CN116836378B - A kind of organosilicon-modified polyarylate and its application in preparing flexible anti-icing film - Google Patents

Abstract

The invention discloses an organosilicon modified polyarylester and application thereof in preparing a flexible anti-icing film, which is characterized in that firstly, double bond-containing polyarylester is synthesized by an interfacial polycondensation method, then, double bond-containing polyarylester is modified by a hydrosilylation method to obtain the organosilicon modified polyarylester, then, the obtained organosilicon modified polyarylester is dissolved in a solvent to prepare a polymer solution with a certain concentration, and finally, the polymer solution is cast on a die or coated on a base material by a solution casting method or a spin coating method, and is dried to form a film. The method is simple in operation and low in technical requirement, and the obtained film has good anti-icing property.

Description

A kind of organosilicon-modified polyarylate and its application in preparing flexible anti-icing film

Technical field: The present invention relates to an organosilicon-modified polyarylate and its application in preparing a flexible anti-icing film, belonging to the technical field of polymer preparation.

Background Art

Ice accumulation in infrastructure and transportation facilities can cause huge economic losses and catastrophic events. Traditional anti-icing strategies, including mechanical, electrothermal and chemical deicing, are commonly used for outdoor infrastructure and transportation. However, these methods are inefficient, energy-consuming or environmentally unfriendly. More efficient and environmentally friendly anti-icing coatings can inhibit ice nucleation and reduce ice adhesion without human intervention, and have attracted increasing attention in recent years. In previous research work, the applicant prepared norbornene-based fluorinated organic gel for use as anti-icing, which has excellent anti-icing performance, but its mechanical properties are poor and are subject to certain limitations in application.

Constructing anti-icing surfaces based on surface properties and morphology is an effective method, but the complexity of icing conditions and the diversity of types make the research on anti-icing surfaces very challenging.

Summary of the invention

The purpose of the present invention is to overcome the above-mentioned deficiencies of the prior art and to provide a silicone-modified polyarylate and its application in the preparation of a flexible anti-icing film.

To achieve the above object, the present invention adopts the following technical solutions:

1. Silicone-modified polyarylate, the structural formula of which is shown in Formula I, wherein m is a natural number of 50 to 100, and the number average molecular weight is 24700 to 49500;

Formula Ⅰ.

2. The preparation method of the aforementioned organosilicon-modified polyarylate is to modify the polyarylate containing double bonds by using heptamethyltrisiloxane, wherein the structural formula of the polyarylate containing double bonds is as shown in Formula II, wherein n is a natural number of 50 to 100, and the number average molecular weight is 15,000 to 40,000;

Formula II.

Preferably, the modification treatment method is: in a nitrogen atmosphere, the double-bond polyarylate is subjected to a hydrosilylation reaction with heptamethyltrisiloxane by the catalytic action of a platinum catalyst, followed by post-treatment to obtain the product.

Further preferred, the specific method is as follows: first dissolve the polyaryl ester containing double bonds and heptamethyltrisiloxane in toluene, pass nitrogen at 60°C for 30 minutes, then add a platinum catalyst, and keep the reaction warm for 24 to 36 hours; wherein the amount ratio of the polyaryl ester containing double bonds, heptamethyltrisiloxane, toluene, and platinum catalyst is 1g: 0.23-0.64g: 30mL: 30mg.

More preferably, the post-treatment includes: removing the solvent by rotary evaporation, dropping the product into methanol for precipitation to remove unreacted substances and catalysts, and vacuum drying at 60° C. for 10 to 12 hours.

Preferably, the double-bond-containing polyarylate is synthesized by interfacial polycondensation reaction of diallyl bisphenol A with terephthaloyl chloride and isophthaloyl chloride.

Further preferred, the specific method is as follows: firstly dissolve diallyl bisphenol A and triethylbenzyl ammonium chloride (catalyst) in a 2 mol/L NaOH aqueous solution to obtain an aqueous phase; then dissolve terephthaloyl chloride and isophthaloyl chloride in dichloromethane to obtain an oil phase; then, at 0-5°C, drop the oil phase into the aqueous phase at a rate of 1-2 s/drop, react for 10 hours after the dropwise addition is completed, terminate the reaction, and purify to obtain; wherein the amount ratio of diallyl bisphenol A, triethylbenzyl ammonium chloride, sodium hydroxide aqueous solution, terephthaloyl chloride, isophthaloyl chloride, and dichloromethane is 2.313 g: 0.176 g: 15 mL: 0.46-0.85 g: 0.85-1.25 g: 22.4 mL.

Even more preferably, purification is achieved by precipitation of the product using methanol.

3. Application of the aforementioned organosilicon-modified polyarylate in the preparation of flexible anti-icing films.

4. A method for preparing a flexible anti-icing film, first dissolving the modified polyarylate in a solvent to prepare a polymer solution; then casting the polymer solution into a mold or evenly coating the surface of a substrate, and drying to obtain the film.

Preferably, the solvent is selected from any one of dichloromethane, tetrahydrofuran, benzene or toluene, or a mixture of two thereof.

Preferably, the mass concentration of the polymer solution is 20-30%.

Preferably, the polymer solution is cast into a mold or uniformly coated on the surface of a substrate by solution casting or spin coating.

More preferably, the specific method is as follows: firstly, the polymer solution is allowed to stand at 25°C for degassing for 2 to 4 hours to obtain a casting solution, and then the casting solution is cast into a mold or evenly spin-coated onto the surface of the substrate.

Preferably, the drying process conditions are: firstly leaving it in the air for 12 hours, and then transferring it to an oven at 80° C. and drying it for 6 to 8 hours.

Beneficial effects of the present invention:

The present invention firstly synthesizes a polyarylate containing double bonds by an interfacial polycondensation method, modifies the polyarylate containing double bonds by a hydrosilylation method to obtain an organosilicon-modified polyarylate, then dissolves the obtained organosilicon-modified polyarylate in a solvent to prepare a polymer solution of a certain concentration, and finally casts the polymer solution on a mold or coats it on a substrate by a solution casting method or a spin coating method, and dries it to form a film to obtain an organosilicon-modified polyarylate film. The present invention has a simple operation method and low technical requirements, and the obtained film has good anti-icing properties. The present invention is an intrinsic anti-icing surface, which has excellent anti-icing properties and can also take into account high mechanical strength.

The film has adjustable mechanical properties, with a tensile strength of 1.9 to 4.9 MPa, an elongation at break of 148 to 252%, an elastic modulus of 89.6 to 129 MPa, good flexibility, and potential applications in flexible sensing.

Since organosilicon-modified polyarylate contains hydrophobic groups and flexible side chains, the organosilicon groups reduce the interaction between the copolymer surface and water molecules; the molecular segments of the flexible surface slip under the action of force, generating internal stress and cracks at the interface between the material surface and the ice layer, thereby reducing ice adhesion. Compared with the polyarylate film before modification, its ice adhesion strength is reduced. Therefore, it has great potential for application in the field of anti-icing coatings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a hydrogen spectrum of organosilicon-modified polyarylate and polyarylate containing double bonds;

FIG. 2 is a graph of ice adhesion strength.

DETAILED DESCRIPTION

The present invention is further described below in conjunction with the accompanying drawings and embodiments. It should be noted that the following description is only for explaining the present invention and does not limit its contents.

Embodiment 1:

1. Preparation of organosilicon polyarylate copolymer

Synthesis of polyarylate containing double bonds:

2.313g of diallyl bisphenol A and 0.176g of triethylbenzyl ammonium chloride (catalyst) were dissolved in a flask containing 15ml of NaOH aqueous solution as the water phase, and 0.85g of terephthaloyl chloride and 0.85g of isophthaloyl chloride were dissolved in 22.4ml of dichloromethane as the oil phase and placed in a constant pressure funnel. At 2°C, the oil phase was dripped into the water phase at a rate of 1s/drop for reaction. After the dripping was completed, the reaction was allowed to proceed for 10h, and the reaction was terminated. The product was purified by precipitation with 30ml of methanol to obtain a polyarylate containing double bonds.

