CN112480862B - Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof - Google Patents

Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof Download PDF

Info

Publication number
CN112480862B
CN112480862B CN202011354922.4A CN202011354922A CN112480862B CN 112480862 B CN112480862 B CN 112480862B CN 202011354922 A CN202011354922 A CN 202011354922A CN 112480862 B CN112480862 B CN 112480862B
Authority
CN
China
Prior art keywords
silicone resin
sensitive adhesive
silicone
trapezoidal
prepolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011354922.4A
Other languages
Chinese (zh)
Other versions
CN112480862A (en
Inventor
李泽勇
姚坤满
郑贵明
柳晨醒
何海
曾祥雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Tinci Materials Technology Co Ltd
Original Assignee
Guangzhou Tinci Materials Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Tinci Materials Technology Co Ltd filed Critical Guangzhou Tinci Materials Technology Co Ltd
Priority to CN202011354922.4A priority Critical patent/CN112480862B/en
Publication of CN112480862A publication Critical patent/CN112480862A/en
Application granted granted Critical
Publication of CN112480862B publication Critical patent/CN112480862B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention belongs to the technical field of silicone rubber, and discloses a trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and a preparation method thereof. The organic silicon pressure-sensitive adhesive comprises addition reaction curing type pressure-sensitive adhesive consisting of methyl vinyl silicone rubber, MQ silicone resin, trapezoidal reinforced silicone resin and hydrogen-containing silicone oil, or comprises peroxide curing type pressure-sensitive adhesive consisting of hydroxyl terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin. The trapezoid silicone resin prepared by adding the pressure-sensitive adhesive into a specific method not only can improve the peeling strength and the high-temperature viscosity, but also has the effects of promoting the dispersion of MQ silicone resin and improving the transparency of products. The obtained organic silicon pressure-sensitive adhesive has no shrinkage cavity phenomenon in the curing process and has no residue after stripping. Has wide market prospect.

Description

Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof
Technical Field
The invention belongs to the technical field of silicone rubber, and particularly relates to a trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and a preparation method thereof.
Background
The organic silicon pressure-sensitive adhesive can be bonded with a low surface energy surface due to good high and low temperature resistance, chemical resistance and low dielectric property. The organic silicon pressure-sensitive adhesive tape can be widely applied to industrial production in the forms of splicing tapes, electrical tapes, plasma spraying tapes, machining tapes and the like. And because of the characteristics of no toxicity, no stimulation, physiological inertia, wide use temperature range, proper bonding strength, medicament permeability and the like, the adhesive also can be widely applied to medical treatment and transdermal therapeutic system preparations.
The organic silicon pressure-sensitive adhesive main body is formed by mixing liquid silicon rubber and MQ silicon resin according to a certain proportion. The liquid silicone rubber can increase the fluidity of the pressure-sensitive adhesive, thereby increasing the interfacial adhesion, has strong initial viscosity, and is used as a main body for crosslinking and curing. At present, the organic silicon pressure-sensitive adhesive on the market is mainly divided into a peroxide curing type and an addition reaction curing type. The reaction mechanism of the peroxide cure type is that alkyl groups (such as methyl groups) on the liquid silicone rubber generate radical crosslinking curing under peroxide initiation: 2Si-CH3→2Si-CH2·→Si-CH2-CH2-Si. The addition reaction curing type reaction mechanism is that the vinyl silicone rubber and the hydrogen-containing silicone oil cross-linking agent are subjected to hydrosilylation reaction crosslinking curing under the action of a catalyst: Si-CH ═ CH2+H-Si→Si-CH2-CH2-Si. The MQ silicon resin as the reinforcing agent has great influence on the adhesive property of the pressure-sensitive adhesive, and the adhesive strength of the organic silicon pressure-sensitive adhesive can be obviously improved through the reinforcement of the MQ silicon resin. However, the MQ silicon resin has a double-layer compact structure spherical structure, the spherical core part is cage-shaped SiO2 with high density and Si-O-Si chain connection, and the spherical shell part is an M layer with low density. Because the internal crosslinking density of the structure is high, the dispersion is difficult to realize in use, and the pre-dispersion is usually required to be performed for a long time and then mixed with the silicone rubber, or the mixing and dispersion are performed at a high temperature. If the mixing is not uniform, the reinforcing effect is not uniform, and finally the pressure-sensitive adhesive generates 'ripples' or 'shrinkage holes' (caused by uneven stress during curing) on the surface of the cured adhesive layer, and the adhesive is easy to remain during peeling (uneven adhesion, peeling of the part with weak adhesion and residue of the part with strong adhesion), thereby obviously influencing the use effect.
In recent years, trapezoidal polysiloxane (R-LPS) has attracted attention from researchers because of its unique double-or multi-chain structure, such as better high temperature resistance, radiation resistance, weather resistance, high strength, and high air tightness than single-chain polysiloxane. The currently known ladder-shaped organic silicon polymers can be divided into three types according to the types of ladder struts: oxygen bridged ladder polysilsesquioxanes, organo bridged ladder polysiloxanes, and siloxane bridged ladder polysiloxanes. More generally, oxygen bridged ladder polysilsesquioxanes exhibit the inorganic properties of polysiloxanes, such as thermal stability, oxidation resistance, etc., and have been used in some composite systems in recent years. However, its application in industry is limited due to its low flexibility and poor compatibility with general polymers. The organic bridged ladder-shaped polysiloxane has higher flexibility and better compatibility with common organic polymers, but has slightly inferior heat resistance to oxygen bridged ladder-shaped polysilsesquioxane. The third class of siloxane bridged ladder-shaped polysiloxane combines the advantages of ladder-shaped polysilsesquioxane and organic bridged ladder-shaped polysiloxane, namely, the siloxane bridged ladder-shaped polysiloxane has high heat resistance, flexibility and good compatibility with general polymers. However, the trapezoidal polysiloxane resin is rarely reported to be used for the organic silicon pressure-sensitive adhesive at present.
Patent CN 110184027 a discloses a conductive silicone pressure-sensitive adhesive and a preparation method thereof. The organic silicon rubber and the MQ silicon resin are taken as base materials, and the addition of organic peroxide, cage-shaped polysilsesquioxane and heat-resistant additives (cerium oxide, cerium fluoride and ferric oxide) is favorable for enhancing the peeling strength and the high-temperature viscosity of the conductive organic silicon pressure-sensitive adhesive. However, the cage-like polysilsesquioxane used in the patent is trisilicol phenyl silsesquioxane or trisilicol isobutyl silsesquioxane, belongs to oxygen bridge-based ladder-shaped polysiloxane, and although the heat resistance can be improved to a certain extent, the compatibility and the dispersibility of the cage-like polysilsesquioxane are poor, and the cage-like polysilsesquioxane cannot promote the dispersion of MQ silicon resin to improve the uniformity of the reinforcing effect.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide the trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive. The trapezoid silicon resin prepared by adding a specific method into the organic silicon pressure-sensitive adhesive can improve the peeling strength and the high-temperature viscosity, and also has the effects of promoting the dispersion of MQ silicon resin to improve the uniformity of the reinforcing effect and improving the transparency of the product.
The invention also aims to provide a preparation method of the trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive.
The purpose of the invention is realized by the following technical scheme:
a ladder-shaped silicone resin reinforced organic silicon pressure-sensitive adhesive comprises the following components in parts by weight (1) or (2):
component (1): 80-120 parts of methyl vinyl silicone rubber, 80-120 parts of MQ silicone resin, 5-25 parts of trapezoidal reinforced silicone resin, 5-12 parts of hydrogen-containing silicone oil, 1-3 parts of inhibitor, a catalytic amount of platinum catalyst, 0-10 parts of functional assistant, and a diluting solvent with solid content of 40-65%;
component (2): 80-120 parts of hydroxyl terminated silicone rubber, 80-120 parts of MQ silicone resin, 5-25 parts of trapezoidal reinforced silicone resin, 1-5 parts of organic peroxide catalyst, 0-10 parts of functional assistant and a diluting solvent with solid content of 40-65%;
the trapezoid reinforced silicone resin is prepared by the following method:
(1) respectively dissolving vinyl-terminated polydimethylsiloxane or vinyl-terminated polyphenyl methylsiloxane in an organic solvent, heating to 60-80 ℃ under the protection of inert atmosphere, adding a platinum catalyst, then dropwise adding methyldimethoxysilane, controlling the temperature to be 75-110 ℃ to carry out addition reaction, and evaporating to remove the organic solvent and low-boiling-point substances after the reaction is finished to respectively obtain a methyl polysiloxane ladder-support prepolymer or a phenyl polysiloxane ladder-support prepolymer;
(2) dissolving the methyl polysiloxane ladder-support prepolymer and the phenyl polysiloxane ladder-support prepolymer in an organic solvent, controlling the temperature to be 25-60 ℃, then dropwise adding an acid solution to carry out a cohydrolysis reaction, adding trimethylchlorosilane to seal the end after the reaction is finished, and separating and drying the product to obtain the trapezoidal reinforced silicon resin.
Further, the number average molecular weight of the methyl vinyl silicone rubber and the hydroxyl-terminated silicone rubber is 20 to 100 ten thousand; the vinyl content (wt.%) of the methyl vinyl silicone rubber is 0.03-2.5%; the viscosity of the hydrogen-containing silicone oil is 10-100 mPa · s, and the hydrogen content (wt.%) of the hydrogen-containing silicone oil is 0.02-2.0%.
Further, the inhibitor is selected from silanized alkynol or ethynyl cyclohexanol.
Further, the platinum catalyst refers to chloroplatinic acid or complex platinum catalyst (such as 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0)), and the concentration of the catalytic amount (in terms of platinum content) of the platinum catalyst in the system is 3-200 ppm.
Further, the functional assistant is selected from at least one of a filler, a silane coupling agent, a heat-resistant additive, an antistatic agent, and the like.
Further, the diluting solvent is one or a mixed solvent of more than two of toluene, xylene, isopropanol, isobutanol, ethyl acetate and isoparaffin solvent oil.
Further, the organic peroxide catalyst is selected from at least one of Benzoyl Peroxide (BPO) and 2, 4-dichlorobenzoyl peroxide (DCBP).
Further, the structure of the vinyl-terminated polydimethylsiloxane in the step (1) is shown as the following formula (I):
Figure BDA0002802331930000041
the structure of the methyl polysiloxane ladder-support prepolymer is shown as the following formula (II):
Figure BDA0002802331930000042
wherein A represents
Figure BDA0002802331930000043
a is an integer of 0 to 50. More preferably, a is an integer of 8 to 25. The length of the methylpolysiloxane bridge affects the overall rigidity of the molecule, and the trapezoidal increase obtained with polysiloxane bridge of the appropriate length is verifiedThe strong silicone resin can achieve obvious effects of capacity increasing, strengthening and high temperature resistance at the same time.
Further, the structure of the vinyl-terminated polyphenyl methyl siloxane in the step (1) is shown as the following formula (III):
Figure BDA0002802331930000044
the structure of the phenyl polysiloxane ladder support prepolymer is shown as the following formula (IV):
Figure BDA0002802331930000045
wherein B represents
Figure BDA0002802331930000046
b is an integer of 1 to 50. More preferably, b is an integer of 8 to 25. The length of the phenyl polysiloxane bridge group influences the integral rigidity of molecules, and the trapezoidal reinforced silicon resin obtained by verifying the phenyl polysiloxane bridge group with proper length can simultaneously achieve obvious effects of compatibilization, reinforcement, high temperature resistance and high transparency.
Further, in the step (1), the organic solvent is one or a mixture of two or more selected from ethanol, n-propanol, isopropanol, tert-butanol, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, tetrahydrofuran, cyclohexanone, dimethyl phthalate, and the like.
Further, the inert atmosphere in the step (1) refers to a nitrogen atmosphere.
Further, the platinum catalyst in the step (1) is chloroplatinic acid or a complex platinum catalyst (such as 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0)), and the concentration of the platinum catalyst (in terms of platinum content) in the reaction system is 3-50 ppm.
Further, the molar ratio of the vinyl-terminated polydimethylsiloxane or the vinyl-terminated polyphenylmethylsiloxane to the methyldimethoxysilane in the step (1) is 0.5 (1-1.2). The proper H excess is favorable for promoting the vinyl-terminated polydimethylsiloxane or the vinyl-terminated polyphenyl methylsiloxane to react as much as possible to generate the ladder support prepolymer, and the excess methyldimethoxysilane can be removed by reduced pressure distillation, so that the purity of the product is ensured.
Further, the time of the addition reaction in the step (1) is 1-4 h.
Further, the molar ratio of the methyl polysiloxane ladder-support prepolymer to the phenyl polysiloxane ladder-support prepolymer in the step (2) is 1: 2-2: 1. The methyl polysiloxane ladder support has better molecular flexibility, the phenyl polysiloxane ladder support has higher cohesive strength and refractive index, and the combination of the methyl polysiloxane ladder support and the phenyl polysiloxane ladder support can simultaneously achieve the effects of obvious compatibilization, reinforcement, high temperature resistance and high transparency.
Further, the organic solvent in the step (2) is one or a mixed solvent of two or more selected from methanol, ethanol, isopropanol, n-butanol, toluene, xylene, acetone, tetrahydrofuran, 1, 4-dioxane, cyclohexane and dimethyl sulfoxide.
Further, the separation and drying of the product in the step (2) means that the reaction product is extracted by toluene, washed to be neutral by water, and then dried in vacuum and the solvent is removed.
The theoretical structure of the trapezoid reinforced silicone resin can be represented as shown in the following formula (V):
Figure BDA0002802331930000061
the corresponding preparation formula is shown below:
Figure BDA0002802331930000062
wherein m and n represent the polymerization degree of each ladder strut chain link and have no definite limit value; however, the value of m and n is in the range of 0 to 120 by GPC molecular weight measurement of the synthesized product under limited conditions.
The preparation method of the ladder-shaped silicone resin reinforced organic silicon pressure-sensitive adhesive comprises the following steps (1) or (2):
(1) adding methyl vinyl silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluting solvent, stirring and dispersing uniformly, then adding hydrogen-containing silicone oil, an inhibitor, a platinum catalyst and a functional assistant, stirring and mixing uniformly to obtain trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive;
(2) adding the hydroxyl-terminated silicone rubber, the MQ silicone resin and the trapezoidal reinforced silicone resin into a diluting solvent, uniformly stirring and dispersing, then adding the organic peroxide catalyst and the functional assistant, and uniformly stirring and mixing to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Compared with the prior art, the invention has the beneficial effects that:
(1) the trapezoid silicon resin prepared by adding a specific method can improve the peeling strength and the high-temperature viscosity, and also has the effects of promoting the dispersion of MQ silicon resin to improve the uniformity of the reinforcing effect and improving the transparency of the product.
(2) The reinforcing effect of the MQ silicone resin can be improved by adding the specific trapezoid silicone resin, the surface of the adhesive layer of the obtained pressure-sensitive adhesive after high-temperature curing has no phenomenon of corrugation or shrinkage cavity, no adhesive remains during stripping, and the using effect is better.
(3) In the preparation process of the ladder-shaped silicon reinforced resin, the methyl polysiloxane ladder-support prepolymer and the phenyl polysiloxane ladder-support prepolymer are prepared by adopting a hydrosilylation reaction, compared with the existing hydrolysis condensation method, the reaction does not need to be adjusted by controlling the hydrolysis degree, and the reaction specificity is good.
Drawings
Fig. 1 to 3 are infrared spectrograms of the vinyl terminated tetramethyldisiloxane, the methylpolysiloxane ladder support prepolymer and the finally obtained ladder-shaped silicone resin in example 2 of the present invention, respectively.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of methyl vinyl silicone rubber (the number average molecular weight is 50 ten thousand, the vinyl content is 0.75%), 100 parts of MQ silicone resin (the molecular weight is 3000-4000, and the M/Q is 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 10 parts of hydrogen-containing silicone oil (the viscosity is 50mPa & s, the hydrogen content is 0.3%), 1 part of inhibitor silanization alkynol, 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) (the platinum content is 10ppm), and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern1300), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 50ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 4 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation to remove residual solvent and low-boiling substances at the temperature of 90 ℃ under the vacuum degree of-0.095 MPa to obtain the methyl polysiloxane ladder stay prepolymer.
(2) Preparing a phenyl polysiloxane ladder support prepolymer:
in a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated polyphenylmethylsiloxane (b: 15, average molecular weight M) was chargedn2200), and mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 deg.C under nitrogen protection, adding calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into four-mouth bottle, and making the systemThe platinum content of the prepolymer is 50ppm, then a constant-pressure dropping funnel is opened to slowly add methyldimethoxysilane (the molar ratio of vinyl to hydrogen is 1: 1.1) into a four-mouth bottle, the temperature is controlled to be 90 ℃ to carry out reflux reaction for 4 hours, after the reaction is finished, isopropanol and ethylene glycol monoethyl ether solvent are firstly recovered under normal pressure, and then the residual solvent and low-boiling-point substances are removed by reduced pressure evaporation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the phenyl polysiloxane ladder-bracing prepolymer.
(3) And (3) carrying out co-condensation to prepare the trapezoidal reinforced silicone resin:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a toluene solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 30 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, taking an organic phase layer by layer, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding methyl vinyl silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding hydrogen-containing silicone oil, an inhibitor and a platinum catalyst, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Comparative example 1
In comparison with example 1, no trapezoidal reinforcing silicone resin was added.
The silicone pressure-sensitive adhesives obtained in example 1 and comparative example 1 above were tested for their adhesive properties, high temperature resistance and transparency:
and uniformly coating the glue solution on a release film, and curing for 5min at 40 ℃ to obtain the organic silicon pressure-sensitive adhesive.
The peel strength (N/25mm) is tested according to standard GB 2792-81.
The high temperature resistance test is carried out according to the following method: adhering an organic silicon pressure sensitive adhesive tape and a polyimide film, carrying out hot pressing at 180 ℃ and 0.3MPa for 15s, removing a release film, adhering an adhesive surface and a stainless steel sheet, carrying out hot pressing at 180 ℃ and 0.3MPa for 30min, then carrying out heat preservation on the test piece at 180 ℃ for 1h, cooling to room temperature, finally subjecting the adhesive tape to 500g of shearing force, and measuring the time required for the adhesive tape to fall off from the stainless steel sheet in a 280 ℃ oven.
The light transmittance test was performed as follows: and measuring the light transmittance (%) of the sample in a visible light wavelength range of 200-800 nm by using an ultraviolet-visible spectrophotometer at 25 ℃.
The test results are shown in table 1 below:
TABLE 1
Test sample Peel strength High temperature hold time Light transmittance
Example 1 15.6 205min 97
Comparative example 1 13.2 127min 86
As can be seen from the results in Table 1, the organic silicon pressure-sensitive adhesive enhanced by adopting the trapezoidal silicone resin has the advantages of obviously improved bonding performance, high temperature resistance and transparency.
Example 2
The silicone pressure-sensitive adhesive reinforced by the trapezoidal silicone resin is prepared from the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP, and 200 parts of diluent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
in a four-neck flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated tetramethyldisiloxane (vinyl double head, a is 0, M)n186) and an isopropanol solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of chloroplatinic acid catalyst into a four-mouth bottle to ensure that the platinum content in the system is 25ppm, then opening a constant-pressure dropping funnel to slowly add methyldimethoxysilane (fed according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, controlling the temperature to be 80 ℃ to carry out reflux reaction for 2 hours, recovering the isopropanol solvent under normal pressure after the reaction is finished, and then evaporating residual solvent and low-boiling-point substances under reduced pressure at the vacuum degree of-0.095 MPa and the temperature of 70 ℃ to obtain the methyl polysiloxane ladder support prepolymer.
(2) Preparation of phenyl polysiloxane ladder support prepolymer:
in a four-neck flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated polyphenylmethylsiloxane (b ═ 1, M)n322) and isopropanol solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of chloroplatinic acid catalyst into a four-mouth bottle to ensure that the platinum content in the system is 25ppm, then opening a constant-pressure dropping funnel to slowly add methyldimethoxysilane (fed according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, controlling the temperature to be 80 ℃ to carry out reflux reaction for 2 hours, recovering the isopropanol solvent under normal pressure after the reaction is finished, and then adding the isopropanol solvent under the vacuum degree of-0.095 MPa,And (3) evaporating residual solvent and low-boiling-point substances at the temperature of 70 ℃ under reduced pressure to obtain the phenyl polysiloxane ladder-support prepolymer.
(3) And (3) preparing the trapezoidal reinforced silicone resin by cocondensation:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in an isopropanol solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 40 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, washing to be neutral, then carrying out vacuum drying and removing the solvent to obtain white powdery trapezoidal reinforced silicon resin.
The infrared spectrums of the vinyl terminated tetramethyldisiloxane, the methylpolysiloxane ladder support prepolymer and the finally obtained ladder-shaped silicone resin are shown in fig. 1, fig. 2 and fig. 3, respectively. As can be seen from the results shown in FIGS. 1 to 3, the absorption peak of vinyl group in the prepolymer of methyl polysiloxane ladder support disappears at 1100 to 1000cm-1Is the strong broad peak of Si-O stretching vibration; the absorption peak of Si-O-Si (1051cm-1) in the ladder-shaped silicon resin is obviously enhanced, which shows that alkoxy in the ladder support prepolymer is hydrolyzed and condensed to completely form a Si-O-Si structure.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 3
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a: 8, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern800) and ethylene glycol monoethyl ether solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 10ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of vinyl to hydrogen of 1: 1.05) into the four-mouth bottle, controlling the temperature to be 100 ℃ to carry out reflux reaction for 3 hours, recovering the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure evaporation to remove residual solvent and low-boiling-point substances under the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the methylpolysiloxane ladder bracing prepolymer.
(2) Preparing a phenyl polysiloxane ladder support prepolymer:
a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer was charged with vinyl-terminated polyphenylmethylsiloxane (b ═ 8, average molecular weight M)n1200) and ethylene glycol monoethyl ether solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 10ppm, then opening a constant-pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of vinyl to hydrogen of 1: 1.05) into the four-mouth bottle, controlling the temperature to be 100 ℃ to carry out reflux reaction for 3 hours, recovering the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced-pressure distillation to remove residual solvent and low-boiling-point substances under the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the phenyl polysiloxane ladder bracing prepolymer.
(3) And (3) preparing the trapezoidal reinforced silicone resin by cocondensation:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in an acetone solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 50 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, washing to be neutral, then carrying out vacuum drying and removing the solvent to obtain white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 4
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
in a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated polydimethylsiloxane (a: 15, average molecular weight M) was chargedn1300), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 50ppm, then opening a constant-pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 4 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then controlling the vacuum degree to be-0.095 MPa,And (3) evaporating residual solvent and low-boiling-point substances at the temperature of 90 ℃ under reduced pressure to obtain the methyl polysiloxane ladder-bracing prepolymer.
(2) Preparation of phenyl polysiloxane ladder support prepolymer:
in a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated polyphenylmethylsiloxane (b: 15, average molecular weight M) was chargedn2200), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 50ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 4 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation to remove residual solvent and low-boiling substances at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the phenyl polysiloxane ladder stay prepolymer.
(3) And (3) carrying out co-condensation to prepare the trapezoidal reinforced silicone resin:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a toluene solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 30 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, taking an organic phase layer by layer, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 5
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
in a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated polydimethylsiloxane (having an average molecular weight M of 25 ═ a) was chargedn2000) and a propylene glycol ether solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 5ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, controlling the temperature to be 110 ℃ to carry out reflux reaction for 1h, recovering the propylene glycol ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure evaporation to remove residual solvent and low-boiling-point substances under the conditions of vacuum degree of-0.095 MPa and temperature of 90 ℃ to obtain the methylpolysiloxane ladder support prepolymer.
(2) Preparing a phenyl polysiloxane ladder support prepolymer:
a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer was charged with vinyl-terminated polyphenylmethylsiloxane (b-25, average molecular weight M)n3600) and propylene glycol ether solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 5ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, controlling the temperature to be 110 ℃ to carry out reflux reaction for 1h,after the reaction is finished, the propylene glycol ether solvent is recycled under normal pressure, and then the residual solvent and low-boiling-point substances are removed by reduced pressure evaporation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the phenyl polysiloxane ladder-bracing prepolymer.
(3) And (3) carrying out co-condensation to prepare the trapezoidal reinforced silicone resin:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a tetrahydrofuran solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 60 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, layering, taking an organic phase, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 6
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP, and 200 parts of diluent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a: 50, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern3900) and cyclohexanone solvent, stirring for dissolving, heating and raising under the protection of nitrogenThe temperature is raised to 80 ℃, the calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst is added into a four-mouth bottle to ensure that the platinum content in the system is 15ppm, then a constant pressure dropping funnel is opened to slowly add methyldimethoxysilane (the molar ratio of vinyl to hydrogen is 1: 1.1) into the four-mouth bottle, the temperature is controlled at 110 ℃ for reflux reaction for 2 hours, the cyclohexanone solvent is recycled under normal pressure after the reaction is finished, and then the residual solvent and low-boiling-point substances are removed by reduced pressure evaporation at the vacuum degree of-0.095 MPa and the temperature of 100 ℃ to obtain the methyl polysiloxane ladder support prepolymer.
(2) Preparation of phenyl polysiloxane ladder support prepolymer:
a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer was charged with vinyl-terminated polyphenylmethylsiloxane (b: 50, average molecular weight M)n7000) and cyclohexanone solvent, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to enable the platinum content in the system to be 15ppm, then opening a constant-pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, controlling the temperature to be 110 ℃ to carry out reflux reaction for 2 hours, recovering the cyclohexanone solvent under normal pressure after the reaction is finished, and then evaporating residual solvent and low-boiling-point substances under reduced pressure at the vacuum degree of-0.095 MPa and the temperature of 100 ℃ to obtain the phenyl polysiloxane ladder support prepolymer.
(3) And (3) preparing the trapezoidal reinforced silicone resin by cocondensation:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a dimethyl sulfoxide solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 50 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, layering, taking an organic phase, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the viscous liquid ladder-shaped reinforced silicone resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 7
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern1300), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to enable the platinum content in the system to be 20ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 3 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to remove residual solvent and low-boiling substances to obtain the methyl polysiloxane ladder stay prepolymer.
(2) Preparation of phenyl polysiloxane ladder support prepolymer:
vinyl-terminated polyphenylmethylsiloxane (b 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrern2200), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to enable the platinum content in the system to be 20ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 3 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to remove residual solvent and low-boiling substances to obtain the phenyl polysiloxane ladder stay prepolymer.
(3) And (3) preparing the trapezoidal reinforced silicone resin by cocondensation:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a toluene solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:2, controlling the temperature to be 40 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, taking an organic phase layer by layer, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 8
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 10 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern1300), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 20ppm, then opening a constant-pressure dropping funnel to slowly add methyldimethoxysilane (fed according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 3 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced-pressure distillation to remove residual solvent and low-boiling substances under the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the methyl polysiloxane ladder support prepolymer.
(2) Preparation of phenyl polysiloxane ladder support prepolymer:
vinyl-terminated polyphenylmethylsiloxane (b 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrern2200), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to enable the platinum content in the system to be 20ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 3 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to remove residual solvent and low-boiling substances to obtain the phenyl polysiloxane ladder stay prepolymer.
(3) And (3) carrying out co-condensation to prepare the trapezoidal reinforced silicone resin:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a toluene solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 2:1, controlling the temperature to be 40 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, taking an organic phase layer by layer, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 9
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 5 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoid reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern1300), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 50ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of vinyl to hydrogen of 1: 1.1) into the four-mouth bottle, and controlling the temperatureReflux reaction is carried out for 4h at the temperature of 90 ℃, isopropanol and ethylene glycol monoethyl ether solvent are recycled under normal pressure after the reaction is finished, and residual solvent and low-boiling-point substances are removed by reduced pressure evaporation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the methyl polysiloxane ladder-strut prepolymer.
(2) Preparing a phenyl polysiloxane ladder support prepolymer:
in a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrer, vinyl-terminated polyphenylmethylsiloxane (b: 15, average molecular weight M) was chargedn2200), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 50ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 4 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation to remove residual solvent and low-boiling substances at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the phenyl polysiloxane ladder stay prepolymer.
(3) And (3) carrying out co-condensation to prepare the trapezoidal reinforced silicone resin:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a toluene solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 30 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, taking an organic phase layer by layer, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Example 10
The trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive comprises the following components in parts by weight:
100 parts of hydroxyl-terminated silicone rubber (with an average molecular weight of 60 ten thousand), 100 parts of MQ silicone resin (with a molecular weight of 3000-4000 and an M/Q value of 0.75-0.8), 25 parts of trapezoidal reinforced silicone resin, 1.6 parts of organic peroxide catalyst BOP and 200 parts of diluent solvent toluene.
The trapezoidal reinforced silicone resin is prepared by the following method:
(1) preparing a methyl polysiloxane ladder support prepolymer:
vinyl-terminated polydimethylsiloxane (a 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer, and electric stirrern1300), and a mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 ℃ under the protection of nitrogen, adding a calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into a four-mouth bottle to ensure that the platinum content in the system is 50ppm, then opening a constant pressure dropping funnel to slowly add methyldimethoxysilane (feeding according to the molar ratio of 1:1.1 of vinyl to hydrogen) into the four-mouth bottle, controlling the temperature to be 90 ℃ to carry out reflux reaction for 4 hours, recovering the isopropanol and the ethylene glycol monoethyl ether solvent under normal pressure after the reaction is finished, and then carrying out reduced pressure distillation to remove residual solvent and low-boiling substances at the temperature of 90 ℃ under the vacuum degree of-0.095 MPa to obtain the methyl polysiloxane ladder stay prepolymer.
(2) Preparation of phenyl polysiloxane ladder support prepolymer:
vinyl-terminated polyphenylmethylsiloxane (b 15, average molecular weight M) was charged into a four-necked flask equipped with a constant pressure dropping funnel, reflux condenser, thermometer and electric stirrern2200), and mixed solvent of isopropanol and ethylene glycol monoethyl ether, stirring and dissolving uniformly, heating to 80 deg.C under nitrogen protection, adding calculated amount of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum (0) catalyst into four-mouth bottle, and making systemThe platinum content in the prepolymer is 50ppm, then a constant-pressure dropping funnel is opened to slowly add methyldimethoxysilane (the molar ratio of vinyl to hydrogen is 1: 1.1) into a four-mouth bottle, the temperature is controlled to be 90 ℃ to carry out reflux reaction for 4 hours, after the reaction is finished, isopropanol and ethylene glycol monoethyl ether solvent are firstly recovered under normal pressure, and then the residual solvent and low-boiling-point substances are removed by reduced pressure evaporation at the vacuum degree of-0.095 MPa and the temperature of 90 ℃ to obtain the phenyl polysiloxane ladder-bracing prepolymer.
(3) And (3) carrying out co-condensation to prepare the trapezoidal reinforced silicone resin:
dissolving the methyl polysiloxane ladder support prepolymer obtained in the step (1) and the phenyl polysiloxane ladder support prepolymer obtained in the step (2) in a toluene solvent, controlling the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer to be 1:1, controlling the temperature to be 30 ℃, then dropwise adding concentrated hydrochloric acid to carry out cohydrolysis reaction, adding Trimethylchlorosilane (TMCS) to terminate the end after the reaction is finished, extracting the product by toluene, taking an organic phase layer by layer, washing the organic phase to be neutral, then carrying out vacuum drying and removing the solvent to obtain the white powdery trapezoidal reinforced silicon resin.
The trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive is prepared by the following method:
adding hydroxyl-terminated silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluent solvent toluene, stirring and dispersing uniformly, then adding an organic peroxide catalyst BOP, stirring and mixing uniformly to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
Comparative example 2
In comparison with example 2, no trapezoidal reinforcing silicone resin was added.
1. And performing MQ silicon resin compatibilization performance test on the trapezoidal reinforced silicon resin obtained in the above embodiments 2-8.
The test conditions were: toluene is used as a dispersing solvent, the mass ratio of toluene to MQ silicon resin (white powder, the molecular weight is 3000-4000, and the M/Q is 0.75-0.8) is 1:1, the adding amount of the trapezoidal reinforced silicon resin is 10% of that of the MQ silicon resin, the stirring speed is 800rpm, the temperature is room temperature, the stirring and the dispersing are carried out until the solution is clear and transparent without white spots, the viscosity of the solution is stable and does not change, the dispersion is uniform, the shortest time required by the uniform dispersion of the solutions is recorded, and the non-added trapezoidal silicon resin is used as a control sample. The test results are shown in table 2 below.
TABLE 2
Test sample Time of dispersion Test sample Time of dispersion
Example 1 12min Example 5 6min
Example 2 9min Example 6 8min
Example 3 7min Example 7 7min
Example 4 7min Control sample 21min
As is apparent from the results in Table 2, the trapezoidal reinforced silicone resin obtained by the invention can obviously enhance the dispersion performance of the MQ silicone resin, and the compatibilization effect is more obvious as the length of the polysiloxane ladder chain increases.
2. The organic silicon pressure-sensitive adhesive obtained in the above examples 2-10 and comparative example 2 was subjected to adhesion performance, high temperature resistance and transparency performance tests:
and (3) uniformly coating the glue solution on a release film, curing for 3min at 150 ℃, and cooling to room temperature to obtain the organic silicon pressure-sensitive adhesive.
The peel strength (N/25mm) is tested according to standard GB 2792-81.
The high temperature resistance test is carried out according to the following method: adhering an organic silicon pressure sensitive adhesive tape and a polyimide film, carrying out hot pressing at 180 ℃ and 0.3MPa for 15s, removing a release film, adhering an adhesive surface and a stainless steel sheet, carrying out hot pressing at 180 ℃ and 0.3MPa for 30min, then carrying out heat preservation on the test piece at 180 ℃ for 1h, cooling to room temperature, finally subjecting the adhesive tape to 500g of shearing force, and measuring the time required for the adhesive tape to fall off from the stainless steel sheet in a 280 ℃ oven.
The light transmittance test was performed as follows: and measuring the light transmittance (%) of the sample in a visible light wavelength range of 200-800 nm by using an ultraviolet-visible spectrophotometer at 25 ℃.
The test results are shown in table 3 below:
TABLE 3
Test sample Peel strength High temperature hold tack time Light transmittance
Example 2 16.1 126min 93
Example 3 18.2 137min 94
Example 4 20.4 155min 95
Example 5 17.5 135min 96
Example 6 15.9 124min 97
Example 7 21.1 168min 98
Example 8 20.6 129min 91
Example 9 16.3 131min 91
Example 10 20.9 162min 97
Comparative example 2 15.6 102min 84
The results in table 3 clearly show that the trapezoidal silicone resin obtained in the invention can significantly enhance the bonding strength, high temperature resistance and transparency of the organic silicon pressure-sensitive adhesive, and the phenyl polysiloxane ladder support is more beneficial to the improvement of the high temperature resistance and transparency.
In addition, in the test curing process, the silicone pressure-sensitive adhesive obtained in comparative example 2 is easy to have a shrinkage cavity phenomenon, and residual adhesive is attached to the test board during stripping, but the samples obtained in examples 2 to 10 of the invention are not found to have the above phenomenon. The trapezoidal silicon resin prepared by adding the specific method into the organic silicon pressure-sensitive adhesive disclosed by the invention has the advantages that the dispersion of the MQ silicon resin is promoted, the reinforcing effect is uniform and stable, and the defects of shrinkage cavity caused by uneven stress during high-temperature curing and easy adhesive residue caused by uneven adhesive force are avoided.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. The organic silicon pressure-sensitive adhesive reinforced by the trapezoid silicon resin is characterized in that: the organic silicon pressure-sensitive adhesive comprises the following components (1) or (2) in parts by weight:
component (1): 80-120 parts of methyl vinyl silicone rubber, 80-120 parts of MQ silicone resin, 5-25 parts of trapezoidal reinforced silicone resin, 5-12 parts of hydrogen-containing silicone oil, 1-3 parts of inhibitor, a catalytic amount of platinum catalyst, 0-10 parts of functional assistant, and a diluting solvent with solid content of 40% -65%;
component (2): 80-120 parts of hydroxyl-terminated silicone rubber, 80-120 parts of MQ silicone resin, 5-25 parts of trapezoidal reinforced silicone resin, 1-5 parts of organic peroxide catalyst, 0-10 parts of functional assistant and a diluting solvent with solid content of 40-65%;
the trapezoid reinforced silicone resin is prepared by the following method:
(1) respectively dissolving vinyl-terminated polydimethylsiloxane or vinyl-terminated polyphenyl methylsiloxane in an organic solvent, heating to 60-80 ℃ under the protection of nitrogen, adding a platinum catalyst, then dropwise adding methyldimethoxysilane, controlling the temperature to be 75-110 ℃ to carry out addition reaction, and evaporating to remove the organic solvent and low-boiling-point substances after the reaction is finished to respectively obtain a methyl polysiloxane ladder-bracing prepolymer or a phenyl polysiloxane ladder-bracing prepolymer;
(2) dissolving a methyl polysiloxane ladder support prepolymer and a phenyl polysiloxane ladder support prepolymer in an organic solvent, controlling the temperature to be 25-60 ℃, then dropwise adding an acid solution to carry out a cohydrolysis reaction, adding trimethylchlorosilane for end capping after the reaction is finished, and separating and drying a product to obtain the trapezoidal reinforced silicon resin;
the structure of the vinyl-terminated polydimethylsiloxane in the step (1) is shown as the following formula (I):
Figure DEST_PATH_IMAGE001
formula (I);
the structure of the methyl polysiloxane ladder-support prepolymer is shown as the following formula (II):
Figure 139279DEST_PATH_IMAGE002
formula (II);
wherein A represents
Figure DEST_PATH_IMAGE003
(ii) a a is an integer of 0 to 50;
the structure of the vinyl-terminated polyphenyl methyl siloxane is shown as the following formula (III):
Figure 259681DEST_PATH_IMAGE004
formula (III);
the structure of the phenyl polysiloxane ladder support prepolymer is shown as the following formula (IV):
Figure DEST_PATH_IMAGE005
formula (IV);
wherein B represents
Figure 242681DEST_PATH_IMAGE006
(ii) a b is an integer of 1 to 50;
the molar ratio of the vinyl-terminated polydimethylsiloxane or the vinyl-terminated polyphenyl methylsiloxane to the methyldimethoxysilane in the step (1) is 0.5 (1-1.2);
the molar ratio of the methyl polysiloxane ladder support prepolymer to the phenyl polysiloxane ladder support prepolymer in the step (2) is 1: 2-2: 1.
2. The silicone pressure sensitive adhesive of claim 1, wherein: the number average molecular weight of the methyl vinyl silicone rubber and the hydroxyl terminated silicone rubber is 20-100 ten thousand; the vinyl content of the methyl vinyl silicone rubber is 0.03-2.5%; the viscosity of the hydrogen-containing silicone oil is 10-100 mPa.s, and the hydrogen content of the hydrogen-containing silicone oil is 0.02% -2.0%.
3. The silicone pressure sensitive adhesive of claim 1, wherein: the inhibitor is selected from silanized alkynol or ethyne cyclohexanol; the platinum catalyst is a complex platinum catalyst, and the concentration of the catalytic amount of the platinum catalyst in the system is 3-200 ppm in terms of platinum content.
4. The silicone pressure sensitive adhesive of claim 1, wherein: the functional auxiliary agent is selected from at least one of a filler, a silane coupling agent, a heat-resistant additive and an antistatic agent; the diluting solvent is one or more than two mixed solvents selected from toluene, xylene, isopropanol, isobutanol, ethyl acetate and isoparaffin solvent oil; the organic peroxide catalyst is at least one selected from benzoyl peroxide and 2, 4-dichlorobenzoyl peroxide.
5. The silicone pressure sensitive adhesive of claim 1, wherein: the organic solvent in the step (1) is one or a mixture of more than two of ethanol, normal propyl alcohol, isopropanol, tertiary butanol, propylene glycol ethyl ether, propylene glycol butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, tetrahydrofuran, cyclohexanone and dimethyl phthalate; the platinum catalyst is a complex platinum catalyst, and the concentration of the platinum catalyst in a reaction system is 3-50 ppm in terms of platinum content.
6. The silicone pressure sensitive adhesive of claim 1, wherein: the time of the addition reaction in the step (1) is 1-4 h.
7. The silicone pressure sensitive adhesive of claim 1, wherein: the organic solvent in the step (2) is one or more than two mixed solvents selected from methanol, ethanol, isopropanol, n-butanol, toluene, xylene, acetone, tetrahydrofuran, 1, 4-dioxane, cyclohexane and dimethyl sulfoxide; the separation and drying of the product refers to extracting the reaction product by toluene, washing the reaction product to be neutral by water, and then carrying out vacuum drying and removing the solvent.
8. The method for preparing the ladder-shaped silicone resin reinforced silicone pressure sensitive adhesive according to any one of claims 1 to 7, comprising the steps of (a) or (b):
(a) adding methyl vinyl silicone rubber, MQ silicone resin and trapezoidal reinforced silicone resin into a diluting solvent, stirring and dispersing uniformly, then adding hydrogen-containing silicone oil, an inhibitor, a platinum catalyst and a functional assistant, stirring and mixing uniformly to obtain trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive;
(b) adding the hydroxyl-terminated silicone rubber, the MQ silicone resin and the trapezoidal reinforced silicone resin into a diluting solvent, uniformly stirring and dispersing, then adding the organic peroxide catalyst and the functional assistant, and uniformly stirring and mixing to obtain the trapezoidal silicone resin reinforced silicone pressure-sensitive adhesive.
CN202011354922.4A 2020-11-27 2020-11-27 Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof Active CN112480862B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011354922.4A CN112480862B (en) 2020-11-27 2020-11-27 Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011354922.4A CN112480862B (en) 2020-11-27 2020-11-27 Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112480862A CN112480862A (en) 2021-03-12
CN112480862B true CN112480862B (en) 2022-07-12

Family

ID=74935730

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011354922.4A Active CN112480862B (en) 2020-11-27 2020-11-27 Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112480862B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113845861A (en) * 2021-09-30 2021-12-28 苏州世华新材料科技股份有限公司 Low-climbing organic silicon protective film and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB755198A (en) * 1954-01-11 1956-08-15 Midland Silicones Ltd Organosiloxane co-polymers
JPH05125192A (en) * 1991-10-15 1993-05-21 Showa Denko Kk Graft modified ladder silicone and its composition
JPH09100352A (en) * 1995-08-03 1997-04-15 Pola Chem Ind Inc Polysiloxane and its production
US6423772B1 (en) * 1999-07-16 2002-07-23 Institute Of Chemistry, Chinese Academy Of Sciences Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same
CN107513367A (en) * 2017-09-20 2017-12-26 成都硅宝科技股份有限公司 A kind of dealcoholized type shelf-stable RTV electronics drapes over one's shoulders deposited glue and preparation method thereof
CN107880267A (en) * 2017-11-17 2018-04-06 长兴（中国）投资有限公司 Siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof
CN108003348A (en) * 2017-12-15 2018-05-08 长兴（中国）投资有限公司 Siloxanes abutting ladder poly-siloxane, its preparation method and application
CN109957110A (en) * 2017-12-25 2019-07-02 北京科化新材料科技有限公司 Trapezoidal organosilicon polymer and its preparation method and application and LED packaging plastic

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB755198A (en) * 1954-01-11 1956-08-15 Midland Silicones Ltd Organosiloxane co-polymers
JPH05125192A (en) * 1991-10-15 1993-05-21 Showa Denko Kk Graft modified ladder silicone and its composition
JPH09100352A (en) * 1995-08-03 1997-04-15 Pola Chem Ind Inc Polysiloxane and its production
US6423772B1 (en) * 1999-07-16 2002-07-23 Institute Of Chemistry, Chinese Academy Of Sciences Organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof, and the method for producing the same
CN107513367A (en) * 2017-09-20 2017-12-26 成都硅宝科技股份有限公司 A kind of dealcoholized type shelf-stable RTV electronics drapes over one's shoulders deposited glue and preparation method thereof
CN107880267A (en) * 2017-11-17 2018-04-06 长兴（中国）投资有限公司 Siloxanes abutting ladder poly-siloxane of siloxane bridge base silane end-blocking and preparation method thereof
CN108003348A (en) * 2017-12-15 2018-05-08 长兴（中国）投资有限公司 Siloxanes abutting ladder poly-siloxane, its preparation method and application
CN109957110A (en) * 2017-12-25 2019-07-02 北京科化新材料科技有限公司 Trapezoidal organosilicon polymer and its preparation method and application and LED packaging plastic

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
超分子构筑调控合成结构规整的梯形聚合物及其应用研究;周奇龙等;《高分子学报》;20071015(第10期);第918-930页 *

Also Published As

Publication number Publication date
CN112480862A (en) 2021-03-12

Similar Documents

Publication Publication Date Title
KR101512529B1 (en) Polysiloxane, method for producing the same, and method for producing cured product of the same
JPH06166740A (en) Uv-curing epoxysilicone carrying pendant silicone resin
EP2452993B1 (en) Thermosetting fluoropolyether adhesive composition and adhesion method
CN100430432C (en) Silicon-containing polymer, process for rpoducing the same, heat-resistant resin composition, and heat-resistant film
JPH0128792B2 (en)
JPS6043872B2 (en) Thermosetting organopolysiloxane composition
KR20110004272A (en) Process for the production of silicone coatings and silicone moldings from photocrosslinkable silicone mixtures
CN106146850B (en) Tackifier for addition type organic silicon impregnating resin and preparation method thereof
EP2896658A1 (en) Curable resin composition
CN112341625B (en) High-temperature-resistant high-compatibility trapezoidal silicone resin and preparation method and application thereof
WO2019087759A1 (en) Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet
CN112480862B (en) Trapezoidal silicone resin reinforced organic silicon pressure-sensitive adhesive and preparation method thereof
US5086192A (en) Photopolymerizable compositions and photoinitiators therefor
JP5139882B2 (en) Photosensitive resin composition and method for producing substrate with resin layer using the same
CN101906114A (en) Cation ultraviolet curing group-containing silicon oxide compound and preparation method thereof
CN105778100B (en) A kind of organic silicon rigidity-increasing stick and preparation method thereof and a kind of addition-type silicon rubber composition
CN111363103A (en) Preparation method of tackifier for addition type organic silicon adhesive
CN111499870A (en) Boiling-resistant organic silicon pressure-sensitive adhesive tackifier and preparation method thereof
CN105255361A (en) Silicone impregnating varnish as well as preparation method and application thereof
JP3681582B2 (en) Epoxy group-containing silicone resin
CN110591557B (en) Organic silicon coating adhesive and preparation method thereof
CN115651602A (en) High-temperature-resistant addition type organic silicon pressure-sensitive adhesive composition and preparation method and application thereof
EP1010714B1 (en) Method for making functionalized siloxanes, compositions containing such siloxanes and articles made therefrom
JP4028672B2 (en) Method for producing reaction product
CN104812807A (en) Photo-dimerization functional group-containing organopolysiloxane, activation energy radiation-curable organopolysiloxane composition, and cured product thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant