CN114940860B

CN114940860B - Hydrophobic and oleophobic polymer film material and preparation method thereof

Info

Publication number: CN114940860B
Application number: CN202210793073.5A
Authority: CN
Inventors: 李江涛; 苏蜜蜜; 蒋西西; 李娜
Original assignee: Shaanxi Dexin Zhongding New Material Technology Co ltd; Xian University
Current assignee: Shaanxi Dexin Zhongding New Material Technology Co ltd; Xian University
Priority date: 2022-07-07
Filing date: 2022-07-07
Publication date: 2023-02-17
Anticipated expiration: 2042-07-07
Also published as: CN114940860A

Abstract

The invention provides a hydrophobic and oleophobic polymer film material and a preparation method thereof, wherein the polymer film material is prepared from the following raw materials in parts by weight: 1-10 parts of hydroxyl-terminated hyperbranched polyester, 1-2 parts of PAMAM, 4-15 parts of curing agent, 1-2 parts of antifouling agent, 5-15 parts of propylene glycol methyl ether acetate, 2-8 parts of organic solvent and 0.01-0.02 part of catalyst; the curing agent is isocyanatopropyl triethoxysilane or 3- (methacryloyloxy) propyl trimethoxysilane. The invention takes IPTS/G-570 as a curing agent, utilizes sufficient alcoholic hydroxyl crosslinking sites provided by HBPE, selects IPTS/G-570 as the curing agent to form heavy crosslinking with the HBPE, and mixes all the reagents to form uniform coating solution. The coating material can be kept in a flowing liquid state after 3 days, and construction is facilitated.

Description

Hydrophobic and oleophobic polymer film material and preparation method thereof

Technical Field

The invention relates to the technical field of multifunctional coating materials, in particular to a hydrophobic and oleophobic polymer film material and a preparation method thereof.

Background

Inspired by the "lotus effect" and the "rose effect", hydrophobic surfaces have attracted the attention of scholars. These surfaces with special wettability have very important application prospects in many fields. Wettability is an important intrinsic property of a solid surface, and generally, the wettability of the solid surface is determined by the chemical composition and the surface topography of the solid surface. Therefore, the main idea for changing the surface property of the material and realizing the control of wettability is to change the microstructure and the surface chemical composition of the solid surface. The adjustment of the wettability of the solid surface by the chemical composition and the microstructure of the solid surface has potential application value.

Zhong Ximing and the like ^[1] Robust hyperbranched polyester-based antifouling coatings for self-cleaning, anti-graffiti and chemical barrier are disclosed, prepared by dissolving HBPE (1.00 g) in DMF (1.00 g) followed by HDIT (2.26 g), DBTDL (0.01 g), PGMEA (2.00 g) and PDMS in different weight ratios (% by weight addition relative to the total weight of HBPE and HDIT) and thoroughly mixed. The antifouling paint is prepared by taking hexamethylene diisocyanate trimer (HDIT) as a curing agent, and shows remarkable repellency to various liquids. However, the antifouling paint is not allowed to stand for a long time due to the aging property of hexamethylene diisocyanate trimer (HDIT), and the emulsion is immediately solidified after standing, which severely limits the large-scale use of the paint.

Disclosure of Invention

In order to solve the technical problems, the invention aims to provide a hydrophobic and oleophobic polymer film material and a preparation method thereof, the film material has the performances of hydrophobicity and oleophobicity, self-cleaning, corrosion resistance and high permeability, and the prepared emulsion can be placed for a long time without solidification, thereby being beneficial to wide application in actual life.

In order to achieve the above object, the technical solution of the present invention is as follows.

A hydrophobic and oleophobic polymer film material is prepared from the following raw materials in parts by weight:

1-10 parts of hydroxyl-terminated hyperbranched polyester, 1-2 parts of PAMAM, 4-15 parts of curing agent, 1-2 parts of antifouling agent, 5-15 parts of propylene glycol methyl ether acetate, 2-8 parts of organic solvent and 0.01-0.02 part of catalyst;

the curing agent is isocyanatopropyl triethoxysilane or 3- (methacryloyloxy) propyl trimethoxysilane.

Further, the antifouling agent is polydimethylsiloxane.

Further, the organic solvent is any one of DMF, ethylene glycol monomethyl ether, NMP, ethyl benzoate and isophorone.

Further, the mass ratio of the hydroxyl-terminated hyperbranched polyester to the organic solvent to the curing agent to the propylene glycol monomethyl ether acetate is 1-2: 1 to 2:2 to 4:2 to 5.

Further, the catalyst is dibutyltin dilaurate.

