CN114163645B - Anchoring agent and preparation method and application thereof - Google Patents

Abstract

The invention provides an anchoring agent, a preparation method and application thereof, wherein the anchoring agent has a structure shown in a formula 1:

Description

Anchoring agent and preparation method and application thereof

Technical Field

The invention relates to an anchoring agent, in particular to an organic silicon modified anchoring agent, a preparation method and application thereof, and belongs to the field of fine chemical engineering.

Background

The anchoring agent is mainly used for organic silicon pressure-sensitive adhesive or release agent, and is used for improving the adhesion of the coating to the base material and improving the adhesive force of the coating. Most of the existing anchoring agents are silane coupling agents or modified silane coupling agent mixtures, have strong volatility and pungent odor, and have poor compatibility with a system due to the fact that the existing anchoring agents are small molecules and contain polar groups such as methoxy groups.

The patent publication CN105295414A proposes an anchoring agent prepared by (glycidoxy) propyl-trimethyl-phenyl-silane or glycidoxypropyl-trimethoxy-silane and vinyl triacetoxy-silane under the action of ion exchange resin; the patent publication CN106916309A proposes a tackifier prepared from gamma-glycidoxypropyltrimethoxysilane and vinyltriacetoxysilane under the action of a catalyst.

The modified silane coupling agent prepared from the two silane coupling agents can be added into a resin or adhesive system to improve the adhesive force of the organic silicon coating to the base material. However, acetoxysilane has irritant sour taste, and the modified silane coupling agent is still small molecule, has strong volatility, contains polar groups such as methoxy group, has poor compatibility with an organic silicon system, and has poor transparency in applications such as organic silicon pressure-sensitive adhesive and parting agent.

The publication patent CN104774333A discloses an addition type organic silicon rubber tackifier capable of improving adhesion of addition type silicon rubber and a base material after medium-temperature curing, and a preparation method and an application method thereof. The patent publication CN108329477A discloses a preparation method of an organosilicon tackifier taking dimethyl hydroxyl silicone oil, vinyl trimethoxy silane and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane as raw materials. The patent publication CN104892942A discloses a siloxane oligomer tackifier with a degree of polymerization of 3-6 prepared by cohydrolytic condensation of three or more alkoxysilanes with different functionalities, which can be added into addition type silicone rubber to enhance the adhesion properties with metals, ceramics, polar polymers, etc. The organosilicon tackifier prepared by the reaction of the vinyl hydroxyl silicone oil and the silane coupling agent has the function of improving the bonding strength of the silicone rubber and the base material, but the silane coupling agent contains more alkoxy, so that more VOC can be released in the action process, and the application of the organosilicon pressure-sensitive adhesive in the electronic and electric industry is limited. The silane oligomer prepared by cohydrolytic polycondensation of several silane coupling agents has a random structure and poor compatibility with a silicone oil system, and influences the transparency of a PET film in the use of the organic silicon pressure-sensitive adhesive.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides an anchoring agent and a preparation method thereof. The anchoring agent combines silicone oil with vinyl-containing side groups and silane oligomer with adhesive groups, so that the compatibility with an organic silicon system can be enhanced, the transparency of the system can be improved, and the anchoring agent can also play a role in adhesion.

The vinyl contained in the anchoring agent can participate in the reaction of an addition system, so that the adhesion between the coating and the base material can be further enhanced; meanwhile, the silane coupling agent is subjected to further polymerization reaction, so that the VOC release is lower.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides an anchoring agent, which has a structure shown in a formula 1:

in the formula: r independently represents (2, 3-epoxypropoxy) propyl, (3, 4-epoxycyclohexyl) ethyl;

R ₁ each independently represents a methyl group or an ethyl group; me represents a methyl group;

m =1 to 20, preferably 3 to 7; n =1 to 8, preferably 1 to 3; more preferably, m + n =4 to 10;

r =2 to 20, preferably 3 to 10.

The (2, 3-glycidoxy) propyl group and the (3, 4-epoxycyclohexyl) ethyl group represented by the above formula 1 have the following structures, respectively:

the viscosity of the anchoring agent of the invention is in the range of 20-100 cp, preferably 30-60 cp.

The invention also provides a preparation method of the anchoring agent shown in the formula 1, which comprises the following steps:

1) Preparation of terminal hydroxyl silicone oil with vinyl-containing side group

Mixing dimethyldimethoxysilane, methylvinyldimethoxysilane and water, and carrying out cohydrolysis polycondensation reaction under the action of a catalyst 1 to obtain terminal hydroxyl silicone oil with a vinyl-containing side group;

2) Preparation of silane oligomer containing adhesive group

Mixing a silane coupling agent containing epoxy groups with water, and carrying out hydrolytic condensation reaction under the action of a catalyst 2 to obtain a silane oligomer;

3) Preparation of the anchoring agent

Taking the hydroxyl-terminated silicone oil with the vinyl-containing side group prepared in the step 1) and the silane oligomer with the adhesive group prepared in the step 2) as raw materials, and carrying out condensation reaction under the action of a catalyst 3 and a solvent to prepare the anchoring agent.

