阅读说明：本技术 含氟硅油、制备方法及其应用 (Fluorine-containing silicone oil, preparation method and application thereof ) 是由 蔡露 孙仁斌 于 2020-12-31 设计创作，主要内容包括：本发明提供了一种含氟硅油,结构式如式(Ⅰ)所示,其中,a、m、n、y为自然数,a的范围在1～5,m的范围在1～2,n的范围在1～3,y的范围在1～5。含氟硅油以四氢全氟辛基丙烯酰苯甲酸酯为含氟功能单体,以刚性苯环作为连接基将环境友好的短氟碳链键合至氨基硅油分子中,利用苯环中π-π共轭体系促使短氟碳链朝外垂直于基体表面进行规整排列,提供更为显著有效的氟烷基屏蔽效果,从而带来优异的防水效果；采用的氟烷基均为短氟碳链,不属于全氟辛基磺酰胺衍生物类禁用含氟化学品范围,不存在生物毒性和累积性问题；该含氟硅油采用常规乳化工艺即可获得乳液型含氟硅油,乳化工艺简便,原材料易得,更为适合工业化生产和推广应用。(The invention provides fluorine-containing silicone oil, which has a structural formula shown in a formula (I), wherein a, m, n and y are natural numbers, a ranges from 1 to 5, m ranges from 1 to 2, n ranges from 1 to 3, and y ranges from 1 to 5. The fluorine-containing silicone oil uses tetrahydroperfluorooctyl acryloyl benzoate as a fluorine-containing functional monomer, uses a rigid benzene ring as a connecting group to bond an environment-friendly short fluorocarbon chain into an amino silicone oil molecule, and uses a pi-pi conjugated system in the benzene ring to promote the short fluorocarbon chain to be outward and vertically arranged on the surface of a substrate in a regular way, so that a more obvious and effective fluoroalkyl shielding effect is provided, and an excellent waterproof effect is brought; the adopted fluoroalkyl groups are short fluorocarbon chains, do not belong to the range of forbidden fluorine-containing chemicals in perfluorooctyl sulfonamide derivatives, and do not have the problems of biological toxicity and accumulation; the fluorine-containing silicone oil can be used for obtaining emulsion type fluorine-containing silicone oil by adopting a conventional emulsification process, the emulsification process is simple and convenient, raw materials are easy to obtain, and the method is more suitable for industrial production and popularization and application.)

1. The fluorine-containing silicone oil is characterized in that the structural formula of the fluorine-containing silicone oil is shown as the formula (I):

wherein a, m, n and y are natural numbers, a ranges from 1 to 5, m ranges from 1 to 2, n ranges from 1 to 3, and y ranges from 1 to 5.

2. The fluorosilicone oil of claim 1, wherein a is in the range of 2 to 4, m is in the range of 1 to 2, n is in the range of 1 to 2, and y is in the range of 1 to 2.

3. A method for producing the fluorosilicone oil according to claim 1 or 2, comprising the steps of:

mixing amino silicone oil with an organic solvent, and heating to 50-70 ℃ to obtain an amino silicone oil solution;

mixing a tetrahydroperfluorooctyl acryloyl benzoate functional monomer with an organic solvent to obtain a tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution;

dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution to the amino silicone oil solution, and continuously reacting for 5-10 h at 50-70 ℃ to obtain a first reaction solution;

mixing vinyl triethoxysilane with an organic solvent to obtain a vinyl triethoxysilane solution;

dropwise adding the vinyltriethoxysilane solution into the first reaction solution, and continuously reacting for 3-5 h at 50-70 ℃ to obtain a second reaction solution;

and distilling the second reaction solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and the low-boiling-point substances, thereby obtaining the fluorine-containing silicone oil.

4. The method according to claim 3, wherein the weight ratio of the amino silicone oil, the tetrahydroperfluorooctylacryloyl benzoate, and the vinyltriethoxysilane is (5-10): (5-10): (2-5).

