阅读说明：本技术 一种含氟硅高效整理剂及其制备方法和应用 (Fluorine-silicon-containing efficient finishing agent and preparation method and application thereof ) 是由 刘军 杨之卓 黄尚东 梁永标 于 2020-05-27 设计创作，主要内容包括：本发明提供一种含氟硅高效整理剂及其制备方法、在织物上的应用,所述整理剂按质量百分比包括以下组分：有效物20％和水。本发明提供的整理剂有效物,由含氟多面低聚倍半硅氧烷大分子、亲水大分子和多异氰酸酯反应得到。亲水大分子由聚乙二醇大分子引发剂、两性离子单体用原子转移自由基聚合合成。本发明采用特殊分子结构,相对现有技术,具有更好的三防和易去污效果,耐洗涤性能更佳。(The invention provides a fluorine-silicon-containing efficient finishing agent, a preparation method thereof and application thereof to fabrics, wherein the finishing agent comprises the following components in percentage by mass: 20% of effective substance and water. The finishing agent effective substance provided by the invention is obtained by reacting fluorine-containing polyhedral oligomeric silsesquioxane macromolecules, hydrophilic macromolecules and polyisocyanate. The hydrophilic macromolecule is synthesized by the polymerization of polyethylene glycol macromolecule initiator and zwitter-ion monomer by atom transfer radical. Compared with the prior art, the invention has better three-proofing and easy-decontamination effects and better washing resistance by adopting a special molecular structure.)

1. The fluorine-containing silicon efficient finishing agent is characterized by comprising the following components in percentage by mass: 20% of effective substances and the balance of water; the effective substance is obtained by the reaction of fluorine-containing polyhedral oligomeric silsesquioxane macromolecules, hydrophilic macromolecules and polyisocyanate.

2. The preparation method of the fluorine-containing silicon high-efficiency finishing agent according to claim 1, characterized in that: s1), heating HDI tripolymer to 50 ℃, slowly dripping acetone solution prepared by fluorine-containing polyhedral oligomeric silsesquioxane macromolecules, and performing reflux reaction after dripping is finished; s2), adding 3, 5-dimethylpyrazole, and carrying out reflux reaction; s3), adding an acetone solution prepared from hydrophilic macromolecules, and performing reflux reaction until isocyanate groups are completely reacted to obtain an acetone solution of an effective substance; s4) controlling the system temperature to be 50 ℃, adding deionized water under the condition of vigorous stirring, and continuing stirring after adding the deionized water; and (4) performing rotary evaporation to recover acetone to obtain the fluorine-containing silicon efficient finishing agent.

3. The preparation method of the fluorine-containing silicon high-efficiency finishing agent according to claim 2, characterized in that: the fluorine-containing polyhedral oligomeric silsesquioxane macromolecule is obtained by the following steps: s11) adding absolute ethyl alcohol, deionized water and concentrated hydrochloric acid into a flask in sequence, dripping perfluorohexylethyltrimethoxysilane into a reaction system by using a dropping funnel, and stirring to uniformly mix the materials; after the dropwise addition is finished, sealing the uniformly mixed reaction system, stirring for several hours, heating in a water bath, cooling and standing to obtain white crystalline precipitates, filtering and collecting a product, washing with a small amount of methanol, and drying to obtain an intermediate I; s12) putting the intermediate I into a flask, adding aqueous solutions of tetrahydrofuran and tetraethylammonium hydroxide in sequence, adjusting the pH value after reflux reaction, performing rotary evaporation to remove the solvent, washing with methanol, dissolving the solid in acetone, drying with anhydrous magnesium sulfate, performing suction filtration, performing rotary evaporation again to obtain a product, and performing vacuum drying overnight to obtain an intermediate II; s13) dissolving the intermediate II in anhydrous tetrahydrofuran, adding 3-chloropropyltrichlorosilane, stirring for reaction, reacting at room temperature, removing the solvent by rotary evaporation, washing with methanol, dissolving the solid in chloroform, washing with water, and drying the organic layer with anhydrous magnesium sulfate; adding a large amount of methanol to separate out solids, dissolving the solids obtained by filtering with tetrahydrofuran, and repeating for several times; vacuum drying the product to obtain an intermediate III; s14) dissolving silver nitrate in water, and slowly dropwise adding a sodium hydroxide aqueous solution under the condition of continuous stirring; separating the generated silver oxide precipitate, and washing with deionized water; and dissolving the intermediate III in a mixture of ethanol and tetrahydrofuran, adding newly prepared silver oxide and deionized water, performing reflux reaction in a dark environment under the stirring condition, removing the solvent by rotary evaporation, and performing vacuum drying to obtain the fluorine-containing polyhedral oligomeric silsesquioxane macromolecule.