Synthesis of Siloxane-Modified Polyarylate:

Take 1g polyarylate and 0.64g heptamethyltrisiloxane and dissolve them in 30ml toluene. Pass nitrogen at 60℃ for 30 minutes. Use a syringe to add 30mg platinum catalyst (Aladdin) for reaction. The reaction stops after 24h. Remove the solvent by evaporation under reduced pressure. Drop the product into 20ml methanol for precipitation, and remove the unreacted product and catalyst. Dry the product under vacuum at 40℃ for 10-12h to obtain siloxane-modified polyarylate.

The hydrogen spectra of siloxane-modified polyarylate and polyarylate containing double bonds are shown in Figure 1.

The characterization data are as follows: ¹ H NMR (400 MHz, CDCl ₃ ): The hydrogens with chemical shifts (δ) of 9.02, 8.48 and 7.70 are on the benzene ring of isophthaloyl chloride, the hydrogen at chemical shift of 8.34 is on the benzene ring of terephthaloyl chloride, the hydrogens at chemical shifts of 7.35 and 7.18 are on the benzene ring of allyl bisphenol A, the hydrogens at chemical shifts of 1.67 and 4.96 are between the methyl group and the allyl double bond in allyl bisphenol A; the hydrogens at chemical shifts of 1.7 and 2.5 are the hydrogen positions of the carbon-carbon bond and the adjacent methylene group after the allyl double bond is opened. It can be concluded that the applicant has prepared a polyarylate containing double bonds and its complete hydrosilylation reaction with heptamethyltrisiloxane.

2. Application: Preparation of flexible silicone polyarylate coating

The polymer was dissolved in tetrahydrofuran to prepare a solution with a mass fraction of 20%, and the solution was placed at a constant temperature of 25°C for degassing for 2 hours to obtain a casting solution. The casting solution was spin-coated on a glass sheet or poured on a clean polytetrafluoroethylene mold, and the polymer-coated substrate/mold was left in the air for 12 hours, and placed in an oven at 80°C for 6-8 hours to evaporate the remaining solvent to obtain a flexible silicone polyarylate coating.

The formed 0.2 mm film was subjected to mechanical testing. The film was stretched at a speed of 100 mm/min, and the mechanical properties showed that the tensile strength was 1.79 MPa, the elongation at break was 220%, and the elastic modulus was 89.6 MPa. The film was subjected to an ice adhesion strength test. Icicles were frozen on its surface at -20°C. The strength obtained by pushing down the icicles under the action of a push-pull testing machine was the ice adhesion strength, and the ice adhesion strength was measured to be 72 MPa.

Embodiment 2:

1. Preparation of organosilicon polyarylate copolymer

Synthesis of polyarylate containing double bonds:

2.313g of diallyl bisphenol A and 0.176g of triethylbenzyl ammonium chloride (catalyst) were dissolved in a flask containing 15ml of NaOH aqueous solution as the water phase, and 0.46g of terephthaloyl chloride and 1.25g of isophthaloyl chloride were dissolved in 22.4ml of dichloromethane as the oil phase and placed in a constant pressure funnel. At 2°C, the oil phase was dripped into the water phase at a rate of 1s/drop for reaction. After the dripping was completed, the reaction lasted for 8h and the reaction was terminated. The product was purified by precipitation with 30ml of methanol to obtain a polyarylate containing double bonds.

Synthesis of Siloxane-Modified Polyarylate:

Take 1g polyarylate and 0.64g heptamethyltrisiloxane and dissolve them in 30ml toluene. Pass nitrogen at 60℃ for 30 minutes. Use a syringe to add 30mg platinum catalyst to react. The reaction stops after 24h. Remove the solvent by evaporation under reduced pressure. Drop the product into 20ml methanol for precipitation, and remove the unreacted product and catalyst. Dry the product under vacuum at 40℃ for 10-12h to obtain siloxane-modified polyarylate.

2. Application: Preparation of flexible silicone polyarylate coating

The polymer was dissolved in tetrahydrofuran to prepare a solution with a mass fraction of 20%, and the solution was kept at a constant temperature of 25°C for degassing for 3 hours to obtain a casting solution. The casting solution was spin-coated on a glass sheet or poured on a clean polytetrafluoroethylene mold, and the polymer-coated substrate/mold was left in the air for 12 hours, and placed in an oven at 80°C for 6-8 hours to evaporate the remaining solvent to obtain a flexible silicone polyarylate coating.

The formed 0.2 mm film was subjected to mechanical testing. The film was stretched at a speed of 100 mm/min, and the mechanical properties showed that the tensile strength was 2.57 MPa, the elongation at break was 247%, and the elastic modulus was 96.1 MPa. The film was subjected to an ice adhesion strength test. Icicles were frozen on its surface at -20°C. The strength obtained by pushing down the icicles under the action of a push-pull testing machine was the ice adhesion strength, and the ice adhesion strength was measured to be 61 MPa.

Embodiment 3:

1. Preparation of organosilicon polyarylate copolymer

Synthesis of polyarylate containing double bonds:

2.313g of diallyl bisphenol A and 0.176g of triethylbenzyl ammonium chloride (catalyst) were dissolved in a flask containing 15ml of NaOH aqueous solution as the water phase, and 0.85g of terephthaloyl chloride and 0.85g of isophthaloyl chloride were dissolved in 22.4ml of dichloromethane as the oil phase and placed in a constant pressure funnel. At 2°C, the oil phase was dripped into the water phase at a rate of 1s/drop for reaction. After the dripping was completed, the reaction lasted for 8h and the reaction was terminated. The product was purified by precipitation with 30ml of methanol to obtain a polyarylate containing double bonds.

Synthesis of Siloxane-Modified Polyarylate:

Take 1g polyarylate and 0.43g heptamethyltrisiloxane and dissolve them in 30ml toluene. Pass nitrogen at 60℃ for 30 minutes. Use a syringe to add 30mg platinum catalyst to react. The reaction stops after 24h. Remove the solvent by evaporation under reduced pressure. Drop the product into 20ml methanol for precipitation, and remove the unreacted product and catalyst. Dry the product under vacuum at 40℃ for 10-12h to obtain siloxane-modified polyarylate.

2. Application: Preparation of flexible silicone polyarylate coating

The above-mentioned organosilicon polyarylate polymer was dissolved in toluene to prepare a solution with a mass fraction of 20%, and the solution was placed at a constant temperature of 25°C for degassing for 4 hours to obtain a casting solution. The casting solution was spin-coated on a glass sheet or poured on a clean polytetrafluoroethylene mold, and the polymer-coated substrate/mold was left in the air for 12 hours and placed in an oven at 80°C for 6-8 hours to evaporate the remaining solvent to obtain a flexible organosilicon polyarylate coating.

The formed 0.2 mm film was subjected to mechanical testing. The film was stretched at a speed of 100 mm/min, and the mechanical properties showed that the tensile strength was 4.56 MPa, the elongation at break was 213.5%, and the elastic modulus was 113.6 MPa. The film was subjected to an ice adhesion strength test. Icicles were frozen on its surface at -20°C. The strength obtained by pushing down the icicles under the action of a push-pull testing machine was the ice adhesion strength, and the ice adhesion strength was measured to be 102 MPa.

Embodiment 4:

1. Preparation of organosilicon polyarylate copolymer

Synthesis of polyarylate containing double bonds:

2.313g of diallyl bisphenol A and 0.176g of triethylbenzyl ammonium chloride (catalyst) were dissolved in a flask containing 15ml of NaOH aqueous solution as the water phase, and 0.85g of terephthaloyl chloride and 0.85g of isophthaloyl chloride were dissolved in 22.4ml of dichloromethane as the oil phase and placed in a constant pressure funnel. At 2°C, the oil phase was dripped into the water phase at a rate of 1s/drop for reaction. After the dripping was completed, the reaction was allowed to proceed for 10h, and the reaction was terminated. The product was purified by precipitation with 30ml of methanol to obtain a polyarylate containing double bonds.

Synthesis of Siloxane-Modified Polyarylate:

Take 1g polyarylate and 0.23g heptamethyltrisiloxane and dissolve them in 30ml toluene. Pass nitrogen at 60℃ for 30 minutes. Use a syringe to add 30mg platinum catalyst to react. The reaction stops after 24h. Remove the solvent by evaporation under reduced pressure. Drop the product into 20ml methanol for precipitation, and remove the unreacted product and catalyst. Dry the product under vacuum at 40℃ for 10-12h to obtain siloxane-modified polyarylate.

