阅读说明：本技术 一种环氧基有机硅离型剂及其制备方法与应用 (Epoxy-based organic silicon release agent and preparation method and application thereof ) 是由 林树东 于昕仪 胡继文 胡洋飞 冯超 涂园园 琚兴铭 于 2019-09-23 设计创作，主要内容包括：本发明公开了一种环氧基有机硅离型剂及其制备方法与应用,所述环氧基有机硅离型剂的制备方法包括原料的称取、有机硅预聚物的制备和环氧有机硅离型剂的生成,本发明的制备方法为常温下固化成膜,固化成膜时间低,减少了反应步骤和结构的复杂程度,提高了制备效率,制成的环氧基有机硅离型剂不仅具有交联密度大、剥离力轻和抗氧化的优点,同时制备的有机硅离型剂还在UV光照射下快速固化,离型性能稳定且优良。(The invention discloses an epoxy organosilicon release agent and a preparation method and application thereof, wherein the preparation method of the epoxy organosilicon release agent comprises the steps of weighing raw materials, preparing an organosilicon prepolymer and generating the epoxy organosilicon release agent.)

1. An epoxy-based silicone release agent, which is characterized in that the structural formula of the epoxy-based silicone release agent is as follows:

，

wherein m is 20 to 100 and n is 30 to 50.

2. The preparation method of the epoxy organosilicon release agent is characterized by comprising the following steps:

1) weighing raw materials: according to the weight ratio of 20-25: 10: 0-5: weighing epoxy monomers, high-hydrogen-content silicone oil, short-chain silicone oil and a photoinitiator according to a molar ratio of 1-5, or weighing the epoxy monomers, the high-hydrogen-content silicone oil, the short-chain silicone oil and the photoinitiator according to a molar ratio of 20-25: 10: weighing an epoxy monomer, high-hydrogen silicone oil and a photoinitiator in a molar ratio of 1-5;

2) preparation of silicone prepolymer: adding the epoxy monomer, the high-hydrogen-content silicone oil and the catalyst in the step 1) into a reactor, stirring, heating to 50-60 ℃, reacting for 4-6 h, and performing rotary evaporation on the obtained product to remove unreacted monomer and catalyst to obtain an epoxy group organic silicon prepolymer;

3) generation of epoxy silicone release agent: mixing and stirring the epoxy organosilicon prepolymer obtained in the step 2) with the short-chain silicone oil and the photoinitiator obtained in the step 1) at room temperature, or mixing and stirring the epoxy organosilicon prepolymer obtained in the step 2) with the photoinitiator at room temperature until the photoinitiator is uniformly dispersed in organosilicon to obtain the epoxy organosilicon release agent.

3. The method for preparing epoxy silicone release agent according to claim 2,

the epoxy monomer is an epoxy monomer of alpha-olefin;

the high hydrogen-containing silicone oil has the structural formula:

wherein m is₁＝20～100，n₁30-50, the viscosity at 25 ℃ is 10-100 cp, the hydrogen content is 1.6%, or the high hydrogen silicone oil has the structural formulaWherein m is₃＝20～100，n₃30-50, viscosity at 25 ℃ of 10-100 cp, and hydrogen content of 1.6%;

the catalyst is Karstedt catalyst;

the photoinitiator is at least one of ethyl benzoate, a photoinitiator BMS, a photoinitiator TPO, a sulfonium salt photoinitiator, an iodonium salt photoinitiator and a photoinitiator containing polysiloxane chain segments in the structure.

4. The preparation method of the epoxy silicone release agent according to claim 2, characterized in that when the step (1) is performed according to a ratio of 20-25: 10: 0-5: weighing an epoxy monomer, high-hydrogen-content silicone oil, short-chain silicone oil and a photoinitiator in a molar ratio of 1-5, wherein the short-chain silicone oil has the following structural formula:

wherein m is₂＝1～10，n₂1 to 10 and has a viscosity of 10 to 50cp at 25 ℃.

5. The method for preparing the epoxy-based silicone release agent according to claim 3, wherein the epoxy monomer of the α -olefin is 1, 2-epoxy-9-decene, and the molecular structural formula thereof is as follows:

6. the method for preparing the epoxy group organic silicon parting agent according to claim 4, characterized in that n in the high hydrogen-containing silicone oil structure₃95-100, in the short-chain silicone oil structure, n₂＝2～5。

7. The preparation method of the epoxy silicone release agent according to claims 2 to 6, characterized in that the addition amount of the photoinitiator in the step 3) accounts for 3-5% of the total mass of the reactants.