5. The method according to claim 3, wherein the organic solvent is tetrahydrofuran.

6. The preparation method according to claim 3, wherein the weight ratio of the solute to the solvent in the amino silicone oil solution is (5-10): (10-20);

the weight ratio of solute to solvent in the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is (5-10): 10;

the weight ratio of solute to solvent in the vinyltriethoxysilane solution is (2-5): (5-10).

7. Use of a fluorosilicone oil according to claim 1 or claim 2 for a textile finish.

8. The use of fluorosilicone oil as claimed in claim 7, wherein the fabric finishing agent comprises the following components in parts by weight:

8-12 parts by weight of fluorine-containing silicone oil, 80-100 parts by weight of deionized water, 1-3 parts by weight of nonionic surfactant and 1-3 parts by weight of anionic surfactant;

the preparation method of the fabric finishing agent comprises the step of stirring the components at the rotating speed of 2000 r/min-4000 r/min for 10 min-30 min.

9. Use of fluorosilicone oil according to claim 7 or 8, wherein the working concentration of the fabric finishing agent is 70g/L to 90 g/L.

Technical Field

The invention relates to the technical field of fluorine-containing low-surface-energy materials, in particular to fluorine-containing silicone oil, a preparation method and application thereof.

Background

The polysiloxane is an organic silicon polymer which takes Si-O-Si as a molecular main chain and takes a side chain as an organic substituent group, and has the characteristics of high and low temperature resistance, low dielectric constant, hydrophobicity and the like. Fluorine-containing polysiloxanes are the most widely used silicone polymers and can be obtained by three methods: (a) hydrolytic condensation of fluorine-containing silane; (b) ring-opening polymerization of fluorine-containing cyclosiloxane; (c) hydrosilation of fluoroolefins with hydrogenpolysiloxanes. Because the atomic radii of fluorine atoms and hydrogen atoms are similar, after the hydrogen atoms on the polysiloxane side chain are replaced by the fluorine atoms, the fluorine atoms with strong electronegativity are strongly combined with carbon atoms to form firm C-F bonds, and a 'shielding effect' is formed on the fluorine-containing polysiloxane molecule main chain, so that the fluorine-containing polysiloxane has excellent chemical resistance and weather resistance, low refractive index and good hydrophobic and oleophobic properties, and is widely applied to the fields of building, aviation, ships, textile functional finishing and the like. It has been demonstrated that the length of the fluorocarbon side chain and its crystallinity, and the spacer between the main chain and the fluorocarbon side chain, together affect the surface properties of the fluoropolymer. Especially when the fluorocarbon side chain has more than eight carbon atoms (CnF2n +1, n.gtoreq.8), the fluoropolymer exhibits extremely low surface free energy. However, perfluorocarbon chain compounds containing more than eight carbon atoms are degraded in the natural environment to produce perfluorooctanoic acid or perfluorooctane sulfonic acid compounds (PFOA/PFOS) having bioaccumulation properties. Therefore, the substitution of ecotype fluorine-containing materials for long-chain perfluoroalkyl materials with bioaccumulation is a problem to be solved in the field of the current fluorine-containing low surface energy materials.

Disclosure of Invention

Therefore, it is necessary to provide an environment-friendly ecological fluorine-containing silicone oil, a preparation method and an application thereof, aiming at the technical problem that the traditional fluorine-containing polysiloxane can be degraded to generate a perfluorooctanoic acid or perfluorooctane sulfonic acid compound with bioaccumulation property and has great environmental hazard.

The invention provides fluorine-containing silicone oil, which has a structural formula shown in a formula (I):

wherein a, m, n and y are natural numbers, a ranges from 1 to 5, m ranges from 1 to 2, n ranges from 1 to 3, and y ranges from 1 to 5.

In one embodiment, a ranges from 2 to 4, m ranges from 1 to 2, n ranges from 1 to 2, and y ranges from 1 to 2.