In the step 1) of the invention, the molar ratio of the dimethyldimethoxysilane to the methylvinyldimethoxysilane is 1.5-5: 1, preferably 2.2 to 3.6:1;

in step 1) of the present invention, the catalyst 1 is an alkali metal oxide, preferably magnesium oxide or calcium oxide;

preferably, the catalyst 1 is used in an amount of 0.01 to 0.5%, preferably 0.05 to 0.2%, based on the total mass of the dimethyldimethoxysilane and the methylvinyldimethoxysilane;

in the step 1) of the invention, the amount of the water is 1 to 6 times, preferably 3 to 5 times of the total mole number of the dimethyldimethoxysilane and the methylvinyldimethoxysilane;

in the step 1), the cohydrolysis polycondensation reaction is carried out at the temperature of 20-50 ℃, preferably 25-35 ℃ for 3-6 h, preferably 4-5 h;

preferably, after the completion of the cohydrolytic polycondensation reaction, the method further comprises post-treatment processes such as filtration and reduced pressure distillation, and for the conventional operation in the field, the cohydrolytic polycondensation reaction obtains a reaction solution, the catalyst is removed by filtration, and then the reaction solution is purified by reduced pressure distillation (such as 60 ℃,10 mbar).

In the step 1), the prepared hydroxyl-terminated silicone oil with the vinyl-containing side group has a structure shown in a formula 2:

wherein Me, m and n are the same as those in formula 1, namely Me represents methyl;

m =1 to 20, preferably 3 to 7; n =1 to 8, preferably 1 to 3; preferably, m + n =4 to 10.

In step 2) of the present invention, the epoxy group-containing silane coupling agent is selected from any one of or a combination of at least two of γ - (2, 3-epoxypropoxy) propyltrimethoxysilane, γ - (2, 3-epoxypropoxy) propyltriethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane, more preferably γ - (2, 3-epoxypropoxy) propyltrimethoxysilane and/or β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane;

in step 2) of the present invention, the catalyst 2 is an acidic catalyst, preferably hydrochloric acid, sulfuric acid, trifluoroacetic acid or trifluoromethanesulfonic acid, and the like, more preferably trifluoromethanesulfonic acid;

preferably, the catalyst 2 is used in an amount of 10 to 1000ppm, preferably 100 to 500ppm, based on the mass of the epoxy group-containing silane coupling agent;

in step 2) of the present invention, the molar ratio of the water to the epoxy group-containing silane coupling agent is 0.5 to 1, preferably 0.5 to 0.75:1;

in the step 2), the hydrolysis condensation reaction is carried out at the temperature of 20-60 ℃, preferably 30-40 ℃ for 1-4 h, preferably 2-3 h;

preferably, after the hydrolysis condensation reaction is completed, the post-treatment processes of neutralization, filtration, reduced pressure distillation and the like are also included, and the operation is conventional in the field, wherein the neutralization operation is mainly used for neutralizing the acidity of the catalyst 2, and preferably, the neutralizing agent is calcium carbonate, and the adding amount can be 10-20 times of the molar amount of the catalyst 2.

In step 2) of the present invention, the prepared silane oligomer containing an adhesive group has a structure represented by formula 3:

wherein R represents a bonding group, and R and R are the same as those in formula 1, i.e., R each independently represents a (2, 3-glycidoxy) propyl group or a (3, 4-epoxycyclohexyl) ethyl group;

R ₁ each independently represents a methyl or ethyl group;

r =2 to 20, preferably 3 to 10.

In the step 3), the mass ratio of the hydroxyl-terminated silicone oil with the vinyl-containing side group to the silane oligomer with the adhesive group is 0.5-2: 1, preferably 0.7 to 1.5:1;

in step 3) of the present invention, the catalyst 3 is an alkaline catalyst, preferably sodium hydroxide or potassium hydroxide;

preferably, the catalyst 3 is used in an amount of 1 to 1000ppm, preferably 10 to 100ppm, based on the total mass of the pendant vinyl group-containing hydroxyl-terminated silicone oil and the adhesive group-containing silane oligomer;

in step 3) of the present invention, the solvent is an organic solvent, preferably selected from toluene, xylene, heptane, more preferably heptane;

preferably, the amount of the solvent is 0.2 to 2 times, preferably 0.5 times of the total mass of the hydroxyl-terminated silicone oil with the vinyl-containing side group and the silane oligomer with the adhesive group;

in the step 3), the condensation reaction is carried out at the temperature of 60-100 ℃, preferably 70-90 ℃, and the reaction time is 2-6 hours, preferably 3-5 hours;

preferably, after the condensation reaction is completed, the condensation reaction also comprises post-treatment processes such as filtration, reduced pressure distillation and the like, and for the conventional operation in the field, the condensation reaction obtains a reaction liquid, the catalyst is removed by filtration, and then the reaction liquid is purified by reduced pressure distillation (such as 60 ℃,10 mbar).

The invention further provides the application of the anchoring agent in the fields of organic silicon pressure-sensitive adhesives and release agents, and is particularly suitable for increasing the anchoring property of a pressure-sensitive adhesive layer and a release agent coating on a PET (polyethylene terephthalate) film.

Preferably, the invention provides a silicone pressure-sensitive adhesive composition, which comprises the anchoring agent shown in the formula 1, wherein the addition amount is 0.5-3%, preferably 1-2%, based on 100% of the total mass of the silicone pressure-sensitive adhesive composition.

According to the prior art, the raw materials of the silicone pressure-sensitive adhesive composition of the invention may optionally comprise silicon-containing raw materials, auxiliaries and the like, such as vinyl-terminated polydimethylsiloxane, silicone resin, toluene, hydrogen-containing silicone oil, inhibitors, catalysts and other components; when the organic silicon pressure-sensitive adhesive composition is prepared, all the raw materials except the catalyst are mixed with the anchoring agent, then the catalyst is added, and the mixture is uniformly mixed to obtain the organic silicon pressure-sensitive adhesive composition.

The curing conditions of the organic silicon pressure-sensitive adhesive composition are preferably as follows: the temperature is 130-160 deg.C, and the time is 1-5min.

Compared with the prior art, the invention has the following technical advantages:

(1) The anchoring agent provided by the invention combines silicone oil with a vinyl-containing lateral group and silane oligomer with an adhesive group, can improve the compatibility with systems such as organic silicon pressure-sensitive adhesive, release agent and the like, and obtains transparent bath liquid and a coating;

(2) Compared with silane coupling agent or modified silane coupling agent mixture, the anchoring agent combines the vinyl and silane oligomer containing the bonding group into a whole, the vinyl can participate in the addition reaction of an organic silicon system and is firmly combined with the coating, and the bonding group is interacted with the base material and is tightly connected, so that better anchoring effect can be achieved, and the adhesive force of the coating to the base material is enhanced;

(3) The preparation process of the anchoring agent provided by the invention comprises silane coupling agent polycondensation, namely silane oligomer preparation, wherein in the process, part of alkoxy is hydrolyzed into alcohol to be removed from the system, thereby reducing VOC (volatile organic compound) release of the anchoring agent in the using process, being applicable to industries with higher requirements on VOC release, such as the electronic industry, and having better aging stability when being applied to a pressure-sensitive adhesive or a release agent system.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.

The embodiment of the invention has the following main raw material source information:

dimethyl dimethoxy silane: new materials, ltd, new material, north Hubei, N.B., technical grade;

methylvinyldimethoxysilane: shandong Silicones New materials, inc., industrial grade;

methyltrimethoxysilane: shandong Silicidae New Material Co., ltd, industrial grade;

γ - (2, 3-glycidoxy) propyltrimethoxysilane: shandong Silicidae New Material Co., ltd, industrial grade;

γ - (2, 3-glycidoxy) propyltriethoxysilane: shandong Silicones New materials, inc., industrial grade;

β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane: shandong Silicidae New Material Co., ltd, industrial grade;

β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane: shandong Silicidae New Material Co., ltd, industrial grade;

magnesium oxide: shigaku chemical industries, inc., AR;

calcium oxide: shigaku chemical industries, inc., AR;

trifluoromethanesulfonic acid: aladdin reagents, inc., AR;

hydrochloric acid: aladdin reagents, inc., AR;

sulfuric acid: aladdin reagents, inc., AR;

potassium hydroxide: shigaku chemical industries, inc., AR;

sodium hydroxide: shigaku chemical industries, inc., AR;

heptane: chemical agents of the national drug group, limited, AR;

SA 1500 silicone pressure sensitive adhesive: wanhua chemical group, inc., industrial grade;

SA 1511 Silicone pressure-sensitive adhesive, vanhua chemical group, inc., industrial grade;

SD 8500 catalyst Industrial grade, vanhua chemical group, inc.;

SD 8600 Cross-linking agent Vanhua chemical group, inc., industrial grade;

unless otherwise specified, other raw materials and reagents in the following examples and comparative examples were all commercially available.

The test methods employed in the examples of the invention and the comparative examples are as follows:

1. viscosity was measured using a Brookfield Viscometer DV2T LVT10 Viscometer;

2. measuring the light transmittance and the haze by using a WGT-S light transmittance/haze measuring instrument of Shanghai light-transmitting instrument and meter Limited;

3. the adhesive force of the pressure-sensitive adhesive was measured using AR2000 from chemistruments, usa;

4. the methoxy and epoxy group contents were determined by the internal standard addition method using an AC300 NMR spectrometer from Bruker.

[ example 1 ]

Preparing an anchoring agent M1:

1) 1080g (9 mol) of dimethyldimethoxysilane and 528g (4 mol) of methylvinyldimethoxysilane are mixed, 1.61g of magnesium oxide is added under stirring, 1404g (78 mol) of water is added dropwise, the mixture is subjected to cohydrolysis and polycondensation reaction at 25 ℃ for 5 hours, the catalyst is removed by filtration, and the by-product methanol and the excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the terminal hydroxyl silicone oil with the side group containing vinyl; the viscosity was 25.8cp.