4. The preparation method of the fluorine-containing silicon high-efficiency finishing agent according to claim 2, characterized in that: the hydrophilic macromolecule is synthesized by polymerization of a polyethylene glycol macromolecule initiator and a zwitterionic monomer by atom transfer radical; the hydrophilic macromolecule is synthesized by the following steps: s21) rapidly and uniformly mixing N, N, N' -pentamethyldiethylenetriamine, cuprous bromide, polyethylene glycol macroinitiator, 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and toluene, cooling in liquid nitrogen, performing three cycles of freezing, vacuumizing and melting, and reacting in a preheated oil bath; diluting the product with dichloromethane, filtering with active alumina column to remove catalyst, and purifying with chromatographic column to obtain intermediate V; s22) dissolving silver nitrate in water, and slowly dropwise adding a sodium hydroxide aqueous solution under the condition of continuous stirring; and (3) separating out the generated silver oxide precipitate, dissolving the intermediate V in ethanol and tetrahydrofuran, adding newly prepared silver oxide and deionized water, carrying out reflux reaction in a dark environment under the stirring condition, removing the solvent by rotary evaporation, and carrying out vacuum drying to obtain the hydrophilic macromolecule.

5. The preparation method of the fluorine-containing silicon high-efficiency finishing agent according to claim 4, characterized in that: the polyethylene glycol macroinitiator is obtained by the following steps: s31) adding toluene into the flask, introducing nitrogen for protection and heating, dripping a solution prepared from methoxy polyethylene glycol acrylate, 2-mercaptoethanol, azobisisobutyronitrile and toluene into the flask, and after the dripping is finished, replenishing azobisisobutyronitrile for continuous reaction; then, carrying out chromatographic purification on the product to obtain an intermediate IV; s32) uniformly mixing the intermediate IV, tetrahydrofuran and triethylamine to prepare a solution, then placing the solution into an ice water bath, slowly dropwise adding a mixture of 2, 2-dichloroacetyl chloride and dichloromethane, removing the ice water bath after dropwise adding is stopped to heat the system to 25 ℃, filtering a product after reaction is finished, washing the product for 3 times by using deionized water, a diluted sodium carbonate solution, a diluted hydrochloric acid solution and deionized water respectively, and drying the product over night by using anhydrous magnesium sulfate; most of the solvent is evaporated and precipitated in cold ether to obtain the polyethylene glycol macroinitiator.

6. The preparation method of the fluorine-containing silicon high-efficiency finishing agent according to claim 2, characterized in that: the polyisocyanate is selected from one or more of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer and toluene diisocyanate trimer.

7. The preparation method of the fluorine-containing silicon high-efficiency finishing agent according to claim 6, characterized in that: the polyisocyanate is preferably hexamethylene diisocyanate trimer.

8. The application of the fluorine-containing silicon high-efficiency finishing agent according to claim 1 is characterized in that: the fluorine-containing silicon efficient finishing agent is diluted and then applied to the fabric; removing excessive liquid and drying.

Technical Field

The invention relates to the field of textile auxiliary agents, in particular to a fluorine-silicon-containing efficient finishing agent and a preparation method thereof.

Background

The three-proofing soil-release finishing agent has application in many aspects. Currently, the following problems are mainly faced:

1. the oil-repellent property is insufficient. The Chinese patent CN105297439 adopts hexafluorobutyl acrylate, and the fluoroalkyl-containing chain segment is too short to provide effective oil-proof performance. Meanwhile, the regular structure formed by perfluoroalkyl chain segments of carbon eight and above is not easy to form by carbon six, so that the oil resistance is insufficient when the carbon six is directly used according to the use mode of the carbon eight. Practice shows that carbon six must be matched with a specific structural design to form effective oil resistance.

2. Insufficient affinity with the fiber. Both chinese patent CN105297439 and chinese patent application CN110317307 adopt cationic and nonionic emulsifiers and have limited affinity for nylon-based fabrics. The functional monomer adopted by the Chinese patent application CN110317307 has the defects of releasing formaldehyde or insufficient reaction with cotton and the like.

3. Small molecule surfactants affect the water and oil repellency properties. Both the chinese patent CN105297439 and the chinese patent application CN110317307 adopt cationic and nonionic emulsifiers, which have negative effects on water and oil repellency.

Disclosure of Invention

The invention aims to provide a fluorine-silicon-containing efficient finishing agent and a preparation method thereof, and the fluorine-silicon-containing efficient finishing agent has efficient water-proof, oil-proof and easy-to-clean performances.

The invention also aims to provide the application of the fluorine-containing silicon high-efficiency finishing agent on textiles

In order to achieve the purpose, the invention firstly provides a fluorine-containing silicon efficient finishing agent which is characterized by comprising the following components in percentage by mass: 20% of effective substances and the balance of water;

the effective substance is obtained by reacting fluorine-containing polyhedral oligomeric silsesquioxane macromolecules, hydrophilic macromolecules and polyisocyanate.

The fluorine-containing polyhedral oligomeric silsesquioxane macromolecule is obtained by the following steps: (1) adding 300mL of absolute ethyl alcohol, 12.9g of deionized water and 13.4g of concentrated hydrochloric acid into a flask in sequence, dripping 17.1g of perfluorohexylethyltrimethoxysilane into a reaction system by using a dropping funnel, and stirring continuously for 30min to uniformly mix the materials; after the dropwise addition is finished, sealing the uniformly mixed reaction system, stirring for 8h at 40 ℃, heating in a water bath to 70 ℃, reacting for 24h, cooling to room temperature, standing for 7d, allowing white crystalline precipitate to appear, filtering, collecting a product, washing for 2 times by using a small amount of methanol, and drying to obtain an intermediate I; (2) putting 15.5g of the intermediate I into a flask, sequentially adding 2mL of aqueous solution of 125mL of tetrahydrofuran and 35% of tetraethylammonium hydroxide in mass fraction, and carrying out reflux reaction at 65-70 ℃ for 5 hours; then adjusting the pH value to about 7 by using hydrochloric acid, carrying out rotary evaporation to remove the solvent, washing the solution by using methanol for several times, dissolving the solid in acetone, drying the solution by using anhydrous magnesium sulfate, carrying out suction filtration, carrying out rotary evaporation again to obtain a product, and carrying out vacuum drying overnight to obtain an intermediate II; (3) dissolving 28.2g of the intermediate II in 250mL of anhydrous tetrahydrofuran, adding 3.18g of 3-chloropropyltrichlorosilane, reacting for 3h at 0 ℃ under the condition of stirring, then reacting for 3h at room temperature, removing the solvent by rotary evaporation, washing for several times by using methanol, dissolving the solid in chloroform, washing by using water, and drying an organic layer by using anhydrous magnesium sulfate; adding a large amount of methanol to separate out solids, dissolving the solids obtained by filtering with tetrahydrofuran, and repeating for several times; vacuum drying the product at 60 ℃ for 48h to obtain an intermediate III; (4)0.2468g of silver nitrate is dissolved in 10g of water, and 0.0581g of 10 percent (mass percent) sodium hydroxide aqueous solution is slowly dropped under the condition of continuous stirring; separating the generated silver oxide precipitate, and washing with deionized water for three times; dissolving 2.84g of the intermediate III in a mixture of 25mL of ethanol and 25mL of tetrahydrofuran, adding the newly prepared silver oxide and 0.5g of deionized water, carrying out reflux reaction for 48h in a dark environment under the stirring condition, carrying out rotary evaporation to remove the solvent, and carrying out vacuum drying for 48h at 60 ℃ to obtain the fluorine-containing polyhedral oligomeric silsesquioxane macromolecule;

the hydrophilic macromolecule is synthesized by polymerization of a polyethylene glycol macromolecule initiator and a zwitterionic monomer by atom transfer radical;

the polyethylene glycol macroinitiator is obtained by the following steps: (1) 200 g of toluene is added into a flask, nitrogen is introduced for protection, and after the flask is heated to 110 ℃, a solution prepared from 100 g of methoxypolyethylene glycol acrylate (average molecular weight 1000), 3.91 g of 2-mercaptoethanol, 0.017 g of azobisisobutyronitrile and 200 g of toluene is dripped into the flask within 2.5 h. After the dropwise addition is finished for 0.5h, 0.017 g of azobisisobutyronitrile is added again for continuous reaction for 4 h; then, carrying out chromatographic purification on the product to obtain an intermediate IV; (2) uniformly mixing 10.39g of the intermediate IV, 40mL of tetrahydrofuran and 1.01g of triethylamine to prepare a solution, then placing the solution in an ice water bath, slowly dropwise adding a mixture of 2.21g of 2, 2-dichloroacetyl chloride and 5mL of dichloromethane for 1 hour, removing the ice water bath after the dropwise adding is stopped to heat the system to 25 ℃, stopping the reaction after the reaction is carried out for 20 hours, filtering the product, washing the product for 3 times by using deionized water, 10% sodium carbonate dilute solution, 10% dilute hydrochloric acid solution and deionized water respectively, and drying the product over night by using anhydrous magnesium sulfate; most of the solvent is evaporated in a rotary manner and precipitated in cold ether to obtain the polyethylene glycol macroinitiator;

the hydrophilic macromolecule is synthesized by the following steps: (1) 13.86mg of N, N, N' -pentamethyldiethylenetriamine, 5.8mg of cuprous bromide, 22.56mg of polyethylene glycol macroinitiator, 8.44mg of 3- [ N, N-dimethyl- [2- (2-methylpropane-2-enoyloxy) ethyl ] ammonium ] propane-1-sulfonic acid inner salt and 2.5mL of toluene were rapidly mixed well and cooled in liquid nitrogen, subjected to three cycles of freeze-vacuum-thaw and reacted for 4h in an oil bath preheated to 110 ℃. Diluting the product with dichloromethane, filtering with active alumina column to remove catalyst, and purifying with chromatographic column to obtain intermediate V; (2)

0.2468g of silver nitrate is dissolved in 10g of water, and 0.0581g of 10 percent (mass percent) sodium hydroxide aqueous solution is slowly dropped under the condition of continuous stirring; separating the generated silver oxide precipitate, and washing with deionized water for three times; dissolving 2.00g of the intermediate V in 25mL of ethanol and 25mL of tetrahydrofuran, adding the newly prepared silver oxide and 0.5g of deionized water, carrying out reflux reaction for 48h in a dark environment under the stirring condition, removing the solvent by rotary evaporation, and carrying out vacuum drying for 48h at 60 ℃ to obtain hydrophilic macromolecules;

the polyisocyanate is selected from one or more of hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate trimer and toluene diisocyanate trimer, and HDI trimer is preferred.

The fluorine-containing silicon efficient finishing agent is prepared by the following steps: (1) taking 42g of HDI tripolymer (NCO percent is 21.9 percent), heating to 50 ℃, slowly dropwise adding 20 mass percent acetone solution prepared from 212g of fluorine-containing polyhedral oligomeric silsesquioxane macromolecules, and carrying out reflux reaction for 8 hours after dropwise adding; (2) then adding 7.02g of 3, 5-dimethylpyrazole, and carrying out reflux reaction for 1 h; (3) then adding 20 mass percent acetone solution prepared by 216.5g of hydrophilic macromolecules, and carrying out reflux reaction until all isocyanate groups are reacted to obtain acetone solution of an effective substance; (4) controlling the temperature of the system at 50 ℃, adding 1882g of deionized water under the condition of vigorous stirring, and continuing stirring for 15 min; and (4) performing rotary evaporation to recover acetone to obtain the fluorine-containing silicon efficient finishing agent.

In the application of the fluorine-containing silicon efficient finishing agent, the finishing agent is diluted and then applied to the fabric; removing excessive liquid and drying.

The invention has the beneficial effects that:

(1) the perfluoroalkyl chain segment is effectively combined with polyhedral oligomeric silsesquioxane to form a good microstructure, so that the fabric finished by the fluorine-containing silicon efficient finishing agent has excellent water-proof and oil-proof effects;

(2) the amphoteric ion monomer and the polyethylene glycol are combined to form a hydrophilic part, so that the fluorine-containing silicon efficient finishing agent has better acid and alkali stability, and has stronger affinity with various fabrics by adjusting the pH value of the fluorine-containing silicon efficient finishing agent; by introducing the blocked isocyanate group, the modified polyester has reactivity with fabrics and better washing resistance;

(3) the fluorine-containing silicon efficient finishing agent has more excellent water-proof and oil-proof effects without a small molecular surfactant.

Detailed Description

In order to verify the water-repellent, oil-repellent, and stain-release effects of textiles treated with the fluorosilicone-containing high-efficiency finishing agent of the present invention, the results were examined by standard methods for comparison. The waterproof test method adopts AATCC 22-2005 textile water repellency test: spraying method, oil proofing test method is that AATCC118-2002 oil repellency: hydrocarbon impedance test, stain removal test method AATCC130-2010 antifouling: oil stain release method. The effect of the sample after washing with water is also examined, the washing conditions are that the standard synthetic detergent is 1g/L, the washing machine bath ratio is 1: washing at 30 deg.C, rinsing, dewatering, and drying at 100 deg.C for 3 min.