The invention also provides a preparation method of the fluorine-containing silicone oil, which comprises the following steps:

mixing amino silicone oil with an organic solvent, and heating to 50-70 ℃ to obtain an amino silicone oil solution;

mixing a tetrahydroperfluorooctyl acryloyl benzoate functional monomer with an organic solvent to obtain a tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution;

dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution to the amino silicone oil solution, and continuously reacting for 5-10 h at 50-70 ℃ to obtain a first reaction solution;

mixing vinyl triethoxysilane with an organic solvent to obtain a vinyl triethoxysilane solution;

dropwise adding the vinyltriethoxysilane solution into the first reaction solution, and continuously reacting for 3-5 h at 50-70 ℃ to obtain a second reaction solution;

and distilling the second reaction solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and the low-boiling-point substances, thereby obtaining the fluorine-containing silicone oil.

In one embodiment, the weight ratio of the amino silicone oil, the tetrahydroperfluorooctylacryloyl benzoate and the vinyl triethoxysilane is (5-10): (5-10): (2-5).

In one embodiment, the organic solvent is tetrahydrofuran.

In one embodiment, the weight ratio of the solute to the solvent in the amino silicone oil solution is (5-10): (10-20);

the weight ratio of solute to solvent in the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is (5-10): 10;

the weight ratio of solute to solvent in the vinyltriethoxysilane solution is (2-5): (5-10).

The invention also provides an application of the fluorine-containing silicone oil, and the fluorine-containing silicone oil is used for a textile finishing agent.

In one embodiment, the fabric finishing agent comprises the following components in parts by weight:

8-12 parts by weight of fluorine-containing silicone oil, 80-100 parts by weight of deionized water, 1-3 parts by weight of nonionic surfactant and 1-3 parts by weight of anionic surfactant;

the preparation method of the fabric finishing agent comprises the step of stirring the components at the rotating speed of 2000 r/min-4000 r/min for 10 min-30 min.

In one embodiment, the working concentration of the fabric finishing agent is 70g/L to 90 g/L.

In the molecular structure of the fluorine-containing silicone oil, the tetrahydroperfluorooctyl acryloyl benzoate is taken as a fluorine-containing functional monomer, a rigid benzene ring is taken as a connecting group to bond an environment-friendly short fluorocarbon chain into a molecule of the aminosilicone oil, and a pi-pi conjugated system in the benzene ring is utilized to promote the short fluorocarbon chain to be outward and vertically arranged on the surface of a substrate in a regular manner, so that a more obvious and effective fluoroalkyl shielding effect is provided, and an excellent waterproof effect is brought; in addition, the adopted fluoroalkyl groups are short fluorocarbon chains, which do not belong to the range of forbidden fluorine-containing chemicals in the perfluorooctyl sulfonamide derivatives, and the problems of biological toxicity and accumulation do not exist; furthermore, the fluorine-containing silicone oil can be used for obtaining the emulsion type fluorine-containing silicone oil by adopting a conventional emulsification process, the emulsification process is simple and convenient, the raw materials are easy to obtain, and the method is more suitable for industrial production and popularization and application.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention. In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.

FIG. 1 is an infrared spectrum of a fluorosilicone oil obtained in examples 1 to 3 of the present invention;

FIG. 2 is a graph showing the results of a fabric contact angle test after treatment with the fabric conditioner prepared in example 1 of the present invention;

FIG. 3 is an infrared spectrum of a fluorine-containing silicone oil obtained in examples 4 to 6 of the present invention and a modified silicone oil obtained in comparative example 2.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

The reaction reagents used in the present invention are commercially available and are chemically pure or more.

The invention provides fluorine-containing silicone oil, which has a structural formula shown as a formula (I):

wherein a, m, n and y are natural numbers, a ranges from 1 to 5, m ranges from 1 to 2, n ranges from 1 to 3, and y ranges from 1 to 5; preferably, a ranges from 2 to 4, m ranges from 1 to 2, n ranges from 1 to 2, and y ranges from 1 to 2.