The invention also provides a preparation method of the hydrophobic and oleophobic polymer film material, which comprises the following steps:

dissolving hydroxyl-terminated hyperbranched polyester and PAMAM in an organic solvent at 30-90 ℃, then adding a curing agent, propylene glycol methyl ether acetate, an antifouling agent and a catalyst under the stirring condition, and obtaining the hydrophobic and oleophobic high polymer film material after the reaction is finished.

The invention also provides an application, wherein the hydrophobic and oleophobic polymer film material is coated on a substrate, and then is heated and treated for 1-2 h at 100-150 ℃ to obtain the hydrophobic and oleophobic polymer film.

Further, the substrate is heated for 50 to 90 seconds at 30 to 90 ℃ before coating.

Further, the substrate is a glass plate or a tin plate, but other base materials may be used.

The invention has the beneficial effects that:

1. the invention discloses a novel hydrophobic and oleophobic polymer film material which is developed by taking hydroxyl-terminated hyperbranched polyester as a coating precursor, hydroxyl-terminated Polydimethylsiloxane (PDMS) as an antifouling agent and Isocyanatopropyltriethoxysilane (IPTS)/3- (methacryloyloxy) propyltrimethoxysilane (G-570) as a curing agent, wherein HBPE hyperbranched polymer is taken as the coating precursor to provide enough crosslinking sites, PDMS is adopted to enable the coating to have lower surface energy, isocyanatopropyltriethoxysilane/3- (methacryloyloxy) propyltrimethoxysilane is selected as the curing agent to form heavier crosslinking, and all the reagents are mixed to form uniform coating solution.

2. The hydrophobic and oleophobic polymer film material prepared by the invention has good hydrophobic property, corrosion resistance, mechanical stability and chemical stability, can be kept in a flowing liquid state after 3 days, and is convenient for construction.

Drawings

FIG. 1 shows the synthesis process of preparing polymer film material with IPTS as curing agent.

FIG. 2 is a synthetic process of preparing a polymer film material with G-570 as a curing agent.

FIG. 3 shows the hydrophobic angle of the hydrophobic and oleophobic polymer film material of the invention.

FIG. 4 shows the oil-repelling angle of the hydrophobic and oleophobic polymer film material of the invention.

FIG. 5 is a comparative plot of hydrophobic and oleophobic coatings prepared with different curing agents. Wherein, the number (1) is a macromolecular antifouling paint prepared by using HDIT (hexamethylene diisocyanate trimer) as a curing agent; the serial number (2) is a hydrophobic and oleophobic polymer film material prepared by taking isocyanatopropyltriethoxysilane as a curing agent. The serial number (3) is a hydrophobic and oleophobic polymer film material prepared by using 3- (methacryloyloxy) propyl trimethoxy silane as a curing agent.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.

HBPE is hydroxyl-terminated hyperbranched polyester, and the molecular weight range is 500-1100. PAMAM is polyamide-amine type dendritic polymer. DMF is N, N-dimethylformamide. IPTS is isocyanatopropyltriethoxysilane. G-570 is 3- (methacryloyloxy) propyltrimethoxysilane. PGMEA was propylene glycol methyl ether acetate. PDMS is hydroxyl terminated polydimethylsiloxane. DBTDL is dibutyltin dilaurate.

The synthesis process of preparing the polymer film material by using IPTS as a curing agent is shown in figure 1. The synthesis process of preparing the polymer film material by taking G-570 as the curing agent is shown in figure 2.

The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.

Example 1

A hydrophobic and oleophobic polymer film material is prepared from the following raw materials:

4g of hydroxyl-terminated hyperbranched polyester, 1g of PAMAM, 12g of curing agent, 1g of hydroxyl-terminated polydimethylsiloxane, 7g of propylene glycol monomethyl ether acetate, 2g of DMF (dimethyl formamide), and 0.01g of dibutyltin dilaurate. Wherein the curing agent is isocyanatopropyl triethoxysilane.

The preparation method of the hydrophobic and oleophobic polymer film material comprises the following steps:

dissolving 4g of hydroxyl-terminated hyperbranched polyester and 1g of PAMAM in 2g of DMF (dimethyl formamide) under constant-temperature stirring at 75 ℃, adding 12g of curing agent after the dissolution is finished, stirring uniformly, adding 7g of propylene glycol methyl ether acetate after the full dissolution, adding one drop (about 1 g) of hydroxyl-terminated polydimethylsiloxane after the solution is clear and transparent, mixing uniformly, and adding one drop (about 0.01 g) of dibutyltin dilaurate to obtain the hydrophobic and oleophobic polymer film material.

