CN110183664B

CN110183664B - Preparation method and application of ultraviolet-curing methacrylate-containing silicone oil

Info

Publication number: CN110183664B
Application number: CN201910359411.2A
Authority: CN
Inventors: 林加晖; 薛小强; 蒋必彪; 黄文艳; 杨宏军; 蒋其民; 江力; 孙佳悦
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2019-04-30
Filing date: 2019-04-30
Publication date: 2021-09-28
Anticipated expiration: 2039-04-30
Also published as: CN110183664A

Abstract

The invention relates to a preparation method and application of ultraviolet light curing type methacrylate-containing silicone oil, firstly, synthesizing a methacrylate structure organic matter containing a mercapto structure, namely methacrylic acid-3-mercaptopropionyloxy ethyl ester; secondly, reacting with the polymethylsiloxane containing epoxy at the end group, under the catalysis of organic base, carrying out ring-opening click chemical reaction on propylene oxide by sulfydryl efficiently and quickly, generating no cross-linking side reaction, controlling the reaction, and preparing the polymethylsiloxane (PSi-MMA) containing methacrylate structure at the end group, wherein the grafting rate of the methacrylate is up to more than 95%; the composite photoinitiator is coated on a substrate and is cured by ultraviolet light, the film is rapidly cured at room temperature to form a film, and the film is clean and pollution-free, and has excellent release effect: the residual adhesion rate of the standard adhesive tape is higher than 92%, the release force is stable at about 15-30 g/in, and the adhesive tape is a rapid organic silicon photocuring system which is free of solvent, metal catalyst and high-temperature curing.

Description

Preparation method and application of ultraviolet-curing methacrylate-containing silicone oil

Technical Field

The invention belongs to the field of polymer material science, and particularly relates to a preparation method of an Ultraviolet (UV) curing type silicone oil material, which can be applied to a photo-curing release agent material.

Background

The polymethyl siloxane is called silicone oil for short, the main chain structure is connected by a silicon-oxygen bond, the polymethyl siloxane has excellent flexibility, simultaneously shows high and low temperature resistance, is used in a wider temperature range, has the characteristics of weather resistance and high and low temperature resistance, and has the performances of excellent barrier property, low surface energy, surface tension, corrosion resistance, electric insulation, ozone resistance, water resistance, flame resistance, physiological inertia and the like compared with the conventional polymer, and is widely applied to various industries of national economy such as aerospace, release materials, electronics and electricity, chemical machinery, medical sanitation, transportation and the like.

Traditional silicone oil is cured and formed through a high-efficiency catalyst at high temperature, however, from the perspective of energy conservation and environmental protection, the traditional curing mode is slow in curing speed, high in energy consumption and low in curing efficiency, even the solvent is volatilized in the curing process, and micromolecular organic matters are volatilized to pollute the environment, and the residue of the metal catalyst influences the product performance and the application point, so that the application and popularization of the organic silicon are limited to a great extent.

Ultraviolet (UV) curing is a new energy-saving and environment-friendly technology, has the advantages of high curing speed, uniform normal-temperature curing, energy conservation, high efficiency, greatly improved curing efficiency, pollution reduction, environmental friendliness and the like, is very suitable for forming films on heat-sensitive substrates or devices, and has the characteristics of ultraviolet localization and photoetching of semiconductor circuits, so that photocuring is a vigorously advocated energy-saving and environment-friendly curing method. Therefore, the side chain or the tail end of the polymethylsiloxane is introduced into the photosensitive functional group to be crosslinked and cured under the irradiation of ultraviolet light, so that the defect of high-temperature curing of the traditional silicone oil is overcome, and the advantages of high efficiency, rapid curing and forming, cleanness, environmental protection, energy conservation and the like are embodied, and the traditional silicon-based material has the advantages of temperature resistance, weather resistance, electric insulation, low surface tension, low surface energy and the like. The conventional photosensitive group is usually in a (methyl) acrylate structure, a photoinitiator is added, a small-molecule volatile monomer is not required to be added, the photoinitiator is excited to form a free radical under the radiation of ultraviolet light, the free radical addition polymerization of the (methyl) acrylate is initiated, the (methyl) acrylate is finally crosslinked to form a film, the system has certain antioxidant polymerization capacity, the synthesis method and the process are simple, the preparation cost is low, the method is particularly applied to the streamlined and rapid manufacturing of release films of different base materials (such as paper, PP, PE, PET and the like), the advantages of organosilicon are retained after curing, the film-forming property, the color retention property, the luster and the bonding property of the acrylate are good, the application and the popularization of the organosilicon are improved, and the industries such as coating, paint, leather assistant, packaging and the like.