In the molecular structure of the fluorine-containing silicone oil, the tetrahydroperfluorooctyl acryloyl benzoate is taken as a fluorine-containing functional monomer, a rigid benzene ring is taken as a connecting group to bond an environment-friendly short fluorocarbon chain into a molecule of the aminosilicone oil, and a pi-pi conjugated system in the benzene ring is utilized to promote the short fluorocarbon chain to be outward and vertically arranged on the surface of a substrate in a regular manner, so that a more obvious and effective fluoroalkyl shielding effect is provided, and an excellent waterproof effect is brought; in addition, the adopted fluoroalkyl groups are short fluorocarbon chains, which do not belong to the range of forbidden fluorine-containing chemicals in the perfluorooctyl sulfonamide derivatives, and the problems of biological toxicity and accumulation do not exist; furthermore, the fluorine-containing silicone oil can be used for obtaining the emulsion type fluorine-containing silicone oil by adopting a conventional emulsification process, the emulsification process is simple and convenient, the raw materials are easy to obtain, and the method is more suitable for industrial production and popularization and application.

The invention also provides a preparation method of the fluorine-containing silicone oil, which is characterized in that tetrahydroperfluorooctyl acryloyl benzoate is used as a functional monomer, vinyl triethoxysilane is used as a crosslinking monomer, the functional monomer is bonded to the molecular side chain of the amino silicone oil through the Michael addition reaction, and further, a fluorine-containing silicone oil emulsion with good stability, namely a fabric finishing agent, is prepared under the emulsification action of a non-ionic surfactant and an anionic surfactant. Wherein the reaction formula of the fluorine-containing silicone oil is shown as formula II:

as an alternative embodiment, the present invention provides a method for preparing the above fluorosilicone oil, comprising the following steps:

mixing amino silicone oil with an organic solvent, and heating to 50-70 ℃ to obtain an amino silicone oil solution;

mixing a tetrahydroperfluorooctyl acryloyl benzoate functional monomer with an organic solvent to obtain a tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution;

dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution to the amino silicone oil solution, and continuously reacting for 5-10 h at 50-70 ℃ to obtain a first reaction solution;

mixing vinyl triethoxysilane with an organic solvent to obtain a vinyl triethoxysilane solution;

dropwise adding the vinyltriethoxysilane solution into the first reaction solution, and continuously reacting for 3-5 h at 50-70 ℃ to obtain a second reaction solution;

and distilling the second reaction solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and the low-boiling-point substances, thereby obtaining the fluorine-containing silicone oil.

Among them, the organic solvent is preferably tetrahydrofuran, and the above reaction raw materials have good solubility in tetrahydrofuran, and after the reaction is completed, the organic solvent is easily removed.

The preparation method of the fluorine-containing silicone oil is simple, high in yield and convenient for industrial production, popularization and application.

As an optional embodiment, the weight ratio of the amino silicone oil, the tetrahydroperfluorooctylacryloyl benzoate and the vinyl triethoxysilane is (5-10): (5-10): (2-5).

As an optional embodiment, the weight ratio of the solute to the solvent in the amino silicone oil solution is (5-10): (10-20); the weight ratio of solute to solvent in the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is (5-10): 10; the weight ratio of the solute to the solvent in the vinyltriethoxysilane solution is (2-5): (5-10).

Furthermore, the invention also provides an application of the fluorine-containing silicone oil, and the fluorine-containing silicone oil is used for a textile finishing agent. Preferably, the fabric finishing agent comprises the following components in parts by weight:

8-12 parts by weight of fluorine-containing silicone oil, 80-100 parts by weight of deionized water, 1-3 parts by weight of nonionic surfactant and 1-3 parts by weight of anionic surfactant;

the preparation method of the fabric finishing agent comprises the step of stirring the components at the rotating speed of 2000 r/min-4000 r/min for 10 min-30 min.

The fabric finishing agent can obtain the emulsion type fluorine-containing silicone oil by adopting a conventional emulsification process, the emulsification process is simple and convenient, the raw materials are easy to obtain, and the fabric finishing agent is more suitable for industrial production and popularization and application.