Example 2

4g of hydroxyl-terminated hyperbranched polyester, 1g of PAMAM, 12g of curing agent, 1g of hydroxyl-terminated polydimethylsiloxane, 7g of propylene glycol monomethyl ether acetate, 2g of DMF (dimethyl formamide), and 0.01g of dibutyltin dilaurate. Wherein the curing agent is 3- (methacryloyloxy) propyl trimethoxy silane.

Example 3

1g of hydroxyl-terminated hyperbranched polyester, 1g of PAMAM, 4g of curing agent, 1g of hydroxyl-terminated polydimethylsiloxane, 5g of propylene glycol monomethyl ether acetate, 2g of DMF (dimethyl formamide), and 0.01g of dibutyltin dilaurate. Wherein the curing agent is 3- (methacryloyloxy) propyl trimethoxy silane.

dissolving 1g of hydroxyl-terminated hyperbranched polyester and 1g of PAMAM in 2g of DMF (dimethyl formamide) under constant-temperature stirring at the temperature of 30-90 ℃, adding 4g of curing agent after the dissolution is finished, uniformly stirring, adding 5g of propylene glycol methyl ether acetate after the full dissolution, adding one drop (about 1 g) of hydroxyl-terminated polydimethylsiloxane after the solution is clear and transparent, uniformly mixing, and adding one drop (about 0.01 g) of dibutyltin dilaurate to obtain the hydrophobic and oleophobic polymer film material.

Example 4

10g of hydroxyl-terminated hyperbranched polyester, 2g of PAMAM, 15g of curing agent, 2g of hydroxyl-terminated polydimethylsiloxane, 15g of propylene glycol monomethyl ether acetate, 8g of DMF (dimethyl formamide), and 0.02g of dibutyltin dilaurate. Wherein the curing agent is isocyanatopropyl triethoxysilane.

dissolving 10g of hydroxyl-terminated hyperbranched polyester and 2g of PAMAM in 8g of DMF (dimethyl formamide) under constant-temperature stirring at the temperature of 30-90 ℃, adding 15g of curing agent after the dissolution is finished, stirring uniformly, adding 15g of propylene glycol methyl ether acetate after the full dissolution, adding two drops (about 2 g) of hydroxyl-terminated polydimethylsiloxane after the solution is clear and transparent, mixing uniformly, and adding two drops (about 0.02 g) of dibutyltin dilaurate to obtain the hydrophobic and oleophobic polymer film material.

Examples 5 to 11

The hydrophobic and oleophobic polymer film material and the preparation method thereof are basically the same as those of the hydrophobic and oleophobic polymer film material and the preparation method thereof in example 1, and the difference is that the mixture ratio of PDMS and a curing agent is different, which is shown in Table 1.

TABLE 1 different proportions of PDMS and curing agent

Examples	Hydroxyl-terminated hyperbranched polyester	Curing agent
			5	4g	1.6g
6	4g	2g
			7	4g	4g
8	4g	8g
			1	4g	12g
9	4g	15g
			10	4g	30g
11	4g	70g

Comparative example 1

Robust hyperbranched polyester-based antifouling coatings for self-cleaning, anti-graffiti and chemical shielding ^[1] The feed additive is prepared from the following raw materials:

1.00g of HBPE (hydroxyl terminated hyperbranched polyester), 1.00g of DMF (dimethylformamide), 2.26g of HDIT (hexamethylene diisocyanate trimer), 0.01g of DBTDL (dibutyltin dilaurate), 2.00g of PGMEA (propylene glycol monomethyl ether acetate) and 0.016g of PDMS (monohydroxy terminated polydimethylsiloxane).

The preparation method of the antifouling paint comprises the following steps:

HBPE (1.00 g) was dissolved in DMF (1.00 g), and then dissolved in HDIT (2.26 g), DBTDL (0.01 g), PGMEA (2.00 g) and PDMS (added in 0.5wt% relative to the total weight of HBPE and HDIT), and thoroughly mixed to obtain an antifouling paint.

[1]Ximing Zhong,e.t.,Robust Hyperbranched Polyester-Based Anti-Smudge Coatings for Self-Cleaning,Anti-Graffiti,and Chemical Shielding[J],:ACS Appl.Mater.Interfaces 2019,11,14305-14312.

Application example 1

Heating an original substrate for 80 seconds, then coating the hydrophobic and oleophobic polymer film material prepared in the embodiment 1 on the substrate, placing the coated substrate in an oven at 100-150 ℃, and heating for 1-2 hours to obtain the hydrophobic and oleophobic coating.

Application example 2

Heating an original substrate for 80 seconds, then coating the hydrophobic and oleophobic polymer film material prepared in the embodiment 2 on the substrate, placing the coated substrate in an oven at 100-150 ℃, and heating for 1-2 hours to obtain the hydrophobic and oleophobic coating.

Application examples 3 to 11

The preparation method of the hydrophobic and oleophobic coating is basically the same as that of application example 1, except that the hydrophobic and oleophobic polymer thin film materials prepared in examples 3 to 11 are coated on a substrate.

Comparative application example 1

The antifouling paint mixture prepared in comparative example 1 was heated at 80 ℃ for 90 seconds and then cast onto various substrates, such as glass plates and tin plates. The coated substrates were cured at 120 ℃ for 1 hour and the cured samples were used for further studies.

1. Stability test of coating Material

1.1 stability test of different curing Agents on materials

The hydrophobic and oleophobic polymer film materials of examples 1-2 and the polymer antifouling paint prepared in the comparative example 1 are subjected to a stability test, and the polymer antifouling paint prepared in the comparative example 1 is filled into a sample tube, wherein the number of the sample tube is (1); the hydrophobic and oleophobic polymer film material of example 1 was placed in a sample tube with the number (2), the hydrophobic and oleophobic polymer film material of example 2 was placed in a sample tube with the number (3), and the stability tests were performed on the sample tubes with the numbers (1), (2) and (3), and the results are shown in table 2 and fig. 5.

TABLE 2 comparison of the setting times of coating materials prepared by different methods

Setting time	Comparative example 1	Example 1	Example 2
				0h	Liquid state	Liquid state	Liquid state
20min	Initiation of coagulation	Liquid state	Liquid state
				3h	Completely solidify	Liquid state	Liquid state
12h	Completely solidified	Liquid state	Liquid state
				1d	Completely solidified	Liquid state	Liquid state
3d	Completely solidified	Liquid state	Liquid state
				5d	Completely solidified	Liquid state	Liquid state

As can be seen from table 2 and fig. 4, the antifouling paint of comparative example 1, sample tube (1), which uses hexamethylene diisocyanate trimer (HDIT) as a curing agent, starts to solidify after 20 minutes, and cannot be sprayed or brushed, and completely solidifies after 3 hours: (2) the sample tube is the hydrophobic and oleophobic polymer film material of example 1, uses isocyanic acid propyl triethoxy silane as curing agent, and is still fluid after 3 days, so that it is convenient for construction. (3) The sample tube is the hydrophobic and oleophobic polymer film material of example 2, 3- (methacryloyloxy) propyl trimethoxy silane is used as a curing agent, and the material is still in a flowing liquid state after 3 days, so that the construction is convenient.

As is clear from the comparative analysis, the antifouling paint prepared in comparative example 1 could not be left for a long time due to the aging property of the hexamethylene diisocyanate trimer, and the emulsion immediately solidified after standing, and could not be used on a large scale. In examples 1 to 2 of the present invention, stable emulsions were prepared by adding dibutyltin dilaurate as a catalyst in addition to forming a heavy crosslink with HBPE by using isopropyltriethoxysilane/3- (methacryloyloxy) propyltrimethoxysilane as a curing agent. The hydrophobic and oleophobic polymer film material prepared in the embodiment 1 of the invention can be placed for a long time without solidification, and the performance of the hydrophobic and oleophobic polymer film material is superior to that of the antifouling paint prepared in the comparative example 1.

The antifouling paint prepared in comparative example 1 was an antifouling paint prepared by using hexamethylene diisocyanate trimer (HDIT) as a curing agent, wherein the reaction mechanism of isocyanate with polyol to prepare polyurethane was as follows:

the isocyanates contain isocyanate groups with a high degree of unsaturation (formula: -N = C = O) and are therefore chemically more reactive. The electron resonance structure of isocyanate is shown in the following formula (1), and it can be seen that, due to the action of electrostatic induction effect, there is a shift of electron cloud on oxygen atom, so that there is electronegativity on oxygen atom, there is also a larger electron cloud density on nitrogen atom, carbon atom shows so-called positive valence, forming electrophilic center, i.e., -NCO group, while nucleophilic center is oxygen atom with electronegativity, attracting H to generate-OH, but due to the instability of hydroxyl group on double bond, rearrangement generates carbamate group. The reaction mechanism is as follows:

the methylene diisocyanate trimer (HDIT) of comparative example 1 had three isocyanate groups, the isophorone diisocyanate (IPDI) had two isocyanate groups, and the isocyanatopropyltriethoxysilane had one isocyanate group. The more isocyanate groups reacted with the polyol, the more strongly the reaction of HDIT with the polyol HBPE, and therefore, the more strongly the curing agent used in example 1 of the present invention reacted with the polyol HBPE, and therefore, the more easily the curing was.

1.2 influence of dosage of curing agent on setting time of hydrophobic and oleophobic polymer film material

The hydrophobic and oleophobic polymer film materials of example 1 and examples 5-11 were subjected to stability testing using the method of 1.1 stability test, as shown in tables 1 and 3.

TABLE 3 comparison of setting times for Polymer film materials prepared with different amounts of curing agent

Setting time

0h

3h

12h

1d

3d

5d

Example 5

Liquid state

Initiation of coagulation

Completely solidified

Example 6

Liquid state

Initiation of coagulation

Completely solidified

Example 7

Liquid state

Example 8

Liquid state

Example 1

Liquid state

Example 9

Liquid state

Example 10

Liquid state

Initiation of coagulation

Completely solidified

Completely solidify

Example 11

Liquid state

Initiation of coagulation

Completely solidified

Completely solidify

Completely solidified

As is clear from the results in tables 1 and 3, in each of examples 1 and 5 to 11, isocyanatopropyltriethoxysilane was used as a curing agent. When the mass ratio of the hydroxyl-terminated hyperbranched polyester to the curing agent (isocyanic acid propyl triethoxy silane) meets 1-2: 2-4, the hydrophobic and oleophobic polymer film material prepared in example 1 and examples 7-9 is still in a fluid liquid state after 3 days, which is convenient for construction. When the amount of the isopropyltriethoxysilane isocyanate is too much or too little, the hydrophobic and oleophobic polymer film materials prepared in examples 5 to 6 and examples 10 to 11 have substantially the same properties as those of the hydrophobic and oleophobic polymer film materials prepared in examples 1 and 7 to 9, but the hydrophobic and oleophobic polymer film materials prepared in examples 5 to 6 and examples 10 to 11 have a relatively fast setting speed due to the too much or too little amount of the curing agent, but do not affect the properties before the setting.

2. Contact Angle testing of hydrophobic oleophobic coatings

The hydrophobic and oleophobic coatings prepared in application example 1 were tested for their hydrophobic and oleophobic angles using a JC2000C1 contact angle measuring instrument, and the results are shown in fig. 3 and 4.

Fig. 3 and 4 are photographs of the contact angles of the hydrophobic and oleophobic coating to deionized water and oleic acid, respectively. According to the results shown in fig. 3 and fig. 4, the hydrophobic and oleophobic coating prepared by the application example 1 of the invention has good hydrophobic/oleophobic performance, and the hydrophobic angle is close to 90 °; the oil drainage angle was 86 °.

3. Chemical stability testing of hydrophobic oleophobic coatings

The hydrophobic and oleophobic coatings prepared in application examples 1-11 are tested in concentrated sulfuric acid (98%), concentrated alkali (4M), saturated copper sulfate and sodium chloride salt mist for 72 hours, and the coatings still maintain good anticorrosion performance and hydrophobic and oleophobic performance.

4. Mechanical stability testing of hydrophobic and oleophobic coatings

The hydrophobic and oleophobic coatings prepared in application examples 1-11 are subjected to a high-speed sand blasting machine experiment for one week, and after the coating is subjected to a sand blasting experiment for one week, the hydrophobic angle of the coating is 91 degrees, the oil angle is 86 degrees, and the hydrophobic and oil angle is still higher, so that the coating has good wear resistance and wind-sand erosion resistance.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A hydrophobic and oleophobic polymer film material is characterized by being prepared from the following raw materials in parts by weight:

the curing agent is isocyanatopropyl triethoxysilane or 3- (methacryloyloxy) propyl trimethoxysilane; the antifouling agent is polydimethylsiloxane.

2. The hydrophobic and oleophobic polymer film material according to claim 1, characterized in that the organic solvent is any one of DMF, ethylene glycol monomethyl ether, NMP, ethyl benzoate and isophorone.

3. The hydrophobic and oleophobic polymer film material according to claim 1, characterized in that the mass ratio of hydroxyl-terminated hyperbranched polyester, organic solvent, curing agent and propylene glycol methyl ether acetate is 1-2: 1 to 2:2 to 4:2 to 5.

4. The hydrophobic and oleophobic polymer film material of claim 1, wherein the catalyst is dibutyltin dilaurate.

5. A method for preparing the hydrophobic and oleophobic polymer film material according to any one of claims 1-4, characterized by comprising the following steps: