Antifogging film material and preparation method thereof

文档序号：298435 发布日期：2021-11-26 浏览：22次中文

阅读说明：本技术 一种防雾膜材料及其制备方法 (Antifogging film material and preparation method thereof ) 是由施晓丽丁凯王新才于 2021-09-06 设计创作，主要内容包括：本发明公开了一种防雾膜材料及其制备方法,其特征在于,包括如下步骤：步骤S1、将烯丙基琥珀酰亚胺基碳酸酯、乙二醇二甲基丙烯酸酯、聚乙二醇单烯丙基醚、N-乙烯基咔唑、乙烯基β-环糊精季铵盐、2,3,5,6-四氟对苯二甲酸、端异氰酸酯基聚氨酯预聚体、引发剂、催化剂、纳米二氧化钛加入到有机溶剂中,搅拌均匀后,涂覆于聚四氟乙烯板或玻璃板上,置于惰性气体氛围,85-95℃下干燥至恒重,后揭膜,制得聚合物膜；步骤S2、辐射接枝,得到防雾膜材料。本发明的防雾膜材料防雾效果显著,防油和灰尘污染性能佳,热稳定性、耐磨耗性、力学性能、耐用性和性能稳定性优异。(The invention discloses an antifogging film material and a preparation method thereof, which are characterized by comprising the following steps: step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 85-95 ℃ to constant weight, and then removing the film to obtain a polymer film; and step S2, radiation grafting to obtain the antifogging film material. The antifogging film material disclosed by the invention has the advantages of obvious antifogging effect, good oil and dust pollution prevention performance, and excellent thermal stability, wear resistance, mechanical property, durability and performance stability.)

1. The preparation method of the antifogging film material is characterized by comprising the following steps of:

step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 85-95 ℃ to constant weight, and then removing the film to obtain a polymer film;

and S2, adding the polymer film prepared in the step S1 into a mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, soaking for 2-4 hours, taking out, drying in a blast oven at 80-95 ℃ to constant weight, and carrying out radiation grafting through radiation equipment at normal temperature in a nitrogen atmosphere to obtain the antifogging film material.

2. The preparation method of the antifogging film material of claim 1, wherein in step S1, the mass ratio of the allyl succinimidyl carbonate, the ethylene glycol dimethacrylate, the polyethylene glycol monoallyl ether, the N-vinylcarbazole, the vinyl beta-cyclodextrin quaternary ammonium salt, the 2,3,5, 6-tetrafluoroterephthalic acid, the isocyanate-terminated polyurethane prepolymer, the initiator, the catalyst, the nano titanium dioxide and the organic solvent is 2 (0.5-0.8), (2-3), (1-2), (0.3-0.5), (0.1), (0.8-1.2), (0.07-0.1), (0.1-0.2) and (40-80).

3. The preparation method of the antifogging film material according to claim 1, wherein the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.

4. The preparation method of the antifogging film material according to claim 1, wherein the catalyst is at least one of dibutyltin dilaurate and stannous octoate.

5. The preparation method of the antifogging film material as claimed in claim 1, wherein the particle size of the nano titanium dioxide is 300-600 nm.

6. The preparation method of the antifogging film material according to claim 1, wherein the organic solvent is at least one of dimethylsulfoxide, N-dimethylformamide and N-methylpyrrolidone; the inert gas is any one of nitrogen, helium, neon and argon.

7. The method for preparing an antifogging film material according to claim 1, wherein the solvent of the mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide in step S2 is dimethyl sulfoxide; the mass ratio of the methylvinyl silafluorene to the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide to the dimethyl sulfoxide is 5 (5-10) to 85-90.

8. The method for preparing an antifogging film material according to claim 1, wherein the radiation grafting in step S2 is electron beam radiation grafting, the radiation energy is 8MeV to 18MeV, and the radiation dose is 60KGy to 230 KGy.

9. An antifogging film material prepared by the method for preparing an antifogging film material according to any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of antifogging film materials, in particular to an antifogging film material and a preparation method thereof.

Background

Transparent substrates (such as glasses, window glass, bathroom mirrors, building interior and exterior window glass, agricultural greenhouses and the like) are indispensable materials in daily life, work and production of people, but in the use process of the transparent substrates, a fogging phenomenon often occurs in places with poor high temperature or poor high humidity, so that the light transmittance and the reflectivity of the substrates are reduced, the sight is influenced, inconvenience is brought to the life of people, even danger can occur, and a large amount of manpower and material resources are lost. Therefore, how to overcome the fogging of the water vapor on the surface of the transparent substrate and prevent the fogging phenomenon has generated a hot spot of research of current researchers.