As an alternative embodiment, the working concentration of the fabric finishing agent is 70g/L to 90 g/L. When the fabric finishing agent is used, the fabric finishing agent is prepared into working solution with working concentration of 70 g/L-90 g/L through deionized water. Soaking the cotton fabric in the working solution for 10-20 min, and performing a two-soaking and two-rolling process (the rolling retention rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

Example 1

1. Preparation of fluorine-containing silicone oil

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 15kg of tetrahydrofuran and 7.5kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 60 ℃. 7.5kg of a tetrahydroperfluorooctylacryloyl benzoate functional monomer was dissolved in 10kg of tetrahydrofuran to form a tetrahydroperfluorooctylacryloyl benzoate functional monomer solution. And dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution into an amino silicone oil solution through a constant-pressure dropping funnel, keeping the reaction temperature at 60 ℃, and keeping the temperature at 60 ℃ for continuous reaction for 7.5 hours after the dropwise addition of the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is finished to form a first reaction solution.

Dissolving 3.5kg of vinyltriethoxysilane in 7.5kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, keeping the reaction temperature at 60 ℃, dropwise adding the vinyltriethoxysilane solution into the first reaction solution through a constant-pressure dropping funnel, keeping the reaction temperature at 60 ℃, keeping the temperature at 60 ℃ after the vinyltriethoxysilane solution is completely dropwise added, keeping the temperature at 60 ℃, and continuing to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the fluorine-containing silicone oil.

Referring to FIG. 1, the IR spectrum of the fluorosilicone oil obtained in example 1 of the present invention shows that tetrahydroperfluorooctylacryloyl benzoate was successfully added to the side chain of the aminosilicone.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 10kg of fluorine-containing silicone oil, 90kg of deionized water, 2kg of nonionic surfactant AEO-6 and 2kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 20min at a stirring speed of 3000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 80g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

Referring to fig. 2, the water contact angle of the finished fabric was 142.6 °. The water contact angle of the unfinished fabric was 0 °. It can be seen that the water repellency of the fabric treated with the fabric finishing agent of the present invention is significantly enhanced.

Example 2

1. Preparation of fluorine-containing silicone oil

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 10kg of tetrahydrofuran and 5.0kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 50 ℃. 5.0kg of a tetrahydroperfluorooctylacryloyl benzoate functional monomer was dissolved in 10kg of tetrahydrofuran to form a tetrahydroperfluorooctylacryloyl benzoate functional monomer solution. And dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution into an amino silicone oil solution through a constant-pressure dropping funnel, keeping the reaction temperature at 50 ℃, and keeping the temperature of 50 ℃ for continuous reaction for 5.0h after the dropwise addition of the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is finished to form a first reaction solution.

Dissolving 2.0kg of vinyltriethoxysilane in 5.0kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, keeping the reaction temperature at 50 ℃, dropwise adding the vinyltriethoxysilane solution into the first reaction solution through a constant-pressure dropping funnel, keeping the reaction temperature at 50 ℃, keeping the temperature at 50 ℃ after dropwise adding of the vinyltriethoxysilane solution is finished, and keeping the temperature at 50 ℃ to continue to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the fluorine-containing silicone oil.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 8kg of fluorine-containing silicone oil, 80kg of deionized water, 1kg of nonionic surfactant AEO-6 and 1kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 10min at a stirring speed of 2000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 70g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

The finished fabric from example 2 was tested to have a water contact angle of 140.1 °.

Example 3

1. Preparation of fluorine-containing silicone oil

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 10kg of tetrahydrofuran and 10.0kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 70 ℃. 10.0kg of a tetrahydroperfluorooctylacryloyl benzoate functional monomer was dissolved in 10kg of tetrahydrofuran to form a tetrahydroperfluorooctylacryloyl benzoate functional monomer solution. And dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution into an amino silicone oil solution through a constant-pressure dropping funnel, keeping the reaction temperature at 70 ℃, and keeping the temperature at 70 ℃ for continuous reaction for 5.0h after the dropwise addition of the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is finished to form a first reaction solution.

Dissolving 5.0kg of vinyltriethoxysilane in 10.0kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, maintaining the reaction temperature at 70 ℃, dropwise adding the vinyltriethoxysilane solution into the first reaction solution through a constant-pressure dropping funnel, maintaining the reaction temperature at 70 ℃, keeping the temperature at 50 ℃ after the vinyltriethoxysilane solution is completely dropwise added, and continuing to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the fluorine-containing silicone oil.

Referring to FIG. 1, an infrared spectrum of fluorosilicone oil prepared in example 1 of the present invention is shown; as can be seen from the figure, tetrahydroperfluorooctylacryloyl benzoate was successfully added to the side chain of the aminosilicone.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 8kg of fluorine-containing silicone oil, 80kg of deionized water, 1kg of nonionic surfactant AEO-6 and 1kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 10min at a stirring speed of 2000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 70g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

The finished fabric from example 3 was tested to have a water contact angle of 144.5 °.

Example 4

1. Preparation of fluorine-containing silicone oil

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 10kg of tetrahydrofuran and 8.95kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 70 ℃. 1.95kg of a tetrahydroperfluorooctylacryloyl benzoate functional monomer was dissolved in 10kg of tetrahydrofuran to form a tetrahydroperfluorooctylacryloyl benzoate functional monomer solution. And dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution into an amino silicone oil solution through a constant-pressure dropping funnel, keeping the reaction temperature at 70 ℃, and keeping the temperature at 70 ℃ for continuous reaction for 5.0h after the dropwise addition of the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is finished to form a first reaction solution.

Dissolving 1.90kg of vinyltriethoxysilane in 10.0kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, maintaining the reaction temperature at 70 ℃, dropwise adding the vinyltriethoxysilane solution into the first reaction solution through a constant-pressure dropping funnel, maintaining the reaction temperature at 70 ℃, keeping the temperature at 50 ℃ after the vinyltriethoxysilane solution is completely dropwise added, and continuing to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the fluorine-containing silicone oil.

Referring to FIG. 3 b, the IR spectrum shows that tetrahydroperfluorooctylacryloyl benzoate was successfully added to the side chain of the aminosilicone.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 8kg of fluorine-containing silicone oil, 80kg of deionized water, 1kg of nonionic surfactant AEO-6 and 1kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 10min at a stirring speed of 2000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 70g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

The finished fabric from example 4 was tested to have a water contact angle of 131.7 °.

Example 5

1. Preparation of fluorine-containing silicone oil

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 10kg of tetrahydrofuran and 8.95kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 70 ℃. 5.27kg of a tetrahydroperfluorooctylacryloyl benzoate functional monomer was dissolved in 10kg of tetrahydrofuran to form a tetrahydroperfluorooctylacryloyl benzoate functional monomer solution. And dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution into an amino silicone oil solution through a constant-pressure dropping funnel, keeping the reaction temperature at 70 ℃, and keeping the temperature at 70 ℃ for continuous reaction for 5.0h after the dropwise addition of the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is finished to form a first reaction solution.

Dissolving 1.90kg of vinyltriethoxysilane in 10.0kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, maintaining the reaction temperature at 70 ℃, dropwise adding the vinyltriethoxysilane solution into the first reaction solution through a constant-pressure dropping funnel, maintaining the reaction temperature at 70 ℃, keeping the temperature at 50 ℃ after the vinyltriethoxysilane solution is completely dropwise added, and continuing to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the fluorine-containing silicone oil.

Referring to FIG. 3 c, the IR spectrum shows that tetrahydroperfluorooctylacryloyl benzoate was successfully added to the side chain of the aminosilicone.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 8kg of fluorine-containing silicone oil, 80kg of deionized water, 1kg of nonionic surfactant AEO-6 and 1kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 10min at a stirring speed of 2000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 70g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric. The finished fabric from example 5 was tested to have a water contact angle of 137.9 °.

Example 6

1. Preparation of fluorine-containing silicone oil

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 10kg of tetrahydrofuran and 8.95kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 70 ℃. 10.90kg of a tetrahydroperfluorooctylacryloyl benzoate functional monomer was dissolved in 10kg of tetrahydrofuran to form a tetrahydroperfluorooctylacryloyl benzoate functional monomer solution. And dropwise adding the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution into an amino silicone oil solution through a constant-pressure dropping funnel, keeping the reaction temperature at 70 ℃, and keeping the temperature at 70 ℃ for continuous reaction for 5.0h after the dropwise addition of the tetrahydroperfluorooctyl acryloyl benzoate functional monomer solution is finished to form a first reaction solution.

Dissolving 1.90kg of vinyltriethoxysilane in 10.0kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, maintaining the reaction temperature at 70 ℃, dropwise adding the vinyltriethoxysilane solution into the first reaction solution through a constant-pressure dropping funnel, maintaining the reaction temperature at 70 ℃, keeping the temperature at 50 ℃ after the vinyltriethoxysilane solution is completely dropwise added, and continuing to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the fluorine-containing silicone oil.

Referring to FIG. 3, the spectrum of part d of the infrared spectrum shows that tetrahydroperfluorooctylacryloyl benzoate was successfully added to the side chain of the aminosilicone.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 8kg of fluorine-containing silicone oil, 80kg of deionized water, 1kg of nonionic surfactant AEO-6 and 1kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 10min at a stirring speed of 2000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 70g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

The finished fabric from example 6 was tested to have a water contact angle of 142.6 °.

Comparative example

1. Preparation of modified Silicone oils

In a reactor equipped with a thermometer, a reflux condenser and a magnetic stirrer, 10kg of tetrahydrofuran and 8.95kg of aminosilicone oil were added by weight to form an aminosilicone oil solution, which was heated to 70 ℃.

Dissolving 1.90kg of vinyltriethoxysilane in 10.0kg of tetrahydrofuran solvent to form a vinyltriethoxysilane solution, maintaining the reaction temperature at 70 ℃, dropwise adding the vinyltriethoxysilane solution into the amino silicone oil solution through a constant-pressure dropping funnel, maintaining the reaction temperature at 70 ℃, keeping the temperature at 50 ℃ after the vinyltriethoxysilane solution is completely dropwise added, and continuing to react for 4 hours to form a second solution.

And distilling the second solution under reduced pressure at 45 ℃ and 666Pa to remove the solvent and low-boiling-point substances in the second solution to obtain the modified silicone oil.

Referring to FIG. 3, a partial IR spectrum of comparative example 2 of the present invention, it can be seen that vinyltriethoxysilane groups are successfully grafted onto the side chains of amino silicone oil.

2. Preparation of a Fabric finish

Preparing a fabric finishing agent by adopting a high-speed shearing and dispersing emulsifying machine, putting 8kg of modified silicone oil, 80kg of deionized water, 1kg of nonionic surfactant AEO-6 and 1kg of anionic surfactant SDS into a stirring container by weight, starting the high-speed shearing emulsifying machine, and stirring for 10min at a stirring speed of 2000r/min to obtain milky fluorine-containing silicone oil emulsion, namely the fabric finishing agent.

3. Finishing of textiles

The fabric finishing agent is prepared into finishing working solution with the concentration of 70g/L by deionized water. Soaking the cotton fabric in the finishing working solution for 15min, and performing a two-soaking and two-rolling process (the rolling residual rate is 90% -100%, the room temperature) → pre-baking (80 ℃ multiplied by 3 minutes) → baking (160 ℃ multiplied by 2 minutes), so as to obtain the finished fabric.

The finished fabric from comparative example 2 was tested to have a water contact angle of 119.1 °.

It can be seen from the analysis of the above examples 1 to 6 and the comparison of 1 and 2 that the fluorosilicone oil agent prepared by the present invention can significantly improve the waterproof effect of the fabric, but does not cause environmental pollution due to the change of its own structure. And the prepared fluorine-containing silicone oil has simple preparation process, easily obtained raw materials and convenient emulsification, and is more suitable for industrial production, popularization and application.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.