8. Use of the epoxy-based silicone release agent of any one of claims 1 to 7 for the preparation of release paper or release film.

9. The application of the epoxy-based silicone release agent in preparing release paper or release film according to claim 8, wherein the epoxy-based silicone release agent is prepared by the following specific steps: uniformly coating the epoxy-based organosilicon release agent on a substrate, placing the coated substrate in a UV light instrument, irradiating by using UV light with the wavelength of 320-410 nm, and curing by using the UV light to obtain the epoxy-based organosilicon release film.

Technical Field

The invention relates to the field of preparation of high polymer materials, in particular to an epoxy-based organic silicon release agent and a preparation method and application thereof.

Background

The release agent is a coating material with a separation effect on the surface, which prevents or reduces the adhesion of the composite material to a mold, a substrate and the like. When the substrate is paper, the release paper obtained by coating is generally used in the fields of labels and the like; when the base material is organic thin film material such as PET, the release film obtained by coating has application value in the electronic industry.

The type of the release agent with the highest market share at the present stage is a thermosetting polysiloxane release agent. However, with the increasing demand for release agents in the fields of transportation, food, energy and the like and the increasing demand for release agent performance and the like, the traditional polysiloxane release agent cannot meet the demand, so that the research on novel organic silicon or radiation curing organic silicon becomes a focus.

The epoxy group is an oxygen-containing saturated group, and has three kinds of groups at the introduction position of the silicone, including a prepolymer terminal group, a prepolymer side chain, and both. The introduction of epoxy groups in the three positions can effectively inhibit oxygen inhibition, and the problem that organosilicon cannot be completely cured due to high oxygen sensitivity is avoided, so that the release effect of the release agent is further improved. In other types of existing release agents with epoxy groups introduced, such as acrylate release agents, the introduction of epoxy groups often causes the main chain of the prepolymer to grow, the viscosity to increase, the use of reactive diluents to increase in use is needed, the time required for curing is increased, and the flexibility of the final product is also affected. Therefore, the epoxy group is introduced into the side chain of the siloxane, so that the epoxy group of the prepolymer can be increased, the use of the reactive diluent is reduced due to insignificant viscosity increase, and the curing speed of the release agent is improved while the product performance is maintained and improved.

The existing parting agent mainly adopts a thermal curing mode, namely, hydrosilylation reaction is carried out under the action of platinum or karstedt catalyst. In this way, the reaction needs to be carried out at a higher temperature (not lower than 150 ℃), the operation safety is reduced, meanwhile, the time required by high-temperature curing is longer, the yield is influenced in commercial production, and the energy consumption is higher; meanwhile, the amount of the catalyst for initiating the thermal curing is large, the platinum-containing catalyst is expensive, and a platinum recovery process which can be put into a production line is not found yet, so that the method is not suitable for industrial mass production.

Disclosure of Invention

In order to solve the defects and shortcomings of the prior art, the invention aims to provide the epoxy-based organic silicon release agent, which can improve the oxidation resistance of the organic silicon release agent and reduce the curing temperature of a coating.

One of the purposes of the invention is realized by the following technical scheme:

an epoxy group organic silicon release agent, wherein the structural formula of the epoxy group organic silicon release agent is as follows:

wherein m is 20 to 100 and n is 30 to 50.

The invention also aims to provide a preparation method of the epoxy organosilicon release agent.

The method is realized by the following technical scheme:

the preparation method of the epoxy organosilicon release agent is characterized by comprising the following steps:

1) weighing raw materials: according to the weight ratio of 20-25: 10: 0-5: weighing epoxy monomers, high-hydrogen-content silicone oil, short-chain silicone oil and a photoinitiator according to a molar ratio of 1-5, or weighing the epoxy monomers, the high-hydrogen-content silicone oil, the short-chain silicone oil and the photoinitiator according to a molar ratio of 20-25: 10: weighing an epoxy monomer, high-hydrogen silicone oil and a photoinitiator in a molar ratio of 1-5;

2) preparation of silicone prepolymer: adding the epoxy monomer, the high-hydrogen-content silicone oil and the catalyst in the step 1) into a reactor, stirring, heating to 50-60 ℃, reacting for 4-6 h, and performing rotary evaporation on the obtained product to remove unreacted monomer and catalyst to obtain an epoxy group organic silicon prepolymer;

3) generation of epoxy silicone release agent: mixing and stirring the epoxy organosilicon prepolymer obtained in the step 2) with the short-chain silicone oil and the photoinitiator obtained in the step 1) at room temperature, or mixing and stirring the epoxy organosilicon prepolymer obtained in the step 2) with the photoinitiator at room temperature until the photoinitiator is uniformly dispersed in organosilicon to obtain the epoxy organosilicon release agent.

Preferably, the epoxy monomer is an epoxy monomer of an alpha-olefin;

the high hydrogen-containing silicone oil has the structural formula:

wherein m is₁＝20～100，n₁30-50, viscosity at 25 ℃ of 10-100 cp, and hydrogen content of 1.6%; or the structural formula of the high hydrogen-containing silicone oil is as follows:

wherein m is₃＝20～100，n₃30-50, viscosity at 25 ℃ of 10-100 cp, and hydrogen content of 1.6%;

the catalyst is Karstedt catalyst;

the photoinitiator is at least one of ethyl benzoate, a photoinitiator BMS, a photoinitiator TPO, a sulfonium salt photoinitiator, an iodonium salt photoinitiator and a photoinitiator containing polysiloxane chain segments in the structure.

Preferably, when the step (1) is carried out according to the ratio of 20-25: 10: 0-5: weighing an epoxy monomer, high-hydrogen-content silicone oil, short-chain silicone oil and a photoinitiator in a molar ratio of 1-5, wherein the short-chain silicone oil has the following structural formula:

wherein m is₂＝1～10，n₂1 to 10 and has a viscosity of 10 to 50cp at 25 ℃.

Further preferably, the epoxy monomer of the alpha-olefin is 1, 2-epoxy-9-decene, and the molecular structural formula is as follows:

further preferably, in the high hydrogen-containing silicone oil structure, n is₃95-100, in the short-chain silicone oil structure, n₂＝2～5。

More preferably, the addition amount of the photoinitiator in the step 3) accounts for 3-5% of the total mass of the reactants.

The invention also aims to provide application of the epoxy-based organic silicon release agent in preparation of release paper or release film.

Preferably, the preparation of the release film by using the epoxy organosilicon release agent comprises the following specific steps: uniformly coating the epoxy-based organosilicon release agent on a substrate, placing the coated substrate in a UV light instrument, irradiating by using UV light with the wavelength of 320-410 nm, and curing by using the UV light to obtain the epoxy-based organosilicon release film.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the organic silicon release agent prepared by the invention has the advantages of light stripping force, high temperature resistance and oxidation resistance, and the prepared organic silicon release agent is also rapidly cured under the irradiation of UV light, and has the advantages of stable and excellent release performance.

(2) The preparation method of the invention is curing film forming at normal temperature, and the film forming by ultraviolet curing is faster than the film forming by heat curing, thereby reducing the complexity of reaction steps and structures and improving the preparation efficiency.

(3) The organosilicon release agent prepared by the preparation method has excellent oxidation resistance, and solves the problem of easy oxygen inhibition in the prior art; short-chain silicone oil added in the curing process is used for end sealing, the molecular weight of the prepared release agent is controllable, and the problem of poor release effect caused by overhigh molecular weight in the prior art is solved; the UV light curing is adopted in the curing process of the coating, the preparation process is mild, and the problem of high-temperature energy consumption in the prior art is solved.

Drawings

FIG. 1 is an infrared spectrum of an epoxy-based silicone release agent I of an example;

FIG. 2 is an infrared spectrum of a diepoxy organosilicon release agent II of the example;

FIG. 3 is an infrared spectrum of triepoxy-containing organosilicon release agent III of the example;

FIG. 4 is an infrared spectrum of a tetracycloxy organosilicon release agent IV according to the example;

FIG. 5 is an infrared spectrum of the pentacyclic epoxy group organosilicon release agent V of the example.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

The catalyst used in all the examples of the present application is Karstedt catalyst, and for the convenience of storage, a small amount of toluene is used for dilution and activation, and since the catalyst only plays a catalytic role and does not participate in the compound construction in the present invention, the addition amount is small, and the amount of toluene is more diluted, the reaction can be regarded as a solvent-free reaction.