阅读说明：本技术 一种电子束固化有机硅离型剂及其制备方法 (Electron beam curing organic silicon release agent and preparation method thereof ) 是由 沈树人 程新 高洁 胡国文 朱晓明 韩小兵 胡鹏 姬柳迪 于 2021-07-20 设计创作，主要内容包括：本发明提供了一种电子束固化有机硅离型剂及其制备方法,属于离型剂技术领域。有机硅离型剂的组分包括羟基硅油、含硅丙烯酸酯、阻聚剂、含氟脂肪醇、有机金属催化剂、酸催化剂、份、活性稀释剂。按重量比称取原料,然后将羟基硅油、含硅丙烯酸酯单体、阻聚剂、含氟脂肪醇、有机金属催化剂加入反应容器中进行缩合反应,反应完全后加入酸催化剂进行水解缩聚,减压蒸馏后冷却至室温,加入活性稀释剂搅拌均匀得到电子束固化的有机硅离型剂。本发明的有机硅离型剂生产工艺简单、产品无溶剂,固化时间短、能耗低,氟硅单元的引入提高了离型效果,抗水油污染能力强,耐热性好,可用于各种离型纸及离型膜的生产。(The invention provides an electron beam curing organic silicon release agent and a preparation method thereof, belonging to the technical field of release agents. The components of the organic silicon release agent comprise hydroxyl silicone oil, silicon-containing acrylate, a polymerization inhibitor, fluorine-containing aliphatic alcohol, an organic metal catalyst, an acid catalyst, a component and an active diluent. Weighing raw materials according to a weight ratio, then adding hydroxyl silicone oil, a silicon-containing acrylate monomer, a polymerization inhibitor, fluorine-containing aliphatic alcohol and an organic metal catalyst into a reaction container for condensation reaction, adding an acid catalyst after the reaction is completed for hydrolysis polycondensation, cooling to room temperature after reduced pressure distillation, adding an active diluent, and uniformly stirring to obtain the electron beam cured organic silicon release agent. The organic silicon release agent has the advantages of simple production process, no solvent in the product, short curing time, low energy consumption, capability of resisting water and oil pollution and good heat resistance, improves the release effect by introducing the fluorine-silicon unit, and can be used for producing various release papers and release films.)

1. The electron beam curing organic silicon release agent is characterized by comprising, by weight, 100 parts of hydroxyl silicone oil, 10-50 parts of silicon-containing acrylate, 0.1-1 part of polymerization inhibitor, 1-10 parts of fluorine-containing aliphatic alcohol, 0.1-1 part of organic metal catalyst, 0.1-1 part of acid catalyst and 20-200 parts of active diluent.

2. The electron beam curing silicone release agent according to claim 1, wherein the hydroxy silicone oil has a hydroxyl group content of 4% to 12% and a viscosity of 20 to 2000 mPa-s.

3. The electron beam curing silicone release agent according to claim 1, wherein the silicon-containing acrylate is γ -methacryloxypropyltrimethoxysilane.

4. The electron beam curing silicone release agent according to claim 1, wherein the polymerization inhibitor is one or more of hydroquinone, p-hydroxyanisole, 2-tert-butylhydroquinone.

5. The electron beam curing silicone release agent according to claim 1, wherein the fluorine-containing aliphatic alcohol is a mixture of one or more of pentafluoropropanol, heptafluorobutanol, nonafluoropentanol, and undecafluorohexanol.

6. The electron beam curing silicone release agent according to claim 1, wherein the organic metal catalyst is one of stannous octoate, dibutyltin dilaurate, tetrabutyl titanate, and tetraisopropyl titanate.

7. The electron beam curing silicone release agent according to claim 1, wherein the acid catalyst is one of sulfuric acid and hydrochloric acid, and the mass fraction is 0.5% -10%.

8. The electron beam curing silicone release agent of claim 1, wherein the reactive diluent is a mixture of one or more of isobornyl acrylate, isooctyl acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate.

9. A method of preparing the electron beam curable silicone release agent of any one of claims 1-8, comprising the steps of:

1) weighing 100 parts of hydroxyl silicone oil, 10-50 parts of silicon-containing acrylate, 0.1-1 part of polymerization inhibitor, 1-10 parts of fluorine-containing aliphatic alcohol, 0.1-1 part of organic metal catalyst, 0.1-1 part of acid catalyst and 20-200 parts of active diluent according to the weight ratio;

2) adding hydroxyl silicone oil, a silicon-containing acrylate monomer, a polymerization inhibitor, fluorine-containing aliphatic alcohol and an organic metal catalyst into a reaction vessel for condensation reaction, adding an acid catalyst for hydrolytic polycondensation after complete reaction, cooling to room temperature after reduced pressure distillation, adding an active diluent, and uniformly stirring to obtain the electron beam cured organic silicon release agent.

10. The preparation method of the electron beam curing organic silicon release agent according to claim 9, characterized in that the condensation reaction temperature is 40-80 ℃ and the time is 1-4 h;

the hydrolytic polycondensation temperature is 60-90 ℃ and the time is 3-8 h;

the reduced pressure distillation temperature is 80-150 ℃, and the time is 0.5-2 h.

Technical Field

The invention belongs to the technical field of release agents, and relates to an electron beam curing organic silicon release agent and a preparation method thereof.

Background

The release agent is also called as an isolating agent, is a protective film which can prevent the adhesion of the adhesive and can protect the adhesive from being polluted, mainly comprises addition type and condensation type organic silicon resin, and is more and more widely applied to the adhesive sticker industry. With the development of science and technology, the requirements on the release agent and the technology thereof are higher and higher, such as simple production process, no solvent in the product, short curing time, low energy consumption, good release effect, strong capability of resisting water and oil pollution, good heat resistance and the like.

The release agent is mainly divided into a traditional thermosetting release agent and a modern radiation curing release agent according to a curing mode. The conventional thermosetting release agent mainly has the following problems: 1. the traditional addition type and condensation type organic silicon release agents are required to be cured at a higher temperature (more than 100 ℃), so that the energy consumption is high, paper is easy to deform and curl at a high temperature, water needs to be supplemented, and the process is complex; 2. in the traditional thermosetting production process, in order to achieve complete curing, longer curing time is needed, so that the production efficiency is low; 3. the traditional thermosetting organic silicon release agent is generally high in viscosity, a large amount of organic solvent is added to reduce the viscosity in order to improve the coating efficiency, and the large amount of solvent is directly discharged into the air in the thermosetting process, so that the environmental pollution is serious.

The radiation curing mold release agent is divided into an ultraviolet curing mold release agent and an electron beam curing mold release agent. Uv curable release agents also have some disadvantages: 1. expensive photoinitiator is needed to induce the curing of the photosensitive resin, so that the production cost is greatly increased, and the risk of initiator migration exists; 2. the ultraviolet curing equipment can age rapidly along with the lapse of time, the curing power is reduced, and the quality stability is poorer; 3. the thickness of ultraviolet light penetration is limited, and the curing effect of a thick coating or filled system is poor; 4. the ultraviolet light solidified release agent coating has poor aging resistance and irradiation performance.

The electron beam curing is a novel curing process without heating, and the electron beam has extremely strong penetrating power (more than 1 mm), so the curing is more thorough, 100 percent of curing is carried out to form a film, and no micromolecules are left; the curing speed is high, and the production efficiency is high; meanwhile, due to the high crosslinking density, a coating with excellent heat resistance and good oil water pollution resistance effect can be obtained. Therefore, a release agent suitable for electron beam curing would also bring corresponding value.

Disclosure of Invention

The first purpose of the present invention is to provide an electron beam curing silicone release agent, which aims to solve the technical problem of obtaining an environment-friendly release agent without solvent.

The purpose of the invention can be realized by the following technical scheme: the electron beam curing organic silicon release agent is characterized by comprising, by weight, 100 parts of hydroxyl silicone oil, 10-50 parts of silicon-containing acrylate, 0.1-1 part of polymerization inhibitor, 1-10 parts of fluorine-containing aliphatic alcohol, 0.1-1 part of organic metal catalyst, 0.1-1 part of acid catalyst and 20-200 parts of active diluent.

Furthermore, the hydroxyl content of the hydroxyl silicone oil is 4% -12%, and the viscosity is 20-2000 mPa.

Further, the silicon-containing acrylate is gamma-methacryloxypropyltrimethoxysilane.

Further, the polymerization inhibitor is one or a mixture of more of hydroquinone, p-hydroxyanisole and 2-tert-butylhydroquinone.

Further, the fluorine-containing aliphatic alcohol is one or a mixture of more of pentafluoropropanol, heptafluorobutanol, nonafluoropentanol and undecanohexanol;

further, the organic metal catalyst is one of stannous octoate, dibutyltin dilaurate, tetrabutyl titanate and tetraisopropyl titanate;

further, the acid catalyst is one of sulfuric acid and hydrochloric acid, and the mass fraction of the acid catalyst is 0.5-10%;

further, the reactive diluent is one or a mixture of more of isoborneol acrylate, isooctyl acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate and trimethylolpropane triacrylate.

The second objective of the present invention is to provide a method for preparing an electron beam cured silicone release agent, which aims to solve the technical problem of preparing a release agent suitable for electron beam curing by a simplified process.

The purpose of the invention can be realized by the following technical scheme: the preparation method of the electron beam curing organic silicon release agent is characterized by comprising the following steps:

1) weighing hydroxyl silicone oil, silicon-containing acrylate, a polymerization inhibitor, fluorine-containing aliphatic alcohol, an organic metal catalyst, an acid catalyst and an active diluent according to the weight ratio;

2) adding hydroxyl silicone oil, a silicon-containing acrylate monomer, a polymerization inhibitor, fluorine-containing aliphatic alcohol and an organic metal catalyst into a reaction vessel for condensation reaction, adding an acid catalyst for hydrolytic polycondensation after complete reaction, cooling to room temperature after reduced pressure distillation, adding an active diluent, and uniformly stirring to obtain the electron beam cured organic silicon release agent.

Further, the condensation reaction temperature is 40-80 ℃, and the time is 1-4 h;

further, the hydrolytic polycondensation temperature is 60-90 ℃, and the time is 3-8 h;

further, the reduced pressure distillation temperature is 80-150 ℃, and the time is 0.5-2 h.

Compared with the prior art, the invention has obvious technical progress and the specific beneficial effects as follows:

(1) the electron beam curing organosilicon release agent does not contain an organic solvent, is 100 percent crosslinked, cured and formed into a film, does not cause environmental pollution and product pollution caused by solvent volatilization and residue, and has excellent temperature resistance;

(2) according to the electron beam curing organic silicon release agent, the organic fluorine unit is introduced into the structure, so that the release effect and the oil-water pollution resistance are greatly improved;

(3) the organic silicon release agent can be used for an electron beam curing process, and has the advantages of high curing speed, high energy utilization rate and no need of a photoinitiator, so that the production efficiency is greatly improved, the energy consumption is greatly reduced, and the production cost is also greatly reduced.

(4) Simple process, mild reaction condition and relatively short preparation time.

Detailed Description

The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.

Example 1

An electron beam curing organic silicon release agent is prepared from the following raw materials in parts by weight: 100 parts of hydroxyl silicone oil (the hydroxyl content is 12 percent, and the viscosity is 20 mPa.s), 50 parts of gamma-methacryloxypropyltrimethoxysilane, 0.1 part of hydroquinone, 1 part of pentafluoropropanol, 0.1 part of stannous octoate, 1 part of 10 percent hydrochloric acid and 200 parts of isoborneol acrylate.

The preparation method of the electron beam curing organic silicon release agent comprises the following steps:

adding 100 parts of hydroxyl silicone oil, 50 parts of gamma-methacryloxypropyltrimethoxysilane, 0.1 part of hydroquinone, 1 part of pentafluoropropanol and 0.1 part of stannous octoate into a reaction vessel, carrying out condensation reaction for 4 hours at 40 ℃, adding 1 part of 10% sulfuric acid after the reaction is completed, carrying out hydrolytic polycondensation for 8 hours at 60 ℃, carrying out reduced pressure distillation for 2 hours at 80 ℃, cooling to room temperature, adding 200 parts of isoborneol acrylate, and uniformly stirring to obtain the electron beam cured organosilicon release agent.

Example 2

An electron beam curing organic silicon release agent is prepared from the following raw materials in parts by weight: 100 parts of hydroxyl silicone oil (the hydroxyl content is 4 percent, and the viscosity is 2000mPa & s), 10 parts of gamma-methacryloxypropyltrimethoxysilane, 1 part of p-hydroxyanisole, 10 parts of heptafluorobutanol, 1 part of dibutyltin dilaurate, 0.1 part of 0.5 percent sulfuric acid, and 20 parts of isooctyl acrylate.

The preparation method of the electron beam curing organic silicon release agent comprises the following steps:

adding 100 parts of hydroxyl silicone oil, 10 parts of gamma-methacryloxypropyltrimethoxysilane, 1 part of p-hydroxyanisole, 10 parts of heptafluorobutanol and 1 part of dibutyltin dilaurate into a reaction vessel, carrying out condensation reaction for 1 hour at 80 ℃, adding 1 part of 0.5% sulfuric acid after complete reaction, carrying out hydrolytic polycondensation for 3 hours at 90 ℃, carrying out reduced pressure distillation for 0.5 hour at 150 ℃, cooling to room temperature, adding 20 parts of isooctyl acrylate, and uniformly stirring to obtain the electron beam cured organic silicon release agent.

Example 3

An electron beam curing organic silicon release agent is prepared from the following raw materials in parts by weight: 100 parts of hydroxy silicone oil (8% hydroxyl content, viscosity 1000 mPa. multidot.s), 20 parts of gamma-methacryloxypropyltrimethoxysilane, 0.3 part of each of p-hydroxyanisole and 2-tert-butylhydroquinone, 2 parts of each of nonafluoropentanol and undecafluorohexanol, 0.5 part of tetrabutyl titanate, 0.5 part of 5% sulfuric acid, and 50 parts of each of tripropylene glycol diacrylate and hexanediol diacrylate.

The preparation method of the electron beam curing organic silicon release agent comprises the following steps:

100 parts of hydroxyl silicone oil, 20 parts of gamma-methacryloxypropyl trimethoxy silane, 0.3 part of each of p-hydroxyanisole and 2-tert-butyl hydroquinone, 2 parts of each of nonafluoropentanol and undecyl hexanol and 0.5 part of tetrabutyl titanate are added into a reaction vessel, condensation reaction is carried out for 2 hours at 60 ℃, 0.5 part of 5% sulfuric acid is added after the reaction is completed, hydrolytic polycondensation is carried out for 5 hours at 80 ℃, reduced pressure distillation is carried out for 1 hour at 120 ℃, then cooling is carried out to room temperature, 50 parts of each of tripropylene glycol diacrylate and hexanediol diacrylate are added, and the mixture is uniformly stirred to obtain the electron beam cured organosilicon release agent.

Example 4

An electron beam curing organic silicon release agent is prepared from the following raw materials in parts by weight: 100 parts of hydroxyl silicone oil (the hydroxyl content is 8 percent, and the viscosity is 1000 mPa.s), 30 parts of gamma-methacryloxypropyltrimethoxysilane, 0.5 part of hydroquinone, 2 parts of nonafluoropentanol, 0.5 part of tetraisopropyl titanate, 0.5 part of 5 percent sulfuric acid and 100 parts of polyethylene glycol diacrylate.

The preparation method of the electron beam curing organic silicon release agent comprises the following steps:

100 parts of hydroxyl silicone oil, 30 parts of gamma-methacryloxypropyl trimethoxy silane, 0.5 part of hydroquinone, 2 parts of nonafluoropentanol and 0.5 part of tetraisopropyl titanate are added into a reaction vessel to carry out condensation reaction for 2 hours at 60 ℃, 0.5 part of 5 percent sulfuric acid is added after the reaction is completed, hydrolysis and polycondensation are carried out for 5 hours at 80 ℃, reduced pressure distillation is carried out for 1 hour at 120 ℃, then the mixture is cooled to room temperature, 100 parts of polyethylene glycol diacrylate is added, and the mixture is uniformly stirred to obtain the electron beam cured organic silicon release agent.

Example 5

An electron beam curing organic silicon release agent is prepared from the following raw materials in parts by weight: 100 parts of hydroxyl silicone oil (the hydroxyl content is 8 percent, and the viscosity is 1000 mPa.s), 40 parts of gamma-methacryloxypropyltrimethoxysilane, 0.5 part of hydroquinone, 2 parts of nonafluoropentanol, 0.5 part of tetrabutyl titanate, 0.5 part of 3 percent sulfuric acid, and 100 parts of trimethylolpropane triacrylate.

The preparation method of the electron beam curing organic silicon release agent comprises the following steps:

adding 100 parts of hydroxyl silicone oil, 40 parts of gamma-methacryloxypropyltrimethoxysilane, 0.5 part of hydroquinone, 2 parts of nonafluoropentanol and 0.5 part of tetrabutyl titanate into a reaction vessel, carrying out condensation reaction at 60 ℃ for 2 hours, adding 0.5 part of 3% sulfuric acid after complete reaction, carrying out hydrolytic polycondensation at 80 ℃ for 5 hours, carrying out reduced pressure distillation at 120 ℃ for 1 hour, cooling to room temperature, adding 100 parts of trimethylolpropane triacrylate, and uniformly stirring to obtain the electron beam cured organosilicon release agent.

Comparative example 1:

as a comparison of example 5, in comparative example 1, no fluorine-containing aliphatic alcohol was added, and the other steps were the same. Adding 100 parts of hydroxyl silicone oil, 40 parts of gamma-methacryloxypropyltrimethoxysilane, 0.5 part of hydroquinone, 2 parts of nonafluoropentanol and 0.5 part of tetrabutyl titanate into a reaction vessel, carrying out condensation reaction at 60 ℃ for 2 hours, adding 0.5 part of 3% sulfuric acid after complete reaction, carrying out hydrolytic polycondensation at 80 ℃ for 5 hours, carrying out reduced pressure distillation at 120 ℃ for 1 hour, cooling to room temperature, adding 100 parts of trimethylolpropane triacrylate, and uniformly stirring to obtain the electron beam cured organosilicon release agent.

Comparative example 2:

comparative example 2 is a commercially available conventional two-component silicone release agent, which was coated on a coating of 60g/m after mixing the two components uniformly²On glassine base paper, the coating weight is 1.0g/m²Then, it was baked at 130 ℃ for 30 seconds, and after curing, a test for correlation properties was performed.

The main performance indexes and the determination method of the invention are as follows:

the silicone release agents of the above examples and comparative example 1 were applied to 60g/m²On glassine base paper, the coating weight is 1.0g/m²And irradiating with 5KGy electron beam dose after coating, and testing the correlation performance after curing.

(1) And (3) testing the peeling force: sticking a standard adhesive tape on the surface of the cured release paper, and measuring the stripping force by adopting a stripping tester at the tensile speed of 300mm/min and a 180-degree stripping method;

(2) and (3) testing heat resistance: placing the cured release paper in an oven at 180 ℃ for 1h, and observing whether the coating is yellow;

(3) and (3) solvent resistance test: and (3) dipping absorbent cotton in toluene or ethyl acetate respectively, repeatedly wiping the surface of the cured release paper for 30 times, and observing whether the coating swells or dissolves.

TABLE 1 Release agent Performance test results

As can be seen from Table 1, in comparative example 1, since no fluorine-containing unit is added, the peeling force is large, and the release effect is poor; the comparative example 2 is the traditional thermosetting organic silicon release agent, the stripping force is the largest, and the release effect is the worst; due to low crosslinking degree and poor release effect, the product has poor heat resistance and generates swelling and yellowing. Compared with the comparative examples 1 and 2, the electron beam curing organic silicon release agent has the stripping force within the range of 1-4g/25mm, and has very good release effect. In addition, the paint is not yellowed at 180 ℃, has excellent temperature resistance, is not swelled or dissolved after being wiped by toluene and ethyl acetate, and has excellent oil stain resistance.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.