At present, the common method for preventing the atomization phenomenon is the use of an anti-fog film. The antifogging film is a functional film which prevents water vapor from forming fog on the surface of the film to influence the transparency. The existing antifogging film has the defects of poor antifogging effect, poor oil and dust pollution resistance, and further improvement of thermal stability, wear resistance, mechanical property, durability and performance stability.

In order to solve the above problems, chinese patent document CN102794965B discloses an antifogging polyester film and a preparation method thereof. In order to solve the defects that the existing antifogging film product is thick in thickness, poor in thermal stability and difficult to apply in a high-temperature and high-humidity environment, the invention provides an antifogging polyester film and a preparation method thereof. The anti-fog polyester film provided by the invention comprises a polyester substrate, wherein anti-fog functional layers are arranged on two sides of the substrate; the polyester substrate is a pure polyester layer, and the antifogging functional layer is made of 100 parts of polyester slices, 0.5-2.0 parts of antifogging agent and 0.1-0.5 part of synergist. The film has the advantages of good transparency, good machining performance, small thickness, good thermal stability and good antifogging property, can be applied in a high-temperature and high-humidity environment, and is simple in preparation method and easy to operate. However, the antifogging film has poor performance stability, and the antifogging effect and the abrasion resistance need to be further improved.

Therefore, the development of an antifogging film material with remarkable antifogging effect, excellent oil and dust pollution resistance, excellent thermal stability, abrasion resistance, mechanical property, durability and performance stability is a popular subject of research in the industry at present.

Disclosure of Invention

The invention mainly aims to provide an antifogging film material which has remarkable antifogging effect, excellent oil and dust pollution resistance, excellent thermal stability, wear resistance, mechanical property, durability and performance stability and a preparation method thereof.

In order to achieve the above purpose, the invention provides a preparation method of an antifogging film material, which is characterized by comprising the following steps:

Preferably, in the step S1, the mass ratio of the allyl succinimidyl carbonate, the ethylene glycol dimethacrylate, the polyethylene glycol monoallyl ether, the N-vinylcarbazole, the vinyl beta-cyclodextrin quaternary ammonium salt, the 2,3,5, 6-tetrafluoroterephthalic acid, the isocyanate-terminated polyurethane prepolymer, the initiator, the catalyst, the nano titanium dioxide and the organic solvent is 2 (0.5-0.8): 2-3): 1-2): 0.3-0.5):0.1 (0.8-1.2): 0.07-0.1): 0.2 (40-80).

Preferably, the preparation method of the vinyl beta-cyclodextrin quaternary ammonium salt is disclosed in example 6 in application No. 201610596491. X.

Preferably, the preparation method of the isocyanate-terminated polyurethane prepolymer is as follows: CN 113201114A, example 1.

Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.

Preferably, the catalyst is at least one of dibutyltin dilaurate and stannous octoate.

Preferably, the particle size of the nano titanium dioxide is 300-600 nm.

Preferably, the organic solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.

Preferably, the inert gas is any one of nitrogen, helium, neon and argon.

Preferably, the solvent of the mixed solution of methylvinylsiluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide in the step S2 is dimethyl sulfoxide, wherein the mass ratio of the methylvinylsiluorene, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and the dimethyl sulfoxide is 5 (5-10) to (85-90).

Preferably, the radiation grafting in step S2 is electron beam radiation grafting, the radiation energy is 8MeV to 18MeV, and the radiation dose is 60KGy to 230 KGy.

The second purpose of the invention is to provide an antifogging film material prepared according to the preparation method of the antifogging film material.

Due to the application of the technical scheme, the invention has the following beneficial effects:

(1) the antifogging film material disclosed by the invention is simple in preparation process, convenient to operate, high in preparation efficiency and suitable for continuous large-scale production.

(2) In the antifogging film material disclosed by the invention, in the step S1, monomers containing unsaturated ethylenic bonds, such as allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinyl carbazole and vinyl beta-cyclodextrin quaternary ammonium salt, can generate free radical copolymerization reaction under the initiation action of an initiator; meanwhile, quaternary ammonium salt on the molecular chain can react with carboxyl on the 2,3,5, 6-tetrafluoroterephthalic acid to be connected; hydroxyl on a molecular chain can also react with isocyanate groups on the isocyanate-terminated polyurethane prepolymer under the action of a catalyst to form a three-dimensional network structure, so that the comprehensive performance and the performance stability of the film layer are effectively improved, and the thermal stability, the wear resistance, the mechanical property and the durability of the film layer are excellent.

(3) According to the antifogging film material disclosed by the invention, in the step S1, through the interaction and influence among the raw materials, more hydrophilic groups are introduced into the molecular structure of the film layer, so that a better antifogging effect is achieved; the anti-fog performance can be improved by introducing the beta-cyclodextrin, and the adhesion between the beta-cyclodextrin and a base material and the compatibility between the beta-cyclodextrin and other raw materials can also be improved; the introduced succinimidyl carbonate, carbazole and tetrafluorobenzene interact with each other, so that the prepared antifogging film material has excellent thermal stability, wear resistance, mechanical property, durability and performance stability.