2) Mixing 246g (1 mol) of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 0.03g of trifluoromethanesulfonic acid, dropwise adding 9g (0.5 mol) of water, carrying out hydrolysis condensation reaction at 25 ℃ for 4h, adding 0.4g of calcium carbonate to neutralize trifluoromethanesulfonic acid, filtering, and carrying out reduced pressure distillation (60 ℃,10 mbar) to remove a byproduct methanol to obtain a silane oligomer containing an adhesive group; the viscosity was 8.6cp.

3) Mixing 106g of terminal hydroxyl silicone oil with a vinyl-containing side group, 150g of silane oligomer containing an adhesive group and 128g of heptane, then adding 0.01g of potassium hydroxide, uniformly mixing, carrying out condensation reaction at 90 ℃ for 4h, filtering to remove the catalyst after the reaction is finished, and carrying out reduced pressure distillation (at 60 ℃ and 10 mbar) to remove by-products of methanol and heptane, thereby preparing an anchoring agent M1; the viscosity was 39.1cp.

And (3) performing nuclear magnetic silicon spectrum analysis and test:

chemical shifts δ = -10.19, δ = -24.67 stand for

Wherein the silicon atom, δ = -21.23, δ = -35.34 represents

Wherein the silicon atom, δ = -49.98, δ = -58.71, δ = -68.50 represents

Silicon atom in (2).

The structure of the anchoring agent M1 is proved to be:

[ example 2 ]

Preparing an anchoring agent M2:

1) 1080g (9 mol) of dimethyldimethoxysilane and 396g (3 mol) of methylvinyldimethoxysilane are mixed, 0.74g of magnesium oxide is added under stirring, 1080g (60 mol) of water is added dropwise, the mixture is subjected to cohydrolysis and polycondensation reaction at 25 ℃ for 6 hours, the catalyst is removed by filtration, and the by-product methanol and excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the hydroxyl-terminated silicone oil with the side group containing vinyl; the viscosity was 28.3cp.

2) Mixing 246g (1 mol) of beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane with 0.1g of hydrochloric acid, dropwise adding 13.5g (0.75 mol) of water, carrying out hydrolytic condensation reaction at 30 ℃ for 3 hours, adding 5.4g of calcium carbonate to neutralize the hydrochloric acid, filtering, and carrying out reduced pressure distillation (60 ℃,10 mbar) to remove a byproduct methanol to obtain a silane oligomer containing a bonding group; the viscosity was 12.5cp.

3) Mixing 162g of terminal hydroxyl silicone oil with a vinyl-containing lateral group, 150g of silane oligomer containing an adhesive group and 156g of heptane, then adding 0.02g of potassium hydroxide, uniformly mixing, carrying out condensation reaction at 100 ℃ for 2 hours, filtering to remove the catalyst after the reaction is finished, and carrying out reduced pressure distillation (at 60 ℃,10 mbar) to remove by-products of methanol and heptane so as to obtain an anchoring agent M2; the viscosity was 43.4cp.

[ example 3 ]

Preparing an anchoring agent M3:

1) 1080g (9 mol) of dimethyldimethoxysilane and 528g (4 mol) of methylvinyldimethoxysilane are mixed, 3.2g of calcium oxide is added under stirring, then 702g (39 mol) of water is added dropwise, the mixture is subjected to cohydrolysis and polycondensation reaction at 35 ℃ for 4 hours, the catalyst is removed by filtration, and the by-product methanol and the excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the terminal hydroxyl silicone oil with the side group containing vinyl; the viscosity was 36.9cp.

2) Mixing 236g (1 mol) of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 0.02g of sulfuric acid, dropwise adding 18g (1 mol) of water, carrying out hydrolysis condensation reaction at 50 ℃ for 1h, adding 0.4g of calcium carbonate to neutralize the sulfuric acid, filtering, and carrying out reduced pressure distillation (60 ℃,10 mbar) to remove a byproduct methanol to obtain a silane oligomer containing an adhesive group; the viscosity was 15.3cp.

3) Mixing 90g of terminal hydroxyl silicone oil with a vinyl-containing side group, 150g of silane oligomer containing an adhesive group and 120g of heptane, then adding 0.08g of sodium hydroxide, uniformly mixing, carrying out condensation reaction at 100 ℃ for 3h, filtering to remove the catalyst after the reaction is finished, and carrying out reduced pressure distillation (at 60 ℃ and 10 mbar) to remove by-products of methanol and heptane, thereby preparing an anchoring agent M3; the viscosity was 38.6cp.

[ example 4 ] A method for producing a polycarbonate

Preparing an anchoring agent M4:

1) 1080g (9 mol) of dimethyldimethoxysilane and 660g (5 mol) of methylvinyldimethoxysilane are mixed, 0.17g of calcium oxide is added under stirring, 1008g (56 mol) of water is added dropwise, the mixture is subjected to cohydrolytic polycondensation reaction at 40 ℃ for 6 hours, the catalyst is removed by filtration, and the by-product methanol and excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the hydroxyl-terminated silicone oil with the side group containing vinyl; the viscosity was 34.8cp.

2) Mixing 236g (1 mol) of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 0.12g of trifluoromethanesulfonic acid, dropwise adding 13.5g (0.75 mol) of water, carrying out hydrolysis condensation reaction at 40 ℃ for 2h, adding 1.6g of calcium carbonate to neutralize trifluoromethanesulfonic acid, filtering, and carrying out reduced pressure distillation (60 ℃,10 mbar) to remove a byproduct methanol to obtain a silane oligomer containing an adhesive group; the viscosity was 11.8cp.

3) 210g of terminal hydroxyl silicone oil with a vinyl-containing side group, 150g of silane oligomer containing an adhesive group and 180g of heptane are mixed, 0.03g of potassium hydroxide is added and uniformly mixed, condensation reaction is carried out at 100 ℃ for 2 hours, the catalyst is removed by filtration after the reaction is finished, and by-products of methanol and heptane are removed by reduced pressure distillation (60 ℃ and 10 mbar), so as to prepare an anchoring agent M4; the viscosity was 36.9cp.

[ example 5 ]

Preparing an anchoring agent M5:

1) 1080g (9 mol) of dimethyldimethoxysilane and 264g (2 mol) of methylvinyldimethoxysilane are mixed, 0.81g of magnesium oxide is added under stirring, 396g (22 mol) of water is added dropwise, the mixture is subjected to cohydrolysis and polycondensation reaction at 50 ℃ for 3 hours, the catalyst is removed by filtration, and the by-product methanol and excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the hydroxyl-terminated silicone oil with the side group containing vinyl; the viscosity was 27.5cp.

2) 288g (1 mol) of beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane and 0.02g of trifluoroacetic acid are mixed, 10.8g (0.6 mol) of water are added dropwise, hydrolysis condensation reaction is carried out for 3h at 60 ℃, 0.35g of calcium carbonate is added to neutralize the trifluoroacetic acid, filtration is carried out, and reduced pressure distillation (60 ℃,10 mbar) is carried out to remove by-product ethanol, thus obtaining silane oligomer containing adhesive groups; the viscosity was 9.3cp.

3) Mixing 110g of terminal hydroxyl silicone oil with a vinyl-containing side group, 150g of silane oligomer containing an adhesive group and 130g of heptane, then adding 0.02g of potassium hydroxide, uniformly mixing, carrying out condensation reaction at 100 ℃ for 3h, filtering to remove the catalyst after the reaction is finished, and carrying out reduced pressure distillation (at 60 ℃ and 10 mbar) to remove by-products of ethanol and heptane, thereby obtaining an anchoring agent M5; the viscosity was 46.4cp.

[ example 6 ] A method for producing a polycarbonate

Preparing an anchoring agent M6:

1) 1080g (9 mol) of dimethyldimethoxysilane and 396g (3 mol) of methylvinyldimethoxysilane are mixed, 5.9g of magnesium oxide is added under stirring, 1080g (60 mol) of water is added dropwise, the mixture is subjected to cohydrolysis and polycondensation reaction at 45 ℃ for 3 hours, the catalyst is removed by filtration, and the by-product methanol and the excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the hydroxyl-terminated silicone oil with the side group containing vinyl; the viscosity was 36.4cp.

2) 288g (1 mol) of beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane and 0.25g of trifluoromethanesulfonic acid are mixed, 14.4g (0.8 mol) of water are added dropwise, hydrolysis and condensation reaction is carried out at 35 ℃ for 3h, 3.3g of calcium carbonate is added to neutralize trifluoromethanesulfonic acid, filtration is carried out, and ethanol as a byproduct is removed by reduced pressure distillation (60 ℃,10 mbar) to obtain a silane oligomer containing an adhesive group; the viscosity was 12.7cp.

3) 158g of terminal hydroxyl silicone oil with a vinyl-containing lateral group, 150g of silane oligomer containing an adhesive group and 154g of heptane are mixed, then 0.2g of sodium hydroxide is added and uniformly mixed, condensation reaction is carried out for 4 hours at 80 ℃, the catalyst is removed by filtration after the reaction is finished, and ethanol and heptane which are byproducts are removed by reduced pressure distillation (60 ℃ and 10 mbar) to prepare an anchoring agent M6; the viscosity was 48.9cp.

[ example 7 ]

Preparing an anchoring agent M7:

1) 1080g (9 mol) of dimethyldimethoxysilane and 264g (2 mol) of methylvinyldimethoxysilane are mixed, 1.08g of magnesium oxide is added under stirring, 594g (33 mol) of water is added dropwise, the cohydrolytic polycondensation reaction is carried out for 4 hours at 35 ℃, the catalyst is removed by filtration, and the by-product methanol and excessive water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the hydroxyl-terminated silicone oil with the side group containing vinyl; the viscosity was 29.8cp.

2) 278g (1 mol) of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane and 0.01g of hydrochloric acid are mixed, 13.5g (0.75 mol) of water is added dropwise, hydrolysis condensation reaction is carried out at 45 ℃ for 2h, 0.5g of calcium carbonate is added to neutralize the hydrochloric acid, filtration is carried out, and reduced pressure distillation (60 ℃,10 mbar) is carried out to remove by-product ethanol, thus obtaining silane oligomer containing adhesive groups; the viscosity was 10.4cp.

3) Mixing 130g of terminal hydroxyl silicone oil with a vinyl-containing side group, 150g of silane oligomer containing an adhesive group and 140g of heptane, then adding 0.03g of potassium hydroxide, uniformly mixing, carrying out condensation reaction at 70 ℃ for 5 hours, filtering to remove a catalyst after the reaction is finished, and carrying out reduced pressure distillation (at 60 ℃ and 10 mbar) to remove by-products of ethanol and heptane, thereby obtaining an anchoring agent M7; the viscosity was 53.5cp.

[ example 8 ]

Preparing an anchoring agent M8:

1) 1080g (9 mol) of dimethyldimethoxysilane and 330g (2.5 mol) of methylvinyldimethoxysilane are mixed, 1g of calcium oxide is added under stirring, 414g (23 mol) of water is then added dropwise, the mixture undergoes a cohydrolytic polycondensation reaction at 35 ℃ for 6 hours, the catalyst is removed by filtration, and the by-product methanol and excess water are removed by reduced pressure distillation (60 ℃,10 mbar) to obtain the hydroxyl-terminated silicone oil with the side group containing vinyl; the viscosity was 32.1cp.

2) 278g (1 mol) of gamma- (2, 3-epoxypropoxy) propyltriethoxysilane and 0.06g of hydrochloric acid are mixed, 16.2g (0.9 mol) of water is added dropwise, hydrolysis condensation reaction is carried out at 45 ℃ for 4h, 3.3g of calcium carbonate is added to neutralize the hydrochloric acid, filtration is carried out, and reduced pressure distillation (60 ℃,10 mbar) is carried out to remove by-product ethanol, thus obtaining silane oligomer containing adhesive groups; the viscosity was 10.8cp.

3) Mixing 114g of terminal hydroxyl silicone oil with a vinyl-containing side group, 150g of silane oligomer containing an adhesive group and 132g of heptane, then adding 0.07g of potassium hydroxide, uniformly mixing, carrying out condensation reaction at 60 ℃ for 6 hours, filtering to remove the catalyst after the reaction is finished, and carrying out reduced pressure distillation (at 60 ℃,10 mbar) to remove by-products of ethanol and heptane, thereby obtaining an anchoring agent M8; the viscosity was 38.3cp.

Comparative example 1

Referring to the method of step 3) of example 1, except that the silane oligomer having a bonding group prepared in step 2) was replaced with equal mass of β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the other operations were not changed, an anchoring agent D1 was prepared; the viscosity was 32.4cp.

Comparative example 2

Referring to the procedure of example 1, step 3), except that the hydroxyl-terminated silicone oil having a vinyl group in the side group prepared in step 1) was changed to methylvinyldimethoxysilane by equimolar dimethyldimethoxysilane, and the other operations were not changed, an anchoring agent D2 was prepared; the viscosity was 35.9cp.

Comparative example 3

Silane oligomer was prepared by replacing β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane by an equimolar amount of methyltrimethoxysilane in step 2) of example 1;

referring to the method of step 3) of example 1, except that the silane oligomer prepared in step 2) to contain an adhesive group was replaced with the above silane oligomer, and the other operations were not changed to prepare an anchoring agent D3; the viscosity was 43.2cp.

The anchoring agents M1 to M8 synthesized in the above examples and the anchoring agents D1 to D3 synthesized in proportion were used respectively, glue was prepared according to the formula of the pressure-sensitive adhesive in table 1 (without adding an anchoring agent as a blank control), a coating bar was used to coat the corona surface of the PET film, the coating bar was baked at 150 ℃ for 3 minutes, the PET film and the steel plate were cut to be a tape, and the properties such as light transmittance, haze, adhesion and the like were measured, and the results are shown in table 2.

TABLE 1 Anchor evaluation formulation

Components	Parts by mass
		SA 1500	58
SA 1511	42
		SD 8600	0.48
SD 8500	1.2
		Anchoring agent	1

Wherein, the light transmittance and the haze are measured by a WGT-S light transmittance/haze measuring instrument of Shanghai Shenguan instrument and meter Limited;

the anchorage is judged according to whether silicon is dropped or not by hand rubbing after the grid division by a check method, the silicon is graded by 1-5 points, the silicon is qualified after 3 points, is unqualified below 3 points, is good after 4 points and is excellent after 5 points, and the anchorage of 2 hours of water boiling and 1 week of high temperature and high humidity (the temperature is 85 ℃, the humidity is 85%) are respectively measured;

the adhesion was measured by AR2000 from Chemistrutens, USA, and the normal temperature adhesion (20 min at room temperature) and the high temperature adhesion (3 days at 70 ℃) were measured, respectively.

As can be seen from the data in Table 2, the pressure-sensitive adhesive added with the anchoring agents M1-M8 has excellent anchoring property, the bath liquid is colorless and transparent, the light transmittance of the cured adhesive film is more than 90%, the adhesive film has high transparency, the haze is less than 2, the aging stability is good, and the climbing amplitude of the high-temperature adhesive force is lower than that of the normal-temperature adhesive force. The anchoring agent has good compatibility with an organic silicon system, bath liquid and an adhesive film both have good transparency, and both have excellent anchoring property after boiling in water and high temperature and high humidity, so that the adhesive film is bonded and a base material is bonded by combining silicone oil containing vinyl and a silane coupling agent, so that the adhesive film plays a real anchoring role.

TABLE 2 Effect of Anchor on pressure sensitive adhesive Properties

Therefore, compared with the blank (without adding an anchoring agent), the M1-M8 provides good anchoring property for the pressure-sensitive adhesive, has small influence on the transparency of bath liquid and adhesive film, can still keep a transparent state, and meets the application requirement.

Compared with D1, M1-M8 has better aging stability, D1 has higher content of methoxyl (the content of D1 and M1 groups is shown in Table 3), so that the high-temperature adhesive force (14.4 g/inch) climbs by more than 60% compared with the normal-temperature adhesive force (8.4 g/inch), and the aging adhesive forces of M1-M8 are all below 50% compared with the normal-temperature adhesive force, and the aging stability is better, such as M3 is lower than 25%.

TABLE 3 comparison of Anchor group content

Number of	Methoxy radical (wt.%)	(3, 4-epoxycyclohexyl) ethyl (wt.).％)
			D1	19.32	35.09
M1	14.64	36.26

Compared with D2, M1-M8 has better anchorage, and D2 cannot react with a pressure-sensitive adhesive system into a whole because the side group does not contain vinyl, so that the anchorage performance cannot be constructed between the pressure-sensitive adhesive layer and a base material.

Compared with D3, M1-M8 has better anchoring property, and D3 does not contain an adhesive group, so that the adhesive property of the adhesive to a base material cannot be exerted, and the anchoring property is poor.

Claims (32)

1. An anchoring agent having a structure represented by formula 1:

in the formula: r independently represents (2, 3-epoxypropoxy) propyl, (3, 4-epoxycyclohexyl) ethyl;

R ₁ each independently represents a methyl group or an ethyl group; me represents a methyl group;

m＝1～20，n＝1～8，r＝2～20。

2. the anchoring agent according to claim 1, wherein m =3 to 7, n =1 to 3, r =3 to 10.

3. The anchoring agent as claimed in claim 1, wherein m + n = 4-10.

4. The anchoring agent according to claim 1, wherein the viscosity is 20 to 100cp.

5. The anchoring agent according to claim 4, wherein the viscosity is 30 to 60cp.

6. A method for preparing the anchoring agent according to any one of claims 1 to 5, comprising the steps of:

1) Mixing dimethyldimethoxysilane, methylvinyldimethoxysilane and water, and carrying out cohydrolysis polycondensation reaction under the action of a catalyst 1 to obtain terminal hydroxyl silicone oil with a vinyl-containing side group;

2) Mixing a silane coupling agent containing an epoxy group with water, and carrying out hydrolytic condensation reaction under the action of a catalyst 2 to obtain a silane oligomer containing an adhesive group;

3) Taking the hydroxyl-terminated silicone oil with the vinyl-containing side group prepared in the step 1) and the silane oligomer with the adhesive group prepared in the step 2) as raw materials, and carrying out condensation reaction under the action of a catalyst 3 and a solvent to prepare the anchoring agent.

7. The method according to claim 6, wherein the molar ratio of dimethyldimethoxysilane to methylvinyldimethoxysilane in the step 1) is 1.5 to 5:1;

the catalyst 1 is alkali metal oxide;

the dosage of the catalyst 1 is 0.01 to 0.5 percent of the total mass of the dimethyldimethoxysilane and the methylvinyldimethoxysilane;

the dosage of the water is 1 to 6 times of the total mole number of the dimethyl dimethoxy silane and the methyl vinyl dimethoxy silane;

the cohydrolysis polycondensation reaction is carried out at the temperature of 20-50 ℃ for 3-6 h.

8. The preparation method according to claim 7, wherein the molar ratio of dimethyldimethoxysilane to methylvinyldimethoxysilane is 2.2 to 3.6:1.

9. the production method according to claim 7, characterized in that the catalyst 1 is magnesium oxide or calcium oxide.