2. Application: Preparation of flexible silicone polyarylate coating

The above-mentioned organosilicon polyarylate polymer is dissolved in chloroform to prepare a solution with a mass fraction of 20%, and the solution is placed at a constant temperature of 25°C for degassing for 2-4 hours to obtain a casting solution. The casting solution is spin-coated on a glass sheet or poured on a clean polytetrafluoroethylene mold, and the polymer-coated substrate/mold is placed in the air for 12 hours and placed in an oven at 80°C for 6-8 hours to evaporate the remaining solvent to obtain a flexible organosilicon polyarylate coating.

The formed 0.2 mm film was subjected to mechanical testing. The film was stretched at a speed of 100 mm/min, and the mechanical properties showed that the tensile strength was 5.39 MPa, the elongation at break was 150.6%, and the elastic modulus was 129 MPa. The film was subjected to an ice adhesion strength test. Icicles were frozen on its surface at -20°C. The strength obtained by pushing down the icicles under the action of a push-pull testing machine was the ice adhesion strength, and the ice adhesion strength was measured to be 124 MPa.

The mechanical property test results and ice adhesion strength of the films obtained in Examples 1 to 4 are shown in Table 1 and FIG. 2 .

Table 1. Mechanical properties test results

Elastic modulus (MPa) Elongation at break (%) Tensile strength (MPa) Example 1 89.6±1.59 220±3.89 1.79±0.41 Example 2 96.1±1.16 247±2.58 2.57±0.77 Example 3 113.6±1.91 213.5±1.85 4.56±0.94 Example 4 129±2.48 150.6±1.44 5.39±0.62

Note: The values in Table 1 are mean ± standard deviation

Although the above describes the specific implementation mode of the present invention in conjunction with the accompanying drawings, it is not intended to limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims (9)

1. An organosilicon-modified polyarylate, characterized in that its structural formula is as shown in Formula I, wherein m is a natural number of 50 to 100, and the number average molecular weight is 24700 to 49500; 2. The method for preparing the organosilicon-modified polyarylate according to claim 1, characterized in that the polyarylate containing double bonds is modified by using heptamethyltrisiloxane, wherein the structural formula of the polyarylate containing double bonds is as shown in Formula II, wherein n is a natural number of 50 to 100, and the number average molecular weight is 15000 to 40000; 3. The preparation method according to claim 2 is characterized in that the modification treatment method is: under a nitrogen atmosphere, the double-bond polyarylate and heptamethyltrisiloxane are subjected to a hydrosilylation reaction by a platinum catalyst, followed by post-treatment to obtain the product. 4. The preparation method according to claim 3 is characterized in that the specific method is as follows: firstly, polyarylate containing double bonds and heptamethyltrisiloxane are dissolved in toluene, nitrogen is passed through at 60° C. for 30 minutes, then a platinum catalyst is added, and the reaction is kept warm for 24 to 36 hours; wherein the amount ratio of polyarylate containing double bonds, heptamethyltrisiloxane, toluene, and platinum catalyst is 1g:0.42-1.02g:30mL:30mg. 5. The preparation method according to claim 2, characterized in that the double-bond-containing polyarylate is synthesized by interfacial polycondensation reaction of diallyl bisphenol A with terephthaloyl chloride and isophthaloyl chloride. 6. Use of the organosilicon-modified polyarylate according to claim 1 in the preparation of a flexible anti-icing film. 7. A method for preparing a flexible anti-icing film, characterized in that the organosilicon-modified polyarylate according to claim 1 is first dissolved in a solvent to prepare a polymer solution; the polymer solution is then cast into a mold or evenly coated on the surface of a substrate, and dried to obtain the film. 8. The preparation method according to claim 7, characterized in that the solvent is selected from any one of dichloromethane, tetrahydrofuran, benzene or toluene, or a mixture of two thereof. 9 . The preparation method according to claim 7 , characterized in that the mass concentration of the polymer solution is 20-30%.