(4) In the step S2, the surface of the film layer is grafted with the silicon fluorenyl, the cyano trifluoromethyl phenyl and the amido by the radiation grafting method, the hydrophobic groups can effectively improve the performances of fog prevention, oil prevention and dust pollution, and the hydrophobic groups interact with each other, so that the anti-aging performance, the durability and the wear resistance of the anti-fogging film material are better. The groups are tightly connected with the film layer by a radiation grafting method, so that the defects of insufficient adhesion and poor durability of double-layer films in the prior art are effectively overcome.

Detailed Description

The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.

Example 1

The preparation method of the antifogging film material is characterized by comprising the following steps of:

step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 85 ℃ to constant weight, and then uncovering the film to prepare a polymer film;

and S2, adding the polymer film prepared in the step S1 into a mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, soaking for 2 hours, taking out, drying in a blast oven at 80 ℃ to constant weight, and carrying out radiation grafting through radiation equipment at normal temperature in a nitrogen atmosphere to obtain the antifogging film material.

In the step S1, the mass ratio of the allyl succinimidyl carbonate, the ethylene glycol dimethacrylate, the polyethylene glycol monoallyl ether, the N-vinylcarbazole, the vinyl beta-cyclodextrin quaternary ammonium salt, the 2,3,5, 6-tetrafluoroterephthalic acid, the isocyanate-terminated polyurethane prepolymer, the initiator, the catalyst, the nano titanium dioxide and the organic solvent is 2:0.5:2:1:0.3:0.1:0.8:0.07:0.1:0.2: 40.

The preparation method of the vinyl beta-cyclodextrin quaternary ammonium salt is disclosed in example 6 in application No. 201610596491. X; the preparation method of the isocyanate-terminated polyurethane prepolymer is as follows: CN 113201114A, example 1.

The initiator is azobisisobutyronitrile; the catalyst is dibutyltin dilaurate; the particle size of the nano titanium dioxide is 300 nm; the organic solvent is dimethyl sulfoxide; the inert gas is nitrogen.

In the step S2, the solvent of the mixed solution of methylvinylsiluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide is dimethyl sulfoxide, wherein the mass ratio of the methylvinylsiluorene, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and the dimethyl sulfoxide is 5:5: 85; the radiation grafting is electron beam radiation grafting, the radiation energy is 8MeV, and the radiation dose is 60 KGy.

An antifogging film material prepared according to the preparation method of the antifogging film material.

Example 2

The preparation method of the antifogging film material is characterized by comprising the following steps of:

step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 87 ℃ to constant weight, and then uncovering the film to prepare a polymer film;

and S2, adding the polymer film prepared in the step S1 into a mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, soaking for 2.5 hours, taking out, drying in a blast oven at 83 ℃ to constant weight, and carrying out radiation grafting through radiation equipment at normal temperature in a nitrogen atmosphere to obtain the antifogging film material.

The initiator is azobisisoheptonitrile; the catalyst is stannous octoate; the particle size of the nano titanium dioxide is 400 nm; the organic solvent is N, N-dimethylformamide; the inert gas is helium.

In the step S2, the solvent of the mixed solution of methylvinylsiluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide is dimethyl sulfoxide, wherein the mass ratio of the methylvinylsiluorene, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and the dimethyl sulfoxide is 5:7: 87; the radiation grafting is electron beam radiation grafting, the radiation energy is 11MeV, and the radiation dose is 120 KGy.

An antifogging film material prepared according to the preparation method of the antifogging film material.

Example 3

The preparation method of the antifogging film material is characterized by comprising the following steps of:

step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 90 ℃ to constant weight, and then uncovering the film to prepare a polymer film;

and S2, adding the polymer film prepared in the step S1 into a mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, soaking for 3 hours, taking out, drying in a blast oven at 88 ℃ to constant weight, and carrying out radiation grafting through radiation equipment at normal temperature in a nitrogen atmosphere to obtain the antifogging film material.

The initiator is azobisisobutyronitrile; the catalyst is dibutyltin dilaurate; the particle size of the nano titanium dioxide is 450 nm; the organic solvent is N-methyl pyrrolidone; the inert gas is neon.

In the step S2, the solvent of the mixed solution of methylvinylsiluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide is dimethyl sulfoxide, wherein the mass ratio of the methylvinylsiluorene, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and the dimethyl sulfoxide is 5:8: 88; the radiation grafting is electron beam radiation grafting, the radiation energy is 14MeV, and the radiation dose is 160 KGy.

An antifogging film material prepared according to the preparation method of the antifogging film material.