10. The preparation method of the catalyst 1 according to claim 7, wherein the amount of the catalyst 1 is 0.05 to 0.2% of the total mass of the dimethyldimethoxysilane and the methylvinyldimethoxysilane.

11. The preparation method of claim 7, wherein the amount of water is 3 to 5 times the total molar amount of dimethyldimethoxysilane and methylvinyldimethoxysilane.

12. The process according to claim 7, wherein the cohydrolytic polycondensation is carried out at a temperature of 25 to 35 ℃ for 4 to 5 hours.

13. The method according to claim 6, wherein the hydroxyl-terminated silicone oil having a vinyl group as a pendant group obtained in step 1) has a structure represented by formula 2:

wherein Me, m and n are the same as in formula 1.

14. The method according to claim 6, wherein in step 2), the epoxy group-containing silane coupling agent is selected from any one of γ - (2, 3-glycidoxy) propyltrimethoxysilane, γ - (2, 3-glycidoxy) propyltriethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltriethoxysilane, or a combination of at least two thereof;

the catalyst 2 is an acid catalyst;

the dosage of the catalyst 2 is 10-1000 ppm of the mass of the silane coupling agent containing epoxy groups;

the molar ratio of the water to the epoxy group-containing silane coupling agent is 0.5-1;

the hydrolysis condensation reaction is carried out at the temperature of 20-60 ℃ for 1-4 h.

15. The method according to claim 14, wherein the epoxy group-containing silane coupling agent is γ - (2, 3-glycidoxy) propyltrimethoxysilane and/or β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

16. The method according to claim 14, wherein the catalyst 2 is hydrochloric acid, sulfuric acid, trifluoroacetic acid, or trifluoromethanesulfonic acid.

17. The production method according to claim 14, wherein the catalyst 2 is used in an amount of 100 to 500ppm by mass based on the epoxy group-containing silane coupling agent.

18. The production method according to claim 14, wherein the molar ratio of water to the epoxy group-containing silane coupling agent is from 0.5 to 0.75:1.

19. the method according to claim 14, wherein the hydrolytic condensation reaction is carried out at a temperature of 30 to 40 ℃ for 2 to 3 hours.

20. The method according to claim 6, wherein the silane oligomer having a bonding group prepared in step 2) has a structure represented by formula 3:

wherein R represents a bonding group, and R and R are the same as those in formula 1.

21. The method according to claim 6, wherein in step 3), the mass ratio of the hydroxyl-terminated silicone oil having a pendant vinyl group to the silane oligomer having an adhesive group is 0.5 to 2:1;

the catalyst 3 is a basic catalyst;

the dosage of the catalyst 3 is 1-1000 ppm of the total mass of the terminal hydroxyl silicone oil with the vinyl-containing side group and the silane oligomer with the adhesive group;

the solvent is an organic solvent;

the dosage of the solvent is 0.2 to 2 times of the total mass of the hydroxyl-terminated silicone oil with the vinyl-containing side group and the silane oligomer with the adhesive group;

the condensation reaction is carried out at the temperature of 60-100 ℃ for 2-6 h.

22. The method according to claim 21, wherein the mass ratio of the terminal hydroxyl silicone oil having a vinyl group as a side group to the silane oligomer having an adhesive group is from 0.7 to 1.5:1.

23. the method of claim 21, wherein the catalyst 3 is sodium hydroxide or potassium hydroxide.

24. The production method according to claim 21, wherein the catalyst 3 is used in an amount of 10 to 100ppm based on the total mass of the hydroxyl-terminated silicone oil having a vinyl group in a side group and the silane oligomer having a bonding group.

25. The method of claim 21, wherein the solvent is toluene, xylene, or heptane.

26. The production method according to claim 21, wherein the solvent is used in an amount of 0.5 times the total mass of the hydroxyl-terminated silicone oil having a vinyl group in a side group and the silane oligomer having a bonding group.

27. The method of claim 21, wherein the condensation reaction is carried out at a temperature of 70 to 90 ℃ for a time of 3 to 5 hours.

28. Use of the anchoring agent according to any one of claims 1 to 5 or prepared by the preparation method according to any one of claims 6 to 27 in the field of silicone pressure-sensitive adhesives, release agents.

29. Use according to claim 28, for increasing the anchorage of pressure-sensitive adhesive layers and release agent coatings to PET films.

30. A silicone pressure-sensitive adhesive composition comprising the anchor agent according to any one of claims 1 to 5 or the anchor agent produced by the production method according to any one of claims 6 to 27, wherein the amount of the anchor agent added is 0.5 to 3% based on 100% by mass of the total silicone pressure-sensitive adhesive composition.

31. The silicone pressure-sensitive adhesive composition of claim 30, wherein the anchoring agent is added in an amount of 1 to 2% based on 100% by mass of the silicone pressure-sensitive adhesive composition.

32. The silicone pressure sensitive adhesive composition of claim 30, wherein the silicone pressure sensitive adhesive composition has the curing conditions: the temperature is 130-160 deg.C, and the time is 1-5min.