-containing ring body modified polysiloxane comprises the following steps:

(1) dissolving fluorine-containing dichlorosilane in a solvent, and hydrolyzing at 40-100 ℃ to obtain a hydrolyzed homopolymer;

(2) adding a first monomer, a second monomer, a blocking agent and a catalyst into the hydrolysis homopolymer, and reacting for 2-10h at the temperature of 60-120 ℃ to obtain fluorine-containing ring body modified polysiloxane;

the fluorine-containing dichlorosilane has the following structure:

the first monomer is a tetramethyl tetravinylcyclotetrasiloxane, trimethyl trivinylcyclotrisiloxane, a methyl vinyl siloxane mixed ring body, tetramethylcyclotetrasiloxane, heptamethylcyclotetrasiloxane and methyl hydrogen cyclosiloxane mixed body;

the second monomer is one or more of octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, octaphenylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, hexaethylcyclotrisiloxane, octaethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, 1,3,5, 7-tetramethyl-2, 4,6, 8-tetracyanopropylcyclotetrasiloxane and 1,3,5, 7-tetraphenyl-2, 4,6, 8-tetracyanopropylcyclotetrasiloxane.

The blocking agent is MDnM, wherein n is an integer between 0 and 12; preferably one of tetramethyldiphenyldisiloxane, tetramethoxydimethyldisiloxane, tetraethoxydimethyldisiloxane, tetramethyldivinyldisiloxane, tetraethoxydivinyldisiloxane, tetramethyldiallyldisiloxane, tetramethyldisiloxane, methylvinyldimethoxysilane, hexamethoxydisiloxane, hexaethyldisiloxane and triethyldimethyldisiloxane.

In the step (1), the solvent is one of trifluoromethylbenzene, methyl pentafluorobenzene, pentafluorodichloropropane, trifluorotrichloroethane, FCH-101, 1,1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether, fluoromethyl-1, 1,1,3,3, 3-hexafluoroisopropyl ether, cyclohexane, n-heptane, n-pentane, xylene, toluene, dichloromethane, chloroform and carbon tetrachloride, and is preferably pentafluorodichloropropane or trifluoromethylbenzene. The dosage of the solvent is 0.8 to 1.5 times of the total mass of the reactants.

In the step (2), the catalyst is styrene-divinylbenzene type strong acid cation exchange resin, acid clay, trifluoromethanesulfonic acid and H₂SO₄One of chloroplatinic acid, sulfonated coal and zirconium solid acid catalyst; the amount of the catalyst is 0.1-1.5% of the total mass of the reactants.

The fluorine-containing ring body modified polysiloxane is applied to the fields of lubricating oil, additives, fabric finishing agents, release agents and hard coating antifouling.

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

(1) according to the invention, the fluorine-containing prepolymer is prepared by hydrolysis, and an organic solvent is used in the reaction process, so that the reaction is milder, the workload of subsequent demulsification and extraction is reduced, and the production efficiency is improved;

(2) according to the invention, the fluorine-containing chain segment is introduced into the polysiloxane main chain, so that the hydrophilic and oleophilic properties can be effectively improved, the surface tension can be reduced, and the oil resistance, chemical stability and solvent resistance of silicone oil can be improved;

(3) the invention can flexibly and efficiently design molecular structure, better control viscosity, fluorine content and other group content, and better quality of silicone oil.

Detailed Description

The invention is further illustrated below with reference to examples.

Examples of the fluorine-containing segment R_f1The following structures are taken as examples:

in the formula, R_fHas the following structure:

R₁₁、R₆is CF₃；R₇、R₈Is F; r₉、R₁₀is-CF₂CF₂-。

Example 1

(1) 206.22g (0.3mol) of fluorine-containing dichlorosilane is added into 150ml of trifluoromethyl benzene solvent dropwise and hydrolyzed for 2h at 60 ℃ in 350ml of deionized water, and then the mixture is neutralized, filtered and dried, and the solvent is removed at 103 ℃ under 50mmHg, so that 172.64g of fluorine-containing hydrolyzed homopolymer is prepared, and the yield is 91%;

(2) 15.71g (5.31X 10) were then added^-2mol) Octamethylcyclotetrasiloxane, 10.43g (3.03X 10)^-2mol) tetravinylcyclotetrasiloxane, 0.099g (6.07X 10)^-4) Hexamethyldisiloxane, then adding a catalyst of trifluoromethanesulfonic acid with the total mass of 0.3% of reactants, reacting for 6h at 80 ℃, neutralizing and decoloring after the reaction is finished, and devolatilizing at 140 ℃/5mmHg to obtain 182.98g of product with the viscosity of 837mm²(s) the product has the following formula: (Me)₃SiO_1/2)₂(R_f1)₄₅₀(Me₂SiO)₃₅₀(MeViSiO)₂₀₀。

Example 2

(1) 206.22g (0.3mol) of fluorine-containing dichlorosilane is added into 150ml of trifluoromethyl benzene solvent dropwise and hydrolyzed for 2h at 60 ℃ in 350ml of deionized water, and then the mixture is neutralized, filtered and dried, and the solvent is removed at 103 ℃ under 50mmHg, so that 176.43g of fluorine-containing hydrolyzed homopolymer is prepared, and the yield is 93%;

(2) 10.66g (3.10X 10) were then added^-2mol) tetravinylcyclotetrasiloxane, 16.06g (5.43X 10)^{- 2}mol) octamethylcyclotetrasiloxane, 0.144g (7.75X 10)^-4) Divinyltetramethyldisiloxane, then adding a catalyst of trifluoromethanesulfonic acid with the total mass of 0.3% of reactants, reacting for 6h at 80 ℃, neutralizing and decoloring after the reaction is finished, and devolatilizing at 140 ℃/5mmHg to obtain 186.02g of product with the viscosity of 608mm²(s) the product has the following formula: (Me)₂ViSiO_1/2)₂(R_f1)₃₆₀(Me₂SiO)₂₈₀(MeViSiO)₁₆₀。

Example 3

(1) 412.43g (0.6mol) of fluorine-containing dichlorosilane is added into 300ml of trifluoromethyl benzene solvent dropwise and hydrolyzed for 2h at 60 ℃ in 700ml of deionized water, and then the mixture is neutralized, filtered, dried and the solvent is removed at 103 ℃ under 50mmHg, so that 339.59g of fluorine-containing hydrolyzed homopolymer is prepared, and the yield is 89.5%;

(2) then 16.11g (6.71X 10) were added^-2mol) tetramethylcyclotetrasiloxane, 0.646g (3.98X 10)^-3) Hexamethyldisiloxane 4.41g (1.49X 10)^-2mol) octamethylcyclotetrasiloxane, adding trifluoromethanesulfonic acid as catalyst in 0.5% of total mass of reactant, reacting at 110 deg.C for 4h, neutralizing, decolorizing after reaction, and devolatilizing at 140 deg.C/5 mmHg to obtain 339.12g product with viscosity of 289mm²(s) the product has the following formula: (Me)₃SiO_1/2)₂(R_f1)₁₃₅(Me₂SiO)₃₀(MeHSiO)₁₃₅。

Example 4

(1) 412.43g (0.6mol) of fluorodichlorosilane was added dropwise to 300ml of a trifluoromethylbenzene solvent and hydrolyzed at 60 ℃ for 2 hours in 700ml of deionized water, followed by neutralization, filtration, drying and removal of the solvent at 103 ℃ under 50mmHg to give 333.91g of a fluorohydrolyzed homopolymer with a yield of 88%.

(2) 15.84g (6.60X 10) were then added^-2mol) tetramethylcyclotetrasiloxane, 0.525g (3.91X 10)^-3) Tetramethyldisiloxane, 4.34g (1.47X 10)^-2mol) octamethylcyclotetrasiloxane, adding trifluoromethanesulfonic acid as catalyst in 0.5% of total mass of reactant, reacting at 110 deg.C for 4h, neutralizing, decolorizing after reaction, devolatilizing at 140 deg.C/5 mmHg to obtain 336.87g product with viscosity of 306mm²(s) the product has the following formula: (Me)₂HSiO_1/2)₂(R_f1)₁₃₅(Me₂SiO)₃₀(MeHSiO)₁₃₅。

Example 5

(1) 206.22g (0.3mol) of fluorine-containing dichlorosilane is added into 150ml of trifluoromethyl benzene solvent dropwise and hydrolyzed for 2h at 60 ℃ in 350ml of deionized water, and then the mixture is neutralized, filtered and dried, and the solvent is removed at 103 ℃ under 50mmHg, so that 176.44g of fluorine-containing hydrolyzed homopolymer is prepared, and the yield is 93%;

(2) 16.06g (5.43X 10) were then added^-2mol) Octagyclotetrasiloxane, 20.34g (3.1X 10)^-2mol) tetramethyltetraphenylcyclotetrasiloxane, 0.101g (6.2X 10)^-4mol) hexamethyldisiloxane, then adding a catalyst of trifluoromethanesulfonic acid with the total mass of 0.3% of reactants, reacting for 6h at 80 ℃, neutralizing and decoloring after the reaction is finished, and devolatilizing under 140/5mmHg to obtain 196.96g of product with the viscosity of 889mm²(s) the product has the following formula: (Me)₃SiO_1/2)₂(R_f1)₄₅₀(Me₂SiO)₃₅₀(Ph₂SiO)₂₀₀。

Example 6

1g of the vinyl silicone oil synthesized in example 2 and 0.1g of the hydrogen-containing silicone oil synthesized in example 3 were mixed, 100ppm of a platinum group metal catalyst was added, and n-heptane was used as a solvent to prepare a mold release agent having a silicone oil content of 5%. Coating the prepared release agent on a PET film with the thickness of 75 μm to ensure that the solid component is 0.4g/m²And heating and curing the mixture in an oven at 120 ℃ for 50 seconds, and then taking out. The obtained release layer was evaluated by FINAT method, and the peel force was 0.12N/25mm and the residual adhesion was 96%.