Example 4

The preparation method of the antifogging film material is characterized by comprising the following steps of:

step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 93 ℃ to constant weight, and then uncovering the film to prepare a polymer film;

and S2, adding the polymer film prepared in the step S1 into a mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, soaking for 3.5 hours, taking out, drying in a blast oven at 93 ℃ to constant weight, and carrying out radiation grafting through radiation equipment at normal temperature in a nitrogen atmosphere to obtain the antifogging film material.

The initiator is a mixture formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5; the catalyst is a mixture formed by mixing dibutyltin dilaurate and stannous octoate according to the mass ratio of 1: 3; the particle size of the nano titanium dioxide is 550 nm; the organic solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to the mass ratio of 1:2: 3; the inert gas is argon.

In the step S2, the solvent of the mixed solution of methylvinylsiluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide is dimethyl sulfoxide, wherein the mass ratio of the methylvinylsiluorene, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and the dimethyl sulfoxide is 5:9: 89; the radiation grafting is electron beam radiation grafting, the radiation energy is 17MeV, and the radiation dose is 210 KGy.

An antifogging film material prepared according to the preparation method of the antifogging film material.

Example 5

The preparation method of the antifogging film material is characterized by comprising the following steps of:

step S1, adding allyl succinimidyl carbonate, ethylene glycol dimethacrylate, polyethylene glycol monoallyl ether, N-vinylcarbazole, vinyl beta-cyclodextrin quaternary ammonium salt, 2,3,5, 6-tetrafluoroterephthalic acid, isocyanate-terminated polyurethane prepolymer, an initiator, a catalyst and nano titanium dioxide into an organic solvent, uniformly stirring, coating on a polytetrafluoroethylene plate or a glass plate, placing in an inert gas atmosphere, drying at 95 ℃ to constant weight, and then uncovering the film to prepare a polymer film;

and S2, adding the polymer film prepared in the step S1 into a mixed solution of methylvinylsilfluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide, soaking for 4 hours, taking out, drying in a blast oven at 95 ℃ to constant weight, and carrying out radiation grafting through radiation equipment at normal temperature in a nitrogen atmosphere to obtain the antifogging film material.

The initiator is azobisisobutyronitrile; the catalyst is dibutyltin dilaurate; the particle size of the nano titanium dioxide is 600 nm; the organic solvent is N, N-dimethylformamide; the inert gas is nitrogen.

In the step S2, the solvent of the mixed solution of methylvinylsiluorene and N- (4-cyano-3-trifluoromethylphenyl) methacrylamide is dimethyl sulfoxide, wherein the mass ratio of the methylvinylsiluorene, the N- (4-cyano-3-trifluoromethylphenyl) methacrylamide and the dimethyl sulfoxide is 5:10: 90; the radiation grafting is electron beam radiation grafting, the radiation energy is 18MeV, and the radiation dose is 230 KGy.

An antifogging film material prepared according to the preparation method of the antifogging film material.

Comparative example 1

The invention provides an antifogging film material, the formula and the preparation method of which are similar to those of example 1, except that N-vinylcarbazole and vinyl beta-cyclodextrin quaternary ammonium salt are not added.

Comparative example 2

The invention provides an antifogging film material, the formula and the preparation method of which are similar to those of the example 1, except that methylvinyl silafluorene is not added.

In order to further illustrate the beneficial technical effects of the antifogging film materials prepared in the embodiments of the present invention, the antifogging film materials prepared in the embodiments 1 to 5 and the comparative examples 1 to 2 were subjected to the related performance tests, the test results are shown in table 1, and the test methods are as follows:

(1) antifogging property: placing the prepared antifogging film material in steam at 95 ℃, ensuring the temperature to be continuous, observing whether the surface has a fogging phenomenon or not, and keeping the time for placing for more than 2 min.

(2) Water resistance: referring to GB/T1733 + 1993, the antifogging product is soaked in deionized water to observe whether the phenomena of foaming, whitening and falling off occur.

(3) The visible light transmittance in the range of 400-800nm was measured using ultraviolet-visible light absorption spectroscopy (UV-Vis).

(4) Wear resistance: using 0000# steel wool, 300g force, one to and fro is noted once: after a certain number of rubs, the scratch was observed and the maximum number of rubs that could be tolerated without scratch was recorded.

(5) Tensile strength: the test was carried out with reference to GB/T1040.1-2006.

(6) Heat aging resistance: the retention of tensile strength after 96 hours of artificially accelerated aging of the film in hot air at 85 ℃ is measured.

As can be seen from the data in Table 1, the antifogging film material prepared by the embodiment of the invention has higher strength, better antifogging effect, aging resistance, wear resistance, water resistance and transparency, which are the results of the synergistic effect of the raw materials.

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

8页详细技术资料下载

Antifogging film material and preparation method thereof

相关技术

网友询问留言