CN116041708A - A kind of preparation method of antistatic agent compound for reactive organosilicon material - Google Patents

Abstract

The invention relates to the technical field of static electricity prevention of organic silicon materials, in particular to a preparation method of an antistatic agent compound for a reactive organic silicon material. The invention provides a preparation method of an antistatic agent compound for a reactive organic silicon material, which comprises the following steps: polysiloxane preparation reactions containing halogenated hydrocarbon groups and polyvinyl groups, preparation of polysiloxane intermediates containing quaternary ammonium salts and polyvinyl groups, and substitution synthesis reactions of fluorine-containing lithium salts and quaternary ammonium-based polysiloxanes. The main chain of the antistatic agent compound is polydiorganosiloxane, and the side chain contains a cationic and anionic antistatic agent structure and a vinyl functional group structure, so that the durability of the antistatic agent and the compatibility between the antistatic agent and the organosilicon material composition are improved.

Description

A kind of preparation method of antistatic agent compound for reactive organosilicon material

technical field

The invention relates to the field of antistatic technology of organosilicon materials, in particular to a preparation method of an antistatic agent compound for reactive organosilicon materials.

Background technique

Silicone materials have excellent properties such as low dielectric constant, low refractive index, low surface energy, chemical corrosion resistance, weather resistance, heat resistance and cold resistance, so they are widely used in high-end fields such as aerospace, automobiles and electronic products. However, due to the characteristics of high insulation and high surface resistance of silicone materials, there are problems such as static electricity due to contact with various substances, and easy to absorb dust in the air, which will greatly reduce the user experience. and look and feel. In particular, with the rapid development of electronic products, in order to prevent the surface of electronic products from being damaged by physical impacts that may occur during the process of transportation, storage, and assembly of products, a large number of protective films are used on the surface of electronic devices such as display screens to protect the surface from scratches and scratches. Clean protection. Because these protective films usually form a silicone-based pressure-sensitive adhesive layer on the surface of polyethylene terephthalate PET, and then stick to the surface of the display; due to the insulation of the silicone material itself, it will A large electrostatic voltage is generated to break down the attached object, resulting in defects in the device or display. In addition, the existence of static electricity may also become the root cause of dust adsorption or safety hazards. Two solutions are usually used for silicone-based protective film pressure-sensitive adhesives. One is to coat the polythiophene-based antistatic liquid on the PET substrate of the protective film to form an antistatic coating; the other is to apply the pressure-sensitive adhesive formula Add conductive substances such as carbon black, metal oxides and carbon nanotubes, as shown in the invention patent CN109016769A and CN109913 142A. However, the former cannot achieve a satisfactory anti-static effect, the surface resistance of the pressure-sensitive adhesive is high, and the tearing voltage is high; the latter has poor compatibility with the silicone formulation system, which will lead to a serious decrease in the transparency of the pressure-sensitive adhesive, and is not suitable for optical devices. Surface application of pressure sensitive tape.

In order to solve the above problems, the present invention provides a preparation method of an antistatic agent compound for reactive silicone materials.

Contents of the invention

The object of the present invention is to provide a method for preparing an antistatic agent compound for reactive silicone materials, so as to solve the problems raised in the above-mentioned background technology.

A preparation method for an antistatic agent compound for a reactive silicone material, comprising the following steps:

S1: Preparation of polysiloxane intermediates containing quaternary ammonium salts and polyvinyl groups

Mix polysiloxane intermediates containing halogenated hydrocarbon groups and polyvinyl groups, organic amines and solvents uniformly, heat up to 50-150°C, keep warm for 2-48 hours, distill under reduced pressure, recover organic amines and solvents, and obtain quaternary Ammonium salts and polyvinyl polysiloxane intermediates;

S2: Substitution synthesis reaction of fluorine-containing lithium salt and quaternary ammonium polysiloxane

Stir the polysiloxane intermediate containing quaternary ammonium salt and polyvinyl group, lithium bis-polyfluoroalkylsulfonimide and water evenly, and stir and react at a temperature of 10-80°C for 1h-48h to obtain the crude intermediate body; cool the above crude intermediate to 25-35°C, add extraction solvent, mix evenly, and extract; reduce pressure and rotary evaporate at a temperature of 20°C to 150°C, remove solvent and water, and obtain a reactive silicone adhesive. Antistatic compound.

More optimally, in S1, the preparation method of polysiloxane intermediates containing halogenated hydrocarbon groups and polyvinyl groups is as follows: terminal haloalkylmethyldialkoxysilane, hydroxyl-terminated vinylpolysiloxane, acidic catalyst Mix evenly, heat up to 50-100°C, keep warm for 2-48h, vacuumize to remove low boiling for 2-8h; add hexamethyldisiloxane, keep warm for 2-48h, slowly vacuumize to remove low boiling for 2-8h, The solid acid catalyst is removed by filtration to obtain a polysiloxane intermediate containing a halogenated hydrocarbon group and a polyvinyl group.

More optimally, in S1, the organic amine is any one or more of trialkylamines and pyrrole compounds, and its structural formula is as follows:

In the formula,

R ₁ , R ₂ , R ₃ and R ₄ are monovalent saturated alkyl structures, and their general structural formula is -C _p H _2p+1 , p is a natural number, 10≥p≥1;

R ₅ , R ₆ , R ₇ and R ₈ are any one of a hydrogen atom and a monovalent saturated alkyl structure, and its general structural formula is -C _t H _2t+1 , t is an integer, and 10≥t≥0.

More optimally, in S1, the solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylpyrrolidone, ethyl acetate, m- Any one or more of ditrifluorotoluene, toluene, xylene, methyl isobutyl ketone and butanone.

More optimally, in S2, the extraction solvent is any one or more of dichloromethane, chloroform, diethyl ether, petroleum ether, and m-trifluorotoluene.

More optimally, the structural formula of the terminal haloalkylmethyldialkoxysilane is as follows:

Any one or more of CH ₂ BrC _q-1 H _2q-2 S _i CH ₃ (OC _s H _2s+1 ) ₂ , CH ₂ ClC _q H _2q S _i CH ₃ (OC _s H _2s+1 ) ₂ kind;

In the formula, q and s are natural numbers, 10≥q≥1, 10≥s≥1;

Terminal haloalkylmethyldialkoxysilane can be γ-chloropropylmethyldipropoxysilane, γ-chloropropylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane , Chlorobutylmethyldiethoxysilane, Chlorobutylmethyldimethoxysilane, γ-Bromopropylmethyldipropoxysilane, γ-Bromopropylmethyldiethoxysilane, γ-Bromopropyl Any one or more of methyldimethoxysilane.

More optimally, the hydroxyl-terminated vinyl polysiloxane is hydroxyl-terminated methyl vinyl silicone oil.

More optimally, the acid catalyst is one or more of concentrated sulfuric acid, acid clay, trifluoromethanesulfonic acid and acid resin catalyst YKCH8501.

More optimally, in S1, the molar ratio of amine group and halogenated hydrocarbon group is 1:1～1.5:1; 1.5:1.

More optimally, the molar ratio of terminal haloalkylmethyldialkoxysilane and terminal hydroxyl vinyl polysiloxane is 1:1 to 1:20, and the amount of solid acid catalyst added is 1% to 1% of the total mass of the reaction substances. 10%.

Compared with the prior art, the beneficial effects achieved by the present invention are:

(1) The present invention provides a method for preparing an antistatic agent compound for reactive silicone materials, including: the preparation reaction of polysiloxane containing halogenated hydrocarbon groups and polyvinyl groups, the polysiloxane containing quaternary ammonium salts and polyvinyl groups The preparation of siloxane intermediates, and the substitution synthesis reaction of fluorine-containing lithium salt and quaternary ammonium polysiloxane. The main chain of the prepared antistatic agent compound is polydiorganosiloxane, and the side chain contains an anion and cation diionic antistatic agent structure and a vinyl functional group structure, which improves the durability of the antistatic agent and the relationship between the antistatic agent and the silicone adhesive composition. Compatibility between.

The introduction of polysiloxane segment can achieve good compatibility between antistatic agent molecules and the existing organic silicon material formulation components, and improve the uniform distribution of antistatic molecules in the adhesive layer, thereby improving the antistatic effect of organic silicon materials , while improving the transparency of pressure-sensitive adhesives. The anion-cation diionic antistatic agent structure can endow the surface of silicone materials with antistatic function. The introduction of the reactive functional group vinyl can realize the chemical bond combination between the antistatic agent molecule and the organic silicon material molecule, and avoid the chemical pollution caused by the organic silicon to the protected surface.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, and are used together with the embodiments of the present invention to explain the present invention, and do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the H ¹ NMR spectrum of antistatic agent compound A for reactive silicone materials prepared in Example 1 of the present invention.

Fig. 2 is the H ¹ NMR spectrum of antistatic agent compound D for reactive silicone materials prepared in Example 5 of the present invention.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Example 1: Preparation of Antistatic Agent Compound A for Reactive Silicone Materials

Step S1: 5.4 g of γ-chloropropylmethyldimethoxysilane (chemical reagent, purchased from Aladdin Company) and hydroxyl-terminated methyl vinyl silicone oil (provided by Jining Tangyi Chemical Co., Ltd., vinyl content 6.0 %) 29.1g into the reaction kettle, start stirring and mix evenly, add 1.6g of acidic resin catalyst Purolite CT275DR (purchased from Purolite (China) Co., Ltd.), slowly raise the temperature to 70°C, keep the temperature for 24h, then slowly vacuumize and remove Boil for 6h; replace the reaction system to normal pressure with nitrogen, add 4.8g of hexamethyldisiloxane (chemical reagent, purchased from Aladdin Company), keep it warm for 24h, slowly vacuumize to remove low boiling for 6h, and use a Buchner funnel The solid acid catalyst was removed by suction filtration to obtain a chloropropylvinyl silicone oil intermediate.

Step S2: Add 4.4 g of tri-n-propylamine (chemical reagent, purchased from Aladdin Company) and 50.0 g of N,N-dimethylformamide (chemical reagent, purchased from Aladdin Company) to the above intermediate, start stirring and Mix evenly, slowly raise the temperature to 110°C, keep the temperature for 24 hours, then slowly distill under reduced pressure to recover tri-n-propylamine and N,N-dimethylformamide, and finally obtain a yellow viscous liquid in the kettle.

Step S3: Add 8.5 g of lithium bistrifluoromethanesulfonimide (brand name HQ115, purchased from 3M Company) and 100 g of water to the liquid product obtained in the above step S2, start stirring and mix evenly, slowly raise the temperature to 50° C., and keep Stir the reaction for 24 hours; after cooling the above reactant intermediate to room temperature, add 100 g of dichloromethane (chemical reagent, purchased from Aladdin Company) and mix evenly, then add the mixed solution into a pear-shaped separatory funnel, vibrate vigorously and mix evenly, Separate the liquid and remove the lower layer; add 100g of water and the lower layer into the pear-shaped separating funnel, shake vigorously to mix evenly, separate the liquid, remove the lower layer, and repeat the above extraction operation twice; at a temperature of 100°C, slowly rotate under reduced pressure Evaporate, and slowly remove the solvent and water to obtain a light yellow transparent liquid, which is the target product: antistatic agent compound A for reactive organosilicon materials.

The product is subjected to H ¹ NMR measurement, and the chemical shift absorption peak near δ=0 is the absorption peak of hydrogen on the carbon atom connected to the silicon atom, which proves that the target product contains polydimethylsiloxane segment structure; δ=5.0- The chemical shift absorption peak splitting in the 5.5 interval belongs to the absorption peak of the hydrogen atom on the Si-CH=CH ₂ group; the three groups of chemical shift absorption peaks in the interval δ=1.0-3.0 are connected by the nitrogen atom S in the quaternary ammonium salt structure The absorption peak of the hydrogen atom-CH ₂ CH ₂ CH ₃ proves the existence of the antistatic agent structure of the target product.

Example 2: Preparation of Antistatic Agent Compound B for Reactive Silicone Materials

Step S1: Mix 4.6 g of γ-chloropropylmethyldiethoxysilane (chemical reagent, purchased from Aladdin Company) and hydroxyl-terminated methyl vinyl silicone oil (provided by Jining Tangyi Chemical Co., Ltd., with a vinyl content of 4.0 %) 34.5g into the reaction kettle, start stirring and mix evenly, add 1.5g of acidic resin catalyst Purolite CT275DR (purchased from Purolite (China) Co., Ltd.), slowly raise the temperature to 80°C, keep the temperature for 36h, and then slowly vacuumize and remove Boil for 6h; replace the reaction system to normal pressure with nitrogen, add 3.5g of hexamethyldisiloxane (chemical reagent, purchased from Aladdin Company), keep it warm for 20h, slowly vacuumize to remove low boiling for 6h, and use a Buchner funnel The solid acid catalyst was removed by suction filtration to obtain a chloropropylvinyl silicone oil intermediate.

Step S2: Add 3.4 g of tri-n-propylamine (chemical reagent, purchased from Aladdin Company) and 60.0 g of N,N-dimethylformamide (chemical reagent, purchased from Aladdin Company) to the above intermediate, start stirring and Mix evenly, slowly raise the temperature to 110°C, keep the temperature for 20 hours, then slowly distill under reduced pressure to recover tri-n-propylamine and N,N-dimethylformamide, and finally obtain a yellow viscous liquid in the kettle.

Step S3: Add 6.9 g of lithium bistrifluoromethanesulfonimide (brand HQ115, purchased from 3M Company) and 100 g of water to the liquid product obtained in the above step S2, start stirring and mix well, slowly raise the temperature to 40°C, and keep Stir the reaction for 24 hours; after cooling the above reactant intermediate to room temperature, add 100 g of dichloromethane (chemical reagent, purchased from Aladdin Company) and mix evenly, then add the mixed solution into a pear-shaped separatory funnel, vibrate vigorously and mix evenly, Separate the liquid and remove the lower layer; add 100g of water and the lower layer into the pear-shaped separating funnel, shake vigorously to mix evenly, separate the liquid, remove the lower layer, and repeat the above extraction operation twice; at a temperature of 100°C, slowly rotate under reduced pressure Evaporate, and slowly remove the solvent and water to obtain a light yellow transparent liquid, which is the target product: Compound B, an antistatic agent for reactive silicone materials.

Example 3: Preparation of Antistatic Agent Compound C for Reactive Silicone Materials

Step S1: 2.1 g of γ-chloropropylmethyldimethoxysilane (chemical reagent, purchased from Aladdin Company) and hydroxyl-terminated methyl vinyl silicone oil (provided by Jining Tangyi Chemical Co., Ltd., vinyl content 2.0 %) 41.9g into the reactor, start stirring and mix evenly, add 1.8g of acidic resin catalyst Purokite CT275DR (purchased from Purokite (China) Co., Ltd.), slowly raise the temperature to 80°C, keep the temperature for 24h, and then slowly vacuumize and remove Boil for 6 hours; replace the reaction system to normal pressure with nitrogen, add 1.9 g of hexamethyldisiloxane (chemical reagent, purchased from Aladdin Company), keep it warm for 24 hours, slowly vacuumize for 6 hours, and use a Buchner funnel The solid acid catalyst was removed by suction filtration to obtain a chloropropylvinyl silicone oil intermediate.

Step S2: Add 1.8 g of tri-n-propylamine (chemical reagent, purchased from Aladdin Company) and 50.0 g of N,N-dimethylformamide (chemical reagent, purchased from Aladdin Company) to the above intermediate, start stirring and Mix evenly, slowly raise the temperature to 110°C, keep the temperature for 18 hours, then slowly distill under reduced pressure to recover tri-n-propylamine and N,N-dimethylformamide, and finally obtain a yellow viscous liquid in the kettle.

Step S3: Add 3.4 g of lithium bistrifluoromethanesulfonimide (brand name HQ115, purchased from 3M Company) and 105 g of water to the liquid product obtained in the above step S2, start stirring and mix evenly, slowly raise the temperature to 40 ° C, keep Stir the reaction for 24 hours; after cooling the above-mentioned reactant intermediate to room temperature, add 105 g of dichloromethane (chemical reagent, purchased from Aladdin Company) and mix evenly, then add the mixed solution into a pear-shaped separatory funnel, vibrate vigorously and mix evenly, Separate the liquid and remove the lower layer; add 105g of water and the lower layer into the pear-shaped separating funnel, shake vigorously to mix evenly, separate the liquid, remove the lower layer, and repeat the above extraction operation twice; Evaporate, and slowly remove the solvent and water to obtain a light yellow transparent liquid, which is the target product: Compound C, an antistatic agent for reactive silicone materials.

Example 4: Preparation of Antistatic Agent Compound D for Reactive Silicone Materials

Step S1: 8.6 g of γ-chloropropylmethyldiethoxysilane (chemical reagent, purchased from Aladdin Company) and hydroxyl-terminated methyl vinyl silicone oil (provided by Jining Tangyi Chemical Co., Ltd., vinyl content 4.0 %) 24.8g into the reactor, start stirring and mix evenly, add 1.4g of acidic resin catalyst Purolite CT275DR (purchased from Purolite (China) Co., Ltd.), slowly raise the temperature to 90°C, keep the temperature for 24h, and then slowly vacuumize and remove Boil for 6h; replace the reaction system to normal pressure with nitrogen, add 2.2g of hexamethyldisiloxane (chemical reagent, purchased from Aladdin Company), keep it warm for 24h, slowly vacuumize to remove low boiling for 8h, and use a Buchner funnel The solid acid catalyst was removed by suction filtration to obtain a chloropropylvinyl silicone oil intermediate.

Step S2: Add 6.0 g of tri-n-propylamine (chemical reagent, purchased from Aladdin Company) and 50.0 g of N,N-dimethylformamide (chemical reagent, purchased from Aladdin Company) to the above intermediate, start stirring and Mix evenly, slowly raise the temperature to 110°C, keep the temperature for 24 hours, then slowly distill under reduced pressure to recover tri-n-propylamine and N,N-dimethylformamide, and finally obtain a yellow viscous liquid in the kettle.

Step S3: Add 12.0 g of lithium bistrifluoromethanesulfonimide (brand name HQ115, purchased from 3M Company) and 100 g of water to the liquid product obtained in the above step S2, start stirring and mix evenly, slowly raise the temperature to 50° C., and keep Stir the reaction for 24 hours; after cooling the above reactant intermediate to room temperature, add 100 g of dichloromethane (chemical reagent, purchased from Aladdin Company) and mix evenly, then add the mixed solution into a pear-shaped separatory funnel, vibrate vigorously and mix evenly, Separate the liquid and remove the lower layer; add 100g of water and the lower layer into the pear-shaped separating funnel, shake vigorously to mix evenly, separate the liquid, remove the lower layer, and repeat the above extraction operation twice; at a temperature of 100°C, slowly rotate under reduced pressure Evaporate, and slowly remove the solvent and water to obtain a light yellow transparent liquid, which is the target product antistatic agent compound D.

Example 5: Preparation of Antistatic Agent Compound E for Reactive Silicone Materials

Step S1: Mix 4.8 g of γ-chloropropylmethyldiethoxysilane (chemical reagent, purchased from Aladdin Company) and hydroxyl-terminated methyl vinyl silicone oil (provided by Jining Tangyi Chemical Co., Ltd., vinyl content 4.0 %) 36.2g into the reactor, start stirring and mix evenly, add 1.6g of acid resin catalyst Purolite CT275DR (purchased from Purolite (China) Co., Ltd.), slowly raise the temperature to 80°C, keep the temperature for 36h, and then slowly vacuumize to remove Boil for 6h; replace the reaction system to normal pressure with nitrogen, add 3.7g of hexamethyldisiloxane (chemical reagent, purchased from Aladdin Company), keep it warm for 20h, slowly vacuumize to remove the low boiling for 6h, and use a Buchner funnel The solid acid catalyst was removed by suction filtration to obtain a chloropropylvinyl silicone oil intermediate.

Step S2: Add 1.9 g of N-methylpyrrole (chemical reagent, purchased from Aladdin Company) and 60.0 g of N,N-dimethylformamide (chemical reagent, purchased from Aladdin Company) to the above intermediate, and start Stir and mix evenly, slowly raise the temperature to 90°C, keep the temperature for 40 hours, and then slowly distill under reduced pressure to recover N-methylpyrrole and N,N-dimethylformamide, and finally obtain a yellow viscous liquid in the kettle.

Step S3: Add 6.9 g of lithium bistrifluoromethanesulfonimide (brand HQ115, purchased from 3M Company) and 50 g of water to the liquid product obtained in the above step S2, start stirring and mix well, slowly raise the temperature to 4°C and keep stirring React for 24 hours; after cooling the above reactant intermediate to room temperature, add 50 g of dichloromethane (chemical reagent, purchased from Aladdin Co.) liquid, remove the lower layer; add 50g of water and the lower layer into a pear-shaped separating funnel, shake vigorously to mix evenly, separate the liquid, remove the lower layer, and repeat the above extraction operation twice; , and slowly remove the solvent and water to obtain a yellowish transparent liquid, which is the target product: Compound E, an antistatic agent for reactive silicone materials.

The product is subjected to H ¹ NMR measurement, and the chemical shift absorption peak near δ=0 is the absorption peak of hydrogen on the carbon atom connected to the silicon atom, which proves that the target product contains polydimethylsiloxane segment structure; δ=5.0- The chemical shift absorption peak in the 5.5 interval belongs to the absorption peak of the hydrogen atom on the Si-CH= _CH2 group; the multiple groups of chemical shift absorption peaks in the interval of δ=5.8-7.0 belong to the hydrogen atom on the antistatic agent pyrrole group The three groups of chemical shift absorption peaks in the interval of δ=1.5-4.0 are the absorption peaks of the hydrogen atom-CH ₂ CH ₂ CH ₂ -connected to the nitrogen atom S in the pyrrole quaternary ammonium salt structure, proving that the target product pyrrolyl is resistant to Presence of electrostatic agent structure.

Example 6: Preparation of Antistatic Agent Compound F for Reactive Silicone Materials

Step S1: 2.1 g of y-chloropropylmethyldimethoxysilane (chemical reagent, purchased from Aladdin Company) and hydroxyl-terminated methyl vinyl silicone oil (provided by Jining Tangyi Chemical Co., Ltd., vinyl content 2.0 %) 42.9g into the reactor, start stirring and mix evenly, add 1.8g of acid resin catalyst Purolite CT275DR (purchased from Purolite (China) Co., Ltd.), slowly raise the temperature to 70°C, keep the temperature for 24h, and then slowly vacuumize Boil for 6 hours; replace the reaction system to normal pressure with nitrogen, add 1.9 g of hexamethyldisiloxane (chemical reagent, purchased from Aladdin Company), keep it warm for 24 hours, slowly vacuumize for 6 hours, and use a Buchner funnel The solid acid catalyst was removed by suction filtration to obtain a chloropropylvinyl silicone oil intermediate.

Step S2: Add 1.0 g of N-methylpyrrole (chemical reagent, purchased from Aladdin Company) and 55.0 g of N,N-dimethylformamide (chemical reagent, purchased from Aladdin Company) to the above intermediate, and start Stir and mix evenly, slowly raise the temperature to 100°C, keep the temperature for 30 hours, and then slowly distill under reduced pressure to recover N-methylpyrrole and N,N-dimethylformamide, and finally obtain a yellow viscous liquid in the kettle.

Step S3: Add 3.5 g of lithium bistrifluoromethanesulfonimide (brand name HQ115, purchased from 3M Company) and 80 g of water to the liquid product obtained in the above step S2, start stirring and mix well, slowly raise the temperature to 40°C, and keep Stir the reaction for 24 hours; after cooling the above reactant intermediate to room temperature, add 80 g of dichloromethane (chemical reagent, purchased from Aladdin Company) and mix well, then add the mixed solution into a pear-shaped separatory funnel, vibrate vigorously and mix well, Separate the liquid and remove the lower layer; add 80g of water and the lower layer into the pear-shaped separating funnel, shake vigorously to mix evenly, separate the liquid, remove the lower layer, and repeat the above extraction operation twice; at a temperature of 100°C, slowly rotate under reduced pressure Evaporate, and slowly remove the solvent and water to obtain a light yellow transparent liquid, which is the target product: Compound F, an antistatic agent for reactive silicone materials.

The preparation embodiment of adhesive, protective film adhesive tape sample

The adhesive formula corresponding to the protective film tape sample is shown in the following table:

experiment:

According to the formula and dosage shown in the table above, weigh polyvinyl polysiloxane resin DOWSIL ^TM 7687 (purchased from Dow Chemical Company) and DY-V401-1000 (purchased from Shandong Dayi Chemical Co., Ltd. ), crosslinking agent and inhibitor DOWSIL7387 (purchased from Dow Chemical Company, containing crosslinking agent hydrogen-containing polysiloxane and inhibitor), adhesion promoter M97A (purchased from Zhejiang Runhe Organic Silicon New Material Co., Ltd.) and solvent, and antistatic agent compound for reactive silicone adhesive, after tightening the bottle cap, put it on the roll glue and roll glue at room temperature for 1h; add platinum catalyst (CSAT-F1, purchased from Dongguan Betley New Material Co., Ltd.) , after tightening the bottle cap, put it on the rolling rubber at room temperature and continue rolling the rubber for 1 hour; the PET base film is 38 μm, scraped with a comma scraper, and the distance between the blades of the scraper is adjusted. The thickness of the adhesive film after curing is 15 μm; the above wet adhesive film Put it in an electric heating blast drying oven at 150°C, take it out after curing for 1min, and stick the glued surface to the release surface of fluorine release film FS-050T (purchased from Yangzhou Wanrun Optoelectronics Technology Co., Ltd.); prepare a protective film Tape samples 1-6.

Repeat the above-mentioned experimental operation of the preparation example of adhesive and protective film tape sample, without adding antistatic agent compound for reactive silicone adhesive, and other conditions remain unchanged, to prepare protective film tape sample comparative example 1.

Repeat the experimental operation of the preparation example of the above-mentioned adhesive and protective film tape samples, and replace the antistatic agent compound for the reactive silicone adhesive with antistatic agent LZA-003 (purchased from Jiaxing Leizhou Composite Materials Co., Ltd.), and other conditions are not changed. Change, prepare protective film tape sample comparative example 2.

The prepared protective film tape sample is characterized and evaluated:

Put the protective film sample into the analytical test environment with a temperature of 23°C and a humidity of 50%RH, and after standing for 24 hours, refer to the standard ASTM D1003-21 "Standard Test Method for Haze and Light Transmittance of Transparent Plastics", using The light transmittance and haze tester is used to test the light transmittance and haze of the protective film.

Evaluate the antistatic property by testing the surface resistance of the rubber. Put the protective film sample into an analysis and test environment with a temperature of 23° C. and a humidity of 50% RH, and perform the surface resistance test and evaluation after standing for 24 hours. Tear off the release film on the surface of each protective film tape, and test the surface resistance with an American Trek Model 152 surface resistance tester.

Put the protective film sample in an analysis and testing environment with a temperature of 23°C and a humidity of 50% RH, let it stand for 24 hours, tear off the release film, and attach the exposed adhesive surface to a clean glass plate; then, put it in the temperature Stand in a constant temperature and humidity test chamber at 60°C and a relative humidity of 90% for 5 days; after the test, take out the glass plate sample with a protective film and place it in an analysis test environment with a temperature of 23°C and a humidity of 50%RH , After standing for 24 hours, tear off the protective film, observe the pollution on the glass surface with the naked eye, and use the pollution on the glass surface to determine the anti-aging performance of the protective film sample under high temperature and high humidity conditions and the pollution to the substrate; according to the glass The pollution of the surface is evaluated as 3 levels:

①The glass surface is completely pollution-free and evaluated as √

② Slightly polluted is evaluated as ×

③Obvious serious pollution is evaluated as ××

The performance test results are shown in the table below:

sample 1 sample 2 sample 3 Sample 4 Sample 5 Sample 6 Comparative example 1 Comparative example 2 Transmittance 91.2% 92.3% 93.5% 92.3% 91.3% 91.7% 90.8% 90.4% Haze 2.8 2.9 3.0 2.9 2.6 2.4 3.2 3.9 Surface resistance (Ω) <![CDATA[5.3×10¹⁰]]> <![CDATA[7.7×10¹⁰]]> <![CDATA[9.1×10¹¹]]> <![CDATA[4.8×10¹⁰]]> <![CDATA[3.3×10¹⁰]]> <![CDATA[4.5×10¹⁰]]> +∞ +∞ Anti-aging √ √ √ √ √ √ √ ××

Conclusion: As can be seen from the above table, the preparation method of the antistatic agent compound for reactive silicone materials provided by the present invention can introduce diionic groups with antistatic activity into the polysiloxane side chain, so that the silicone adhesive It has good antistatic properties; at the same time, vinyl functional groups that can undergo siloxane addition reactions can be introduced into the polysiloxane side chain, thereby greatly improving the durability of silicone pressure-sensitive adhesives without affecting the silicone system transparency. In contrast, the traditional quaternary ammonium antistatic agent LZA-003 has no reactive groups, has poor compatibility with silicone pressure-sensitive adhesive components, and has no chemical reaction sites, so it is difficult to distribute evenly in the silicone system. It cannot reduce the surface resistance, and it will lead to poor high-temperature and high-humidity aging resistance, so it cannot be applied to the antistatic treatment of silicone pressure-sensitive adhesives.

Preparation Example of Silicone Rubber Sample

The adhesive formula corresponding to the silicone rubber sample is shown in the table below:

Sample 9 sample 10 Sample 11 sample 12 Comparative example 3 Comparative example 4 DY-V421-1300 100.0 100.0 100.0 100.0 100.0 100.0 RH-LHC-3 10.0 10.0 10.0 10.0 10.0 10.0 CSAT-F1 2.0 2.0 2.0 2.0 2.0 2.0 1-Ethynylcyclohexanol 0.2 0.2 0.2 0.2 0.2 0.2 Antistatic agent compound A 7.5 0 0 0 0 0 Antistatic agent compound B 0 7.5 0 0 0 0 Antistatic agent compound E 0 0 7.5 0 0 0 Antistatic Agent Compound F 0 0 0 7.5 0 0 LZA-003 0 0 0 0 0 7.5

experiment:

According to the formula and dosage shown in the above table, weigh polyvinyl polysiloxane resin DY-V421-1300 (purchased from Shandong Dayi Chemical Co., Ltd.), hydrogen-containing polysiloxane crosslinking agent RH -LHC-3 (purchased from Zhejiang Runhe Organic Silicon New Material Co., Ltd.) and inhibitor 1-ethynyl cyclohexanol (analytical pure, purchased from Bailingwei Chemical Reagent Co., Ltd.), after tightening the bottle cap, put it on the roller rubber Roll glue at room temperature for 0.5h; add antistatic agent compound for reactive silicone adhesive, tighten the bottle cap, and continue rolling glue for 0.5h; add platinum catalyst syl-off-4000, tighten the bottle cap, place on the roll glue at room temperature and then Continue to roll the rubber for 2 hours; pour the above-mentioned addition-curable liquid silicone rubber mixture into a rectangular polytetrafluoroethylene mold, and the cavity size of the mold is length×width×depth=200mm×100mm×5mm; put the above-mentioned mold into a vacuum drying oven After vacuuming at room temperature to remove air bubbles, put them into an electric heating blast drying oven at 150°C, and take them out after curing for 3 minutes; silicone rubber samples 9-16 were prepared.

Repeat the above-mentioned experimental operation of the preparation example of the silicone rubber sample, without adding the antistatic agent compound for the reactive silicone rubber adhesive, and keep other conditions unchanged, to prepare the comparative example 3 of the protective film tape sample.

Repeat the above-mentioned experimental operation of the preparation example of the silicone rubber sample, replace the antistatic agent compound for the reactive silicone rubber adhesive with the antistatic agent LZA-003 (purchased from Jiaxing Leizhou Composite Materials Co., Ltd.), and keep other conditions unchanged. Prepare protective film tape sample comparative example 4.

Characterization and evaluation of the prepared silicone rubber samples:

Put the silicone rubber sample in a test environment with a temperature of 23°C and a humidity of 50% RH. After standing for 24 hours, the human eye will watch it under the three-wavelength lamp in a dark room with an illumination of 1000lux. The three-wavelength lamp is placed 20cm above the film, the angle between the light and the film surface is 40°, and the human eye is facing the light spot of the film at a distance of 30cm. Two methods of light transmission and reflection are used to visually inspect whether the sample is transparent, whether there is turbidity and crystal. Heterogeneous matter such as dots, which characterizes its appearance transparency.

The antistatic property is characterized by testing the surface resistance of the rubber surface. Put the silicone rubber sample in an analysis and test environment with a temperature of 23°C and a humidity of 50% RH. After standing for 24 hours, the surface resistance was tested with an American Trek Model 152 surface resistance tester.

Put the silicone rubber sample into the analysis and testing environment with a temperature of 23°C and a humidity of 50% RH. After standing for 24 hours, fix the silicone rubber sample on the front and back sides of a clean glass plate with adhesive tape; then, put it in the temperature Stand in a constant temperature and humidity test chamber at 60°C and a relative humidity of 90% for 5 days; after the test, take out the glass plate sample attached to the silicone rubber sample, and perform an analysis test at a temperature of 23°C and a humidity of 50%RH In the environment, after standing for 24 hours, tear off the silicone rubber sample, observe the pollution on the glass surface with the naked eye, and use the pollution on the glass surface to determine the anti-aging performance of the silicone rubber sample under high temperature and high humidity conditions and the substrate. Pollution situation; according to the pollution situation of the glass surface, the evaluation is divided into 3 grades:

The glass surface is completely pollution-free and evaluated as √

Slightly polluted as ×

Obvious severe pollution is evaluated as ××

The performance test results are shown in the table below:

It can be seen from the above table that the antistatic agent prepared according to the preparation method of the antistatic agent compound for reactive silicone materials provided by the present invention can be applied to the antistatic treatment in the field of silicone rubber, and can reduce the surface resistance of silicone rubber To the order of 10 ¹⁰ Ω, this will greatly avoid the adsorption of dust in the air on the surface of the silicone rubber, so that the surface cleanliness of the silicone rubber can not be greatly improved, and the transparency of the original silicone rubber will not be affected.

It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is a relationship between these entities or operations. There is no such actual relationship or order between them. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus comprising a set of elements includes not only those elements, but also includes elements not expressly listed. other elements of or also include elements inherent in such a process, method, article, or device.

Finally, it should be noted that: the above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, it still The technical solutions recorded in the foregoing embodiments may be modified, or some technical features thereof may be equivalently replaced. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims (10)

1. A preparation method of an antistatic compound for a reactive organosilicon material is characterized by comprising the following steps: the method comprises the following steps:

s1: preparation of polysiloxane intermediates containing quaternary ammonium salts and polyvinyl groups

Uniformly mixing a polysiloxane intermediate containing halogenated hydrocarbon groups and polyvinyl, organic amine and a solvent, heating to 50-150 ℃, reacting for 2-48 hours at a temperature, distilling under reduced pressure, and recovering the organic amine and the solvent to obtain a polysiloxane intermediate containing quaternary ammonium salt and polyvinyl;

s2: substitution synthesis reaction of fluorine-containing lithium salt and quaternary ammonium polysiloxane

Uniformly stirring a polysiloxane intermediate containing quaternary ammonium salt and polyvinyl, lithium bis (polyfluoroalkyl) sulfonyl imide and water, and stirring and reacting at 10-80 ℃ for 1-48 h to obtain a crude intermediate; cooling the crude intermediate to 25-35 ℃, adding an extraction solvent, uniformly mixing, and extracting; and (3) performing reduced pressure rotary evaporation at the temperature of 20-150 ℃ to remove the solvent and water, thereby obtaining the antistatic agent compound for the reactive organic silica gel adhesive.

2. The method for producing an antistatic compound for a reactive silicone material according to claim 1, characterized in that: in S1, the preparation method of the polysiloxane intermediate containing halogenated hydrocarbon groups and polyvinyl groups comprises the following steps: uniformly mixing terminal haloalkyl methyl dialkoxysilane, terminal hydroxyl vinyl polysiloxane and an acid catalyst, heating to 50-100 ℃, preserving heat for 2-48h, vacuumizing and removing low boiling point for 2-8h; adding hexamethyldisiloxane, reacting for 2-48h at a constant temperature, slowly vacuumizing to remove low boiling point for 2-8h, and filtering to remove the solid acid catalyst to obtain the polysiloxane intermediate containing halogenated hydrocarbon groups and polyvinyl groups.

3. The method for producing an antistatic compound for a reactive silicone material according to claim 1, characterized in that: in S1, the organic amine is one or more of trialkylamine and pyrrole compounds, and the structural formula is shown as follows:

in the method, in the process of the invention,

R ₁ 、R ₂ 、R ₃ and R is ₄ Is a monovalent saturated alkyl structure, and has a general structural formula of-C _p H _2p+1 P is a natural number, and p is more than or equal to 10 and more than or equal to 1;

R ₅ 、R ₆ 、R ₇ and R is ₈ Is any one of hydrogen atom and monovalent saturated alkyl structure, and has a general structural formula of-C _t H _2t+1 T is an integer, and 10 is more than or equal to t is more than or equal to 0.

4. The method for producing an antistatic compound for a reactive silicone material according to claim 1, characterized in that: in S1, the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-methylpyrrolidone, ethyl acetate, m-xylene, toluene, xylene, methyl isobutyl ketone and butanone.

5. The method for producing an antistatic compound for a reactive silicone material according to claim 1, characterized in that: in S2, the extraction solvent is any one or more of dichloromethane, chloroform, diethyl ether, petroleum ether and m-benzotrifluoride.

6. The method for producing an antistatic compound for a reactive silicone material according to claim 2, characterized in that: the structural formula of the terminal haloalkyl methyl dialkoxysilane is as follows:

CH ₂ BrC _q-1 H _2q-2 S _i CH ₃ (OC _s H _2s+1 ) ₂ 、CH ₂ ClC _q H _2q S _i CH ₃ (OC _s H _2s+1 ) ₂ any one or more of the following;

wherein q and s are natural numbers, q is more than or equal to 10 and more than or equal to 1, and s is more than or equal to 10 and more than or equal to 1;

the terminal haloalkyl methyldialkoxysilane may be any one or more of gamma-chloropropylmethyldipropoxysilane, gamma-chloropropylmethyldiethoxysilane, gamma-chloropropylmethyldimethoxysilane, chlorobutyl methyldiethoxysilane, chlorobutyl methyldimethoxysilane, gamma-bromopropyl methyldipropoxysilane, gamma-bromopropyl methyldiethoxysilane, gamma-bromopropyl methyldimethoxysilane.

7. The method for producing an antistatic compound for a reactive silicone material according to claim 2, characterized in that: the hydroxyl-terminated vinyl polysiloxane is hydroxyl-terminated methyl vinyl silicone oil.

8. The method for producing an antistatic compound for a reactive silicone material according to claim 2, characterized in that: the acid catalyst is one or more of concentrated sulfuric acid, acid clay, trifluoro methane sulfonic acid and acid resin catalyst YKCH 8501.

9. The method for producing an antistatic compound for a reactive silicone material according to claim 1, characterized in that: in S1, the mol ratio of the amino group to the halogenated hydrocarbon group is 1:1-1.5:1; in S2, the molar ratio of the lithium bis (polyfluoroalkyl) sulfonyl imide to the quaternary ammonium salt is 1:1-1.5:1.

10. The method for producing an antistatic compound for a reactive silicone material according to claim 2, characterized in that: the mol ratio of the terminal halogenated alkyl methyl dialkoxysilane to the terminal hydroxyl vinyl polysiloxane is 1:1-1:20, and the addition amount of the solid acid catalyst is 1-10% of the total mass of the reaction substances.

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