At present, a plurality of methods are used for preparing early acrylate polymethylsiloxane containing (methyl) acrylate structures, such as a method for preparing dichlorosilane and hydroxyethyl acrylate (HEA) in polymethylsiloxane through a hydrolysis condensation reaction under the catalysis of alkali, but the modified polysiloxane contains Si-O-C bonds sensitive to humidity, is easy to hydrolyze and has poor stability, and the acrylate structures are easy to dissociate and inactivate, so that the acrylate esterified polymethylsiloxane with the Si-C structure with high stability needs to be synthesized, and the main synthesis methods are a hydrosilylation method, an esterification method and a dealcoholization method. The silylhydride-containing polymethylsiloxanes were reacted directly with symmetrical bisacrylates by hydrosilylation (oestereich S, Struck S. macromol. symp., 2002, 187(1), 333.), H)₂PtO₆ 6H₂Under the catalysis of O, acrylate-based polysiloxane is obtained, and because the diacrylate has the same activity, cross-linking reaction between polymer chains can occur in the addition reaction process, so that the influence is large. Preparing acrylated polysiloxane by an esterification method by using epoxy terminated polydimethylsiloxane and acrylic acid under the catalysis of a catalyst (Carter G R, Watson S L, Pines A N, US 4293678, 1981.); esterification of hydroxyalkyl-terminated polymethylsiloxanes with acrylic acid to give acrylated polysiloxanes (Hockemeyer F, Preiner G. US 4554339, 1985.); he Hua, etc. uses chloropropylpolysiloxane and hydroxypropyl acrylate to react to synthesize acrylate-esterified polysiloxane, and uses it as isolating agent to research ultraviolet light solidifying property and its antisticking property (He Hua, Taoyongjie, Libingo, adhesive, 2)005, 26(6),7.). The activity of the esterification reaction limits the low esterification efficiency, and the grafting rate of the acrylic ester influences the application of the organic silicon.

With the development of science and technology, people have more and more extensive requirements on a polymethylsiloxane rapid curing system, the requirements are higher and higher, the time is greatly saved, the process efficiency is improved, and the product yield and the quality are exponentially improved, for example, when the polymethylsiloxane rapid curing release film is used as a release material, a release film prepared by curing silicone oil has the residual adhesion rate of more than 90 percent on a standard adhesive tape, and has the requirements of good adhesive force on different base materials and the like. Therefore, the grafting efficiency of the acrylate is improved, the preparation cost is reduced, and the popularization of the UV curing type polymethyl siloxane is effectively improved.

Disclosure of Invention

The invention aims to provide a preparation method of end-methacrylate-esterified polymethylsiloxane with excellent performance, high grafting rate and low cost. The obtained end methacrylate-esterified polymethylsiloxane has the advantages of simple preparation, low preparation cost, convenient use, high methacrylate grafting rate and high activity, is an efficient and mild controllable preparation method, has short ultraviolet curing and forming time, does not need to prepare a silicone oil modified photoinitiator in a complicated way by using the photoinitiator, selects a low-price commercial compound photoinitiator, adopts a standard adhesive tape to obtain a cured organic silicon film material, has the residual adhesion rate of more than 92 percent, has the release force of being stable at about 15-30 g/in, has the advantages of high temperature resistance, good weather resistance, good electrical insulation, low surface tension and the like, and is widely applied to industries of release coatings, leather additives, packaging and the like.

The invention adopts the following technical scheme:

an Ultraviolet (UV) curable end methacrylate structured polymethylsiloxane (PSi-MMA) has the general structural formula of formula [1 ]:

[1] chemical Structure of PSi-MMA

In the formula [1 ]: n is 10-200, and the molecular weight is 1200-15000; wherein n is an integer.

The PSi-MMA is prepared by quickly and efficiently carrying out epoxy ring-opening click chemical reaction on a prepared methyl acrylate compound B containing sulfydryl and silicone oil with an end epoxy structure under the catalysis of organic base, and the reaction equation is [2]:

[2] reaction equation for PSi-MMA

The raw material A is epoxy-terminated silicone oil, is self-made, and in the structure, n can be any integer, can be set to be 10-200, and has the molecular weight of 1000-15000.

The raw material B is a methacrylate compound containing sulfydryl, and methacrylic acid-3-mercaptopropionyloxyethyl ester. The purity is more than 98%.

In the reaction process of epoxy ring-opening Click Chemistry (Click Chemistry), the mercapto-epoxy ring-opening reaction is a rapid and efficient normal-temperature reaction, belongs to Click Chemistry (Click Chemistry), is mild and thorough in reaction, does not generate a cross-linking side reaction, can be thorough in reaction by adding B with the same molar group without adding excessive B, and is controllable in reaction, and the grafting ratio of methacrylate is up to more than 95%.

The epoxy ring-opening Click Chemistry (Click Chemistry) reaction condition is that the organic base is usually triethylamine, triphenylphosphine, triethanolamine, 2, 4, 6 tri (dimethylamino methyl) phenol (DMP-30) and the like, the reaction is carried out at normal temperature, the solvent can be tetrahydrofuran, acetone, ethyl acetate, toluene, xylene, butanone and other good solvents, the reaction time is 3 hours, the post-treatment is carried out by reduced pressure rotary evaporation, the solvent can be recycled, and the whole process flow is simple and controllable.

The preparation of the polymethyl siloxane material (PSi-MMA) with the end group containing the methacrylate structure has extremely high grafting rate of the methacrylate, and the grafting rate is more than 94%. In the presence of a photoinitiator, Ultraviolet (UV) irradiation is performed at normal temperature for rapid curing molding, or the film is coated on a film for film formation, the curing time is 1-5 seconds, the photocuring reaction has the advantages of rapid curing, uniform curing, room-temperature curing, energy conservation, high efficiency, environmental friendliness and the like, and the prepared organic silicon film material has the advantages of high temperature resistance, good weather resistance, good electrical insulation, low surface tension and the like, and is widely applied to industries such as release coatings, leather additives, packaging and the like.

The photoinitiator is a conventional initiator sold in the market, has good compatibility with PSi-MMA, further improves the photoinitiation activity and efficiency through a compound photoinitiator, does not need to prepare the silicone oil modified photoinitiator in a complicated way, greatly simplifies the preparation method, reduces the preparation cost of the product, and the compound photoinitiator is as follows: 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) and the like to prepare a high-efficiency organosilicon photoinitiator, and other photoinitiators can also be applied to the technology.

The polymethyl siloxane material with the end group containing the methacrylate structure is subjected to ultraviolet curing film forming to obtain the release film, and the release film has excellent low surface energy and excellent release effect: the residual adhesion rate of the standard adhesive tape is higher than 92%, the release force is stable at about 15-30 g/in, and the adhesive tape is a rapid organic silicon photocuring system which is free of solvent, metal catalyst and high-temperature curing.

Drawings

FIG. 1 is a high performance liquid chromatogram of purified 3-mercaptopropionyloxyethyl methacrylate.

FIG. 2 NMR spectrum of 3-mercaptopropionyloxyethyl methacrylate.

FIG. 3 is an infrared contrast graph of a polymethylsiloxane material with a terminal epoxy group polymethylsiloxane and a terminal methacrylate structure (PSi-MMA) (A is the terminal epoxy group polymethylsiloxane, and B is PSi-MMA 01).

FIG. 4 shows the nuclear magnetic spectrum of epoxy-terminated polymethylsiloxane.

FIG. 5 is a nuclear magnetic spectrum of a polymethyl siloxane material with a terminal methacrylate structure (PSi-MMA 01).

Fig. 6 is a contact angle test chart of thermal printing paper.

FIG. 7 is a contact angle test chart of UV-cured film formation of polymethylsiloxane with terminal methacrylate structure (PSi-MMA 01) coated on a thermal printing paper substrate.

Fig. 8, a diagram of a backing-less thermally printed label.

Detailed Description

The present invention will be further described with reference to the following examples.

Example 1

The synthesis of the methacrylate compound containing sulfhydryl and methacrylic acid-3-mercaptopropionyloxyethyl ester is carried out by esterification of hydroxyethyl methacrylate and mercaptopropionic acid, and the reaction equation is [3]:

[3] synthesis of 3-mercaptopropionyloxyethyl methacrylate

2-hydroxyethyl methacrylate (13.00 g; 0.10 mol), 3-mercaptopropionic acid (11.13 g; 0.105 mol), p-toluenesulfonic acid (1.00 g) as an esterification catalyst, hydroquinone (0.12 g) as a polymerization inhibitor, and benzene (15.00 mL) as a water-carrying agent were gradually added to a 250 mL three-necked flask. After being filled into a water separator, the three-mouth bottle is placed in an oil bath pot to be slowly heated to reflux, and the reaction is carried out for 8 hours at constant temperature. After the reaction is finished, the temperature is reduced to a product, 3% sodium bicarbonate dilute solution is washed for 3 times, distilled water is washed to be neutral, and anhydrous sodium sulfate is dried overnight. The solvent is removed by reduced pressure distillation, and after separation by a chromatographic silica gel column, 3-mercaptopropionyloxyethyl methacrylate (MPOEM) is obtained. FIG. 1 shows a high performance liquid of purified 3-mercaptopropionyloxyethyl methacrylateThe purity of the product after purification by a chromatographic silica gel column can be analyzed and obtained by a phase chromatogram map, and the purity of the product is as high as 98 percent. FIG. 2 is a drawing showing the preparation of 3-mercaptopropionyloxyethyl methacrylate¹H-NMR spectrum. The proton of the structure corresponds to the nuclear magnetic signal peak one by one, and the integral ratio is consistent with the proton ratio, which indicates that the product is the target product.

Example 2

Synthesis of a polymethyl siloxane material (PSi-MMA) with a terminal methacrylate structure.

The structure of the epoxy-terminated polymethoxysiloxane is shown as a formula [2], the self-made epoxy-terminated polymethoxysiloxane is shown in figure 4, the nuclear magnetic spectrogram of the epoxy-terminated polymethoxysiloxane is shown in figure 4, the structure corresponds to nuclear magnetic proton peaks one by one, n =14 and the molecular weight is 1300 through integral calculation.

To a 250 mL three-necked flask equipped with a constant pressure base funnel and a magnetic stirrer were added epoxy-terminated polymethoxysiloxane (13.00 g, 0.01 mol), triethylamine (0.08 g, 0.0008 mol) and acetone (50 mL) as a solvent, respectively. Under normal temperature stirring, dropwise adding an acetone solution (10 mL) of 3-mercaptopropionyloxyethyl methacrylate (4.36 g, 0.02 mol) into the reaction solution, wherein the mass ratio of the epoxy-terminated polymethoxysiloxane to the 3-mercaptopropionyloxyethyl methacrylate is 1: and 2, dropwise adding epoxy-terminated polymethoxysiloxane for 10min, continuously reacting for 1 h, concentrating under reduced pressure to obtain a solution of 30 mL after the reaction is finished, precipitating with ethanol, removing upper ethanol liquid layer by layer, continuously purifying for 3 times, removing small molecules, and drying to obtain the pure polymethoxysiloxane material (PSi-MMA) with a terminal methacrylate structure. FIG. 5 is a nuclear magnetic spectrum of PSi-MMA, which shows that the PSi-MMA structure and nuclear magnetic proton peaks correspond to each other by nuclear magnetic signals, and the integral ratio is also consistent, and the nuclear magnetic integral calculation shows that the grafting rate of the methacrylate reaches 98% and the molecular weight is 1700. Meanwhile, FIG. 3 is a graph showing the comparison of infrared spectra of epoxy-terminated polymethoxysiloxane and PSi-MMA, and the comparison shows that PSi-MMA contains 1731 cm^-11406 cm of the vibration peak of the ester of (1)^-1The signal is a double bond vibration peak, which shows that the methacrylate structure is linked on the end group of the polymethylsiloxane, so that the PSi-MMA, the mark PSi-MMA01, is successfully prepared, the grafting rate reaches 98 percent, the target product is efficiently and quickly prepared, therefore,excessive methacrylic acid-3-mercaptopropionyloxyethyl ester is not required to be added additionally, side reactions such as crosslinking and the like are not generated in the process, and epoxy-terminated polymethoxysiloxane and PSi-MMA are prepared simply, mildly and efficiently at room temperature.

Example 3

In contrast to example 2, the molecular weight of the epoxy-terminated polymethoxysiloxane was 2500, n = 30.

Under the condition of not changing other conditions of example 2, the mass of the epoxy-terminated polymethoxysiloxane and the mass of the 3-mercaptopropionyloxyethyl methacrylate in the preparation process are respectively as follows: 25.0 g and 4.36 g, the solvent dosage is unchanged, tetrahydrofuran, ethyl acetate, toluene, xylene, butanone and the like can be used for replacing acetone, the operation process is unchanged, nuclear magnetic spectrum and infrared characterization prove that the PSi-MMA is successfully prepared, the molecular weight is 2900, and the grafting rate of methacrylate reaches 97%. The label PSi-MMA 02.

Example 4

Different from the example 3, the catalyst triethylamine is changed into triphenylphosphine.

Under the condition of not changing other conditions of example 3, the triethylamine is changed into triphenylphosphine, the solvent dosage is unchanged, tetrahydrofuran, ethyl acetate, toluene, xylene, butanone and the like can be used for replacing acetone, the operation process is unchanged, a nuclear magnetic spectrum and infrared characterization prove that the PSi-MMA is successfully prepared, the molecular weight is 2900, and the grafting rate of the methacrylate reaches 95%. The label PSi-MMA 03.

Example 5

Different from the example 3, the catalyst triethylamine is changed into triethanolamine.

Under the condition of not changing other conditions of example 3, triethylamine is changed into triethanolamine, the using amount of the catalyst and the solvent is unchanged, tetrahydrofuran, ethyl acetate, toluene, xylene, butanone and the like can be used for replacing acetone, the operation process is unchanged, a nuclear magnetic spectrum and infrared characterization prove that the PSi-MMA is successfully prepared, the molecular weight is 2900, and the grafting rate of the methacrylate reaches 97%. The label PSi-MMA 04.

Example 6

Different from the example 3, the catalyst triethylamine is changed into 2, 4 and 6 tri (dimethylaminomethyl) phenol (DMP-30).

Under the condition of not changing other conditions of example 3, triethylamine is changed into 2, 4 and 6 tris (dimethylaminomethyl) phenol (DMP-30), the using amount of catalyst and solvent is unchanged, tetrahydrofuran, ethyl acetate, toluene, xylene, butanone and the like can be used for replacing acetone, the operation process is unchanged, a nuclear magnetic spectrum chart and infrared characterization prove that the PSi-MMA is successfully prepared, the molecular weight is 2900, and the grafting rate of methacrylate reaches 96%. The label PSi-MMA 05.

Example 7

And (3) synthesizing a polymethylsiloxane material (PSi-MMA) with a methacrylate structure in a side group.

In contrast to example 2, the molecular weight of the epoxy-terminated polymethoxysiloxane was 4700, n = 60.

Under the condition of not changing other conditions of example 2, the mass of the epoxy-terminated polymethoxysiloxane and the mass of the 3-mercaptopropionyloxyethyl methacrylate in the preparation process are respectively as follows: 23.5 g and 2.18 g, the solvent dosage is unchanged, tetrahydrofuran, ethyl acetate, toluene, xylene, butanone and the like can be used for replacing acetone, the operation process is unchanged, nuclear magnetic spectrum and infrared characterization prove that the PSi-MMA is successfully prepared, the molecular weight is 5100, and the grafting rate of methacrylate reaches 94%. The label PSi-MMA 06.

Example 8

In contrast to example 2, the molecular weight of the epoxy-terminated polymethoxysiloxane was 6900, n = 90.

Under the condition of not changing other conditions of example 2, the mass of the epoxy-terminated polymethoxysiloxane and the mass of the 3-mercaptopropionyloxyethyl methacrylate in the preparation process are respectively as follows: 34.5 g and 2.18 g, the solvent dosage is unchanged, tetrahydrofuran, ethyl acetate, toluene, xylene, butanone and the like can be used for replacing acetone, the operation process is unchanged, nuclear magnetic spectrum and infrared characterization prove that the PSi-MMA is successfully prepared, the molecular weight is 7300, and the grafting rate of methacrylate reaches 91%. The label PSi-MMA 07.

The preparation of other polymers of different molecular weights can be carried out with reference to example 2.

Example 9

And (3) carrying out ultraviolet curing reaction on the polymethyl siloxane material (PSi-MMA) with a terminal methacrylate structure.

Compounding a photoinitiator: 1-hydroxycyclohexyl phenyl ketone (184) and 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173) in a mass ratio of 1: 1 and mixing.

The PSi-MMA and the compound photoinitiator are mixed to be homogeneous according to the mass ratio of 100:1, inert gas such as high-purity nitrogen (99.99%) or argon is selected for bubbling to remove oxygen, the solution is coated on the surface of thermal printing paper in a rolling mode in the nitrogen atmosphere, ultraviolet irradiation is continuously carried out for 5 seconds, and a PSi-MMA film is prepared, wherein a non-backing paper thermal printing label graph is shown in figure 8, and the non-backing paper thermal printing label graph has an excellent release effect.

The PSi-MMA prepared in examples 2 to 8 was cured to form films, which were labeled PSi-MMA01 to PSi-MMA07, respectively. The cured film was tested for release properties, and fig. 6 and 7 are contact angle test charts of thermal printing paper and UV cured film formed by coating polymethylsiloxane with terminal methacrylate structure on the thermal printing paper substrate, where the thermal printing paper is 107^oThe paper of PSi-MMA02 is 114^o。

TABLE 1 Release parameters for PSi-MMA films

Table 1 shows the release performance results of PSi-MMA films of different structures under the same compound initiator, and shows that the release performance of PSi-MMA02 and PSi-MMA03The residual adhesion rate is the highest and is as high as 95 percent, the release force is about 21g/in, and the contact angle is 107 percent from before modification^oIs lifted to 114^oThe polymer films of other labels also meet the requirements, the PSi-MMA02 and PSi-MMA03 have the best preparation effect, the molecular weight is 2900, the structure is the most reasonable, and the catalysts for preparing the reaction system are triethylamine and triphenylphosphine, which are the optimal reaction conditions.

The embodiment 2-9 shows that the compound initiator can effectively initiate PSi-MMA, the effect difference is small, the molecular weight has little influence on the residual adhesion rate, the larger the molecular weight is, the more methyl siloxane content is, the smaller the release force is, the release films with different release forces can be prepared, the reaction condition is simple, and the popularization and the application are facilitated; PSi-MMA02 and PSi-MMA03 were most efficiently produced, the molecular weight was 2900, the most reasonable structure, examples 2 and 3 were the optimal reaction conditions, and the optimal amount of initiator was 1% of PSi-MMA by mass based on cost considerations.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be obvious to those skilled in the art that modifications may be made in the technical solutions described in the above embodiments, or some technical features may be equivalently replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. An ultraviolet curing type methacrylate-containing silicone oil PSi-MMA is characterized in that the structure of the methacrylate-containing silicone oil is shown as the following formula:

n is any integer from 10 to 200.

2. The preparation method of the ultraviolet-curing methacrylate-containing silicone oil PSi-MMA according to claim 1, is characterized by comprising the following steps: adding epoxy-terminated polymethoxysiloxane A, an organic base catalyst and a solvent into a reaction bottle, dropwise adding a methacrylic acid-3-mercaptopropionyloxyethyl ester B solution into the reaction solution under normal temperature stirring, dropwise adding for 10min, concentrating under reduced pressure after the reaction is finished, removing small molecules through purification treatment, and drying to obtain the pure polymethoxysiloxane material PSi-MMA with a terminal methacrylate structure, wherein the reaction equation is shown as the formula [1 ]:

[1] reaction equation for PSi-MMA.

3. The method for preparing the PSi-MMA-containing methacrylate-based ultraviolet-curable silicone oil according to claim 2, wherein n in the structure of the epoxy-terminated polymethoxysiloxane is an integer of 10 to 200, and the molecular weight is 1000 to 15000.

4. The method for preparing PSi-MMA as claimed in claim 2, wherein the amount of raw material B is 2 times the molar amount of epoxy terminated polymethoxysiloxane, and the organic base is triethylamine, triphenylphosphine, triethanolamine, 2, 4, 6 tris (dimethylaminomethyl) phenol DMP-30.

5. The method for preparing the PSi-MMA as claimed in claim 2, wherein the reaction temperature is 25 ℃ and the solvent is acetone, tetrahydrofuran, ethyl acetate, toluene, xylene or butanone, and the reaction time is 1 hour.

6. The use of the UV-curable methacrylate-containing silicone oil PSi-MMA according to claim 1, wherein the methacrylate-containing silicone oil is used for preparing PSi-MMA films.

7. The application of the PSi-MMA-containing UV-curable methacrylate silicone oil according to claim 6, wherein the preparation method of the PSi-MMA film comprises the following steps: mixing the PSi-MMA and the compound photoinitiator into a homogeneous phase, selecting inert gas or high-purity nitrogen for bubbling to remove oxygen, coating the liquid on a paper substrate in a rolling manner, continuously performing ultraviolet irradiation for 1-5 seconds, and thus obtaining the PSi-MMA film.

8. The application of the UV-curable methacrylate-containing silicone oil PSi-MMA as claimed in claim 7, wherein the compound photoinitiator is: the mass ratio is 1: 1-hydroxycyclohexyl phenyl ketone 184 and 2-hydroxy-2-methyl-1-phenyl-1-acetone 1173 of 1.

9. The application of the UV-curable methacrylate-containing silicone oil PSi-MMA as claimed in claim 7, wherein the amount of the compound photoinitiator is 1% of the mass of PSi-MMA, and the inert gas is: and argon gas.

10. The use of the UV-curable methacrylate-containing silicone oil PSi-MMA according to claim 7, wherein the molecular weight of PSi-MMA is 2900, n is 30, the residual adhesion rate after film formation is up to 95%, and the release force is 21 g/in.