CN110283566B - Solvent-free silicone pressure-sensitive adhesive and preparation and application thereof - Google Patents
Solvent-free silicone pressure-sensitive adhesive and preparation and application thereof Download PDFInfo
- Publication number
- CN110283566B CN110283566B CN201910363583.7A CN201910363583A CN110283566B CN 110283566 B CN110283566 B CN 110283566B CN 201910363583 A CN201910363583 A CN 201910363583A CN 110283566 B CN110283566 B CN 110283566B
- Authority
- CN
- China
- Prior art keywords
- sensitive adhesive
- solvent
- mica tape
- silicone pressure
- silicone
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
- B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a solvent-free silicone pressure-sensitive adhesive and preparation and application thereof, wherein the raw materials of the solvent-free silicone pressure-sensitive adhesive comprise hydroxyl-terminated polydimethylsiloxane with low polymerization degree, amide group or aminoxysilane is introduced to realize chain extension and vulcanization to form diorganopolysiloxane with high polymerization degree, methyl M/Q silicone resin, viscosity regulator, silane coupling agent and coupling catalyst; then adding a viscosity regulator, and removing the solvent brought by the raw materials by reduced pressure distillation; then adding a vulcanized chain extender, mixing and stirring uniformly under the protection of inert atmosphere gas, and finally adding a coupling catalyst and a silane coupling agent, so that the prepared silicone pressure-sensitive adhesive has the advantages of simple synthesis reaction process at the early stage, good storage stability, no need of using a large amount of solvents such as toluene, xylene and the like to dilute the product during later-stage adhesive preparation, good bonding effect and difficulty in back adhesion.
Description
Technical Field
The invention relates to a bonding material technology, in particular to a solvent-free silicone pressure-sensitive adhesive and preparation and application thereof.
Background
The mica paper adhesive tape for the cable is formed by coating silicone pressure-sensitive adhesive on glass fiber cloth, then pasting the glass fiber cloth with various mica papers together, and heating and vulcanizing the mixture to form the adhesive tape with certain adhesive force and flame retardant property. The pressure-sensitive adhesive is a condensation reaction product of methyl MQ resin which endows the surface of the adhesive tape with viscosity and polydimethylsiloxane of molecular chain end hydroxyl, the special reticular structure of the methyl MQ resin, and Si-O-Si flexibility endows the adhesive tape with good adhesiveness and winding property, and is one of bonding materials which are widely used in the power cable industry. When the organic silicon pressure-sensitive adhesive is used, a large amount of solvents such as toluene, xylene and the like are required to be diluted, and then the organic silicon pressure-sensitive adhesive can be coated on a glass fiber cloth substrate, so that a large amount of environmental pollution and occupational disease injury of operators can be caused.
In addition, the mica paper tape is different from other tape base substrates, the mica paper needs to be soaked by using a solvent, a large amount of aromatic solvents such as toluene, xylene and the like are selected as the soaking agents, and although the water-type adhesive is environment-friendly, the mica paper is broken due to water, so that the defect that the mica paper cannot be glued is limited to be used in the mica tape industry.
In the process of storing the mica adhesive tape, due to the influence of the temperature and the humidity of the environment, the permeability and the sulfuration of the mica adhesive are poor or the surface is sticky due to too much oligomer, when the adhesive tape is cut, the tape is broken, and the scattered disk cannot be normally cut.
The adhesive suitable for paper infiltration and meeting the coating requirement is the basis for supporting the green development of the industry, in addition, most drying tunnels adopt electric heating or steam heating for vulcanization, the common method of the traditional mica adhesive is to use resin-shaped organopolysiloxane, organic polysiloxane containing ketoxime groups, amino-containing silane and organic tin to synthesize the adhesive material, the method has the problem of tackifying the adhesive material during storage, the viscosity is unstable, even gel can occur, in addition, the adhesive material can be coated only by diluting with a large amount of solvent during use, in addition, BPO vulcanization is mostly adopted, crosslinking is initiated through peroxide (BPO), the vulcanization is needed at the temperature of more than 160 ℃, the energy consumption is very large, and the peroxide can remain in the adhesive tape to form bad smell. And does not conform to international European Union instructions.
Disclosure of Invention
In order to solve the technical problems, the invention provides a solvent-free silicone pressure-sensitive adhesive and preparation and application thereof, which can avoid the pollution problem of toluene and xylene solvents to industrial workers and the atmospheric environment, and the prepared silicone pressure-sensitive adhesive can be quickly cured at the temperature of below 120 ℃ by utilizing moisture in the air without using BPO (bisphenol A vulcanization).
According to the invention, by introducing acylamino or aminoxysilane as a chain extension crosslinking agent into the formula, the low-viscosity pressure-sensitive adhesive suitable for being directly coated is prepared, the rapid curing at room temperature or below 120 ℃ is realized, and the energy consumption is saved.
In order to achieve the aim of the invention, the invention provides a solvent-free silicone pressure-sensitive adhesive which comprises the following raw materials in parts by mass: 600 parts of 300-600 parts of hydroxyl-terminated polydimethylsiloxane, 40-150 parts of vulcanized chain extender, 800 parts of 400-800 parts of methyl M/Q silicone resin, 0-150 parts of viscosity regulator, 10-50 parts of silane coupling agent and 10-50 parts of coupling catalyst. Optionally, the silicone pressure sensitive adhesive raw material consists of the raw materials.
In the solvent-free silicone pressure-sensitive adhesive provided by the invention, the viscosity of the hydroxyl-terminated polydimethylsiloxane is 100-10000mm2S; the molar mass is 1500-65000 g/mol.
In the solvent-free silicone pressure-sensitive adhesive provided by the invention, the M/Q molar ratio of the methyl M/Q silicone resin is 0.7-1.2; the weight average molecular weight is 4600-8000g/mol, and the number average molecular weight is 2000-4000 g/mol.
In the solvent-free silicone pressure-sensitive adhesive provided by the invention, the vulcanized chain extender is selected from one or two of amidosilane and aminoxysilane.
In the solvent-free silicone pressure sensitive adhesive provided by the present invention, the amidosilane is selected from one or more of methylvinyldi (N-methylacetamido) silane, dimethyldi (N-acetamido) silane, dimethyldi (N-formamido) silane, methylvinyldi (epsilon-caproylamido) silane;
in the solvent-free silicone pressure-sensitive adhesive provided by the invention, the aminoxysilane is linear aminoxysiloxane.
In the solvent-free silicone pressure-sensitive adhesive provided by the invention, the viscosity regulator is selected from one or more of dimethyl silicone oil, MTD silicone oil and MDM silicone oil, and the kinematic viscosity of the viscosity regulator is 20-200mm2/s。
In the solvent-free silicone pressure-sensitive adhesive provided by the present invention, the silane coupling agent is selected from one or more of gamma-methacryloxypropyltrimethoxysilane (kh-570), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (kh-560), N (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (kh792), aminopropyltriethoxysilane, aminopropyltrimethoxysilane and NCO-aminopropyltriethoxysilane.
In the solvent-free silicone pressure sensitive adhesive provided by the invention, the coupling catalyst is selected from one or more of lithium octoate, strontium octoate, zirconate, tetraoctyl orthotitanate, tetraethyl titanate and tetrabutyl titanate.
On the other hand, the invention also provides a preparation method of the solvent-free silicone pressure-sensitive adhesive, which comprises the following steps:
(1) mixing and stirring hydroxyl-terminated polydimethylsiloxane and methyl M/Q silicon resin solution to obtain a mixed solution;
(2) adding a viscosity regulator into the mixed solution obtained in the step (1), uniformly mixing, and then carrying out reduced pressure distillation operation;
(3) adding a vulcanized chain extender into the reaction vessel, and mixing and stirring uniformly under the protection of inert atmosphere gas;
(4) and (4) adding a silane coupling agent and a coupling catalyst into the mixture obtained in the step (3) to obtain the silicone pressure-sensitive adhesive.
Alternatively, the preparation process of the solvent-free silicone pressure sensitive adhesive consists of the steps.
In the preparation method of the solvent-free silicone pressure-sensitive adhesive provided by the invention, the solvent of the methyl M/Q silicone resin solution is selected from toluene, xylene and C5-C20An isoparaffin, a,C5-C15One or more of the olefins of (a), MDT silicone oil and ethyl acetate.
In the preparation method of the solvent-free silicone pressure-sensitive adhesive provided by the invention, in the step (1), the solid content of the methyl M/Q silicone resin solution is 60-70%; the mixing and stirring time is 3-5 hours.
In the preparation method of the solvent-free silicone pressure-sensitive adhesive provided by the invention, in the step (2), in the reduced pressure distillation operation, the container pressure is-0.1 MPa, and the temperature is 70-80 ℃.
In the preparation method of the solvent-free silicone pressure-sensitive adhesive provided by the invention, the reaction temperature of the step (3) is 20-40 ℃; the inert atmosphere gas is selected from one or more of nitrogen and inert gas.
In another aspect, the present invention also provides a mica tape comprising the solvent-free silicone pressure sensitive adhesive as described above as a binder.
The invention also provides a preparation method of the mica tape containing the solvent-free silicone pressure-sensitive adhesive as a bonding material, which comprises the following steps:
(a) coating the silicone pressure-sensitive adhesive on a mica tape base material, wherein the mica tape base material is selected from one or more of glass fiber cloth, non-woven fabric and nylon;
(b) and completely bonding the mica tape substrate and the mica paper through the silicone pressure sensitive adhesive to obtain the mica tape.
Alternatively, the preparation method of the mica tape using the solvent-free silicone pressure sensitive adhesive as the binder consists of the steps (a) and (b).
In the preparation method of the mica tape using the solvent-free silicone pressure-sensitive adhesive as the binder, the side of the mica paper in contact with the silicone pressure-sensitive adhesive in the step (b) is coated with an organic solvent;
in the preparation method of the mica tape using the solvent-free silicone pressure-sensitive adhesive as the binder, the organic solvent is selected from toluene, xylene and C5-C20Isoalkane of (C)5-C15One or more of the olefins and ethyl acetate of (a);
in the preparation method of the mica tape using the solvent-free silicone pressure sensitive adhesive as the adhesive, the substrate and the mica paper are completely jointed by the silicone pressure sensitive adhesive in the step (b) and then vulcanized for 30-60s at 90-120 ℃.
The invention is characterized in that only trace amount of sulfur-free aromatic environment-friendly solvent is used, the mica paper is slightly soaked, the pressure-sensitive adhesive does not contain solvent, chain extender is introduced during the preparation of the pressure-sensitive adhesive, the pressure-sensitive adhesive is cured while chain extension is carried out, the viscosity of the adhesive material is low, the adhesive material can be coated without being diluted by the solvent, the adhesive is stable to store, the pollution problem of toluene and xylene solvents to industrial workers and the atmospheric environment is avoided, the BPO vulcanization is not used, and the adhesive can be rapidly cured at the temperature below 120 ℃ by utilizing moisture in the air.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
To make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the claims. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.
The embodiment of the invention provides a solvent-free silicone pressure-sensitive adhesive, which comprises the following raw materials in parts by mass: 600 parts of 300-600 parts of hydroxyl-terminated polydimethylsiloxane, 40-150 parts of vulcanized chain extender, 800 parts of 400-800 parts of methyl M/Q silicone resin, 0-150 parts of viscosity regulator, 10-50 parts of silane coupling agent and 10-50 parts of coupling catalyst. Optionally, the silicone pressure sensitive adhesive raw material consists of the raw materials.
In the embodiment of the invention, the viscosity of the hydroxyl-terminated polydimethylsiloxane is 100-10000mm2S; the molar mass is 1500-65000 g/mol.
In the embodiment of the invention, the M/Q molar ratio of the methyl M/Q silicon resin is 0.7-1.2; the weight average molecular weight is 4600-8000g/mol, and the number average molecular weight is 2000-4000 g/mol.
In embodiments of the invention, the sulfurized chain extender is selected from one or both of amidosilanes and aminoxysilanes.
In an embodiment of the invention, the amidosilane is selected from one or more of methylvinyldi (N-methylacetamido) silane, dimethyldi (N-acetamido) silane and dimethyldi (N-formylamino) silane, methylvinyldi (. epsilon. -caproylamino) silane;
in an embodiment of the invention, the aminoxysilane is a linear aminoxysilane.
In the embodiment of the invention, the viscosity regulator is selected from one or more of dimethyl silicone oil, MTD silicone oil and MDM silicone oil, and the kinematic viscosity of the viscosity regulator is 20-200mm2/s。
In an embodiment of the present invention, the silane coupling agent is selected from one or more of gamma-methacryloxypropyltrimethoxysilane (kh-570), gamma- (2, 3-glycidoxy) propyltrimethoxysilane (kh-560), N (. beta. -aminoethyl) -gamma-aminopropyltrimethoxysilane (kh792), aminopropyltriethoxysilane, aminopropyltrimethoxysilane and NCO-aminopropyltriethoxysilane.
In an embodiment of the invention, the coupling catalyst is selected from one or more of lithium octoate, strontium octoate, zirconate series coupling agents, tetraoctyl orthotitanate, tetraethyl titanate, and tetrabutyl titanate.
In an embodiment of the invention, the solvent of the methyl M/Q silicone resin solution is selected from toluene, xylene, C5-C20Isoparaffin, C5-C15One or more of the olefins of (a), MDT silicone oil and ethyl acetate.
In the embodiment of the invention, the solid content of the methyl M/Q silicon resin solution is 60-70%; the mixing and stirring time is 3-5 hours.
In the embodiment of the invention, in the reduced pressure distillation operation, the pressure of a container is-0.1 MPa, and the temperature is 70-80 ℃.
In embodiments of the present invention, optionally, the side of the mica paper in contact with the silicone pressure sensitive adhesive is coated with an organic solvent; the organic solvent is selected from toluene, xylene and C5-C20Isoalkane of (C)5-C15And ethyl acetate.
In the embodiment of the invention, the viscosity is selected to be 100-2Hydroxyl-terminated polydimethylsiloxane (viscosity is too low, self-adhesion is lacked after curing, viscosity is too high, coating is not easy, diorganopolysiloxane with chain extension being high polymerization degree is formed in the vulcanization process by introducing amido or aminoxysilane (aminoxysilane) as a chain extender), and methyl M/Q silicone resin with the molar ratio of M/Q being 0.7-1.2 is selected as a vulcanization chain extender, and methylvinyldi (N-methylacetamido) silane is selected as a vulcanization chain extender.
Example 1
The silicone pressure sensitive adhesive provided in this example was prepared according to the following procedure:
(1) will have a kinematic viscosity of 1000mm2400g of hydroxyl-terminated polydimethylsiloxane with the molar mass of 26000g/mol per second is put into a three-neck flask with stirring, then 750g of toluene solution containing methyl M/Q silicone resin with the solid content of 67 percent is put into the flask, the molar ratio of M/Q is 0.78, the weight-average molecular weight is 6900g/mol, the number-average molecular weight is 2300g/mol, and the mixture is mixed and stirred for 3 hours at normal temperature.
(2) Then 50g of a mixture with a kinematic viscosity of 100mm was added2Uniformly mixing dimethyl silicon oil/s, heating to 80 ℃, decompressing under-0.1 MPa, discharging toluene, condensing, recycling and recycling.
(3) And then cooling the reactant to 40 ℃, adding 45g of methyl vinyl di (N-methylacetamido) silane, mixing and stirring uniformly under the protection of nitrogen to prepare the organic silicon solvent-free environment-friendly pressure-sensitive adhesive precursor, and sealing and packaging. The viscosity of the finished product is 3000mm2/s。
(4) And (3) adding a silane coupling agent KH-792 and tetrabutyl titanate into the pressure-sensitive adhesive precursor prepared in the step (3), adding 2g of the silane coupling agent and 1.5g of tetrabutyl titanate catalyst into 100g of the pressure-sensitive adhesive precursor, and uniformly mixing to obtain the solvent-free silicone pressure-sensitive adhesive.
Sample preparation and performance testing:
the mica paper with thickness of 0.09-0.12mm is coated with glass fiber cloth, and then coated with solvent-free silicone pressure sensitive adhesive with coating amount of 10-20 g/m (12 g/m is selected for sample preparation), and the mixture is cured at 120 deg.C for 60s to obtain test piece.
Evaluation of flexibility: the test piece was cut into 1cm, wound around a guide wire, and observed for flexibility.
Anti-blocking evaluation: cutting the test piece into 10 × 10cm pieces, overlapping 5 pieces at 10kg/cm2After the temperature was maintained at 80 ℃ for 3 hours under the pressure of (2), the temperature was returned to normal temperature, and the state of migration to the mica layer was observed.
Evaluation of permeability:
4ml of solvent-free silicone pressure-sensitive adhesive was placed in an aluminum box, and mica paper of 25X 30mm was impregnated into the box from the back side, and the time for which the mica paper was completely impregnated with the solution was measured, and the impregnation time was required to be in the range of 15 to 20 seconds.
Testing the adhesive force: the test pieces were cut into 0.01 square meters, and the test pieces were stretched along opposite corners to observe whether the glass fiber cloth and the mica paper were separated.
And (3) testing results: flexibility, winding the fiber rapidly for 5 m, and breaking the fiber for 0 time; wettability, and total immersion time is 16 seconds; taking 3 samples, respectively stretching along opposite angles, and separating the mica layer from the cloth base for 0 time; blocking resistance, tested on 5 sheets, from 1 to 5 layers released naturally, no sound, no glue migration on the surface.
Example 2
The silicone pressure sensitive adhesive provided in this example was prepared according to the following procedure:
(1) will have kinematic viscosity of 6000mm2500g of hydroxyl-terminated polydimethylsiloxane having a molar mass per second of 52000g/mol was put into a three-necked flask equipped with a stirrer, 1050g of a toluene solution having a weight-average molecular weight of 7410g/mol and a number-average molecular weight of 2640g/mol and containing methyl M/Q silicone resin with a solid content of 67% was put into the flask, the molar ratio of M/Q was 0.85, and the mixture was stirred at room temperature for 5 hours,
(2) then 150g of a kinematic viscosity of 100mm was added2The dimethyl silicone oil/s is mixed evenly and thenHeating to 80 deg.C, vacuum-extracting under-0.1 MPa to obtain toluene, condensing, recovering, and recycling.
(3) Then the reactant is cooled to 40 ℃, 96.28 g of methyl vinyl di (N-methyl acetamido) silane is added, and the mixture is mixed and stirred evenly under the protection of nitrogen to prepare the organic silicon solvent-free environment-friendly pressure sensitive adhesive precursor. Hermetically packaging, and the viscosity of the finished product is 3800mm2/s。
(4) And (3) adding a silane coupling agent kh-570, a kh-560 mixed solution (mass ratio is 1: 1) and lithium octoate into the pressure-sensitive adhesive precursor prepared in the step (3), adding 3g of silane coupling agent and 2g of coupling catalyst into 100g of the pressure-sensitive adhesive precursor, and uniformly mixing to obtain the solvent-free silicone pressure-sensitive adhesive.
And (3) performance testing:
the same test method as in example 1 was used for the test, and the test results were as follows: flexibility, winding the fiber rapidly for 5 m, and breaking the fiber for 0 time; wettability, and total immersion time is 17 seconds; taking 3 samples, respectively stretching along opposite angles, and separating the mica layer from the cloth base for 0 time; blocking resistance, 5 sheets tested, from 1 layer of 5 layers can be naturally released, no sound, no glue migration on the surface.
Example 3
The silicone pressure sensitive adhesive provided in this example was prepared according to the following procedure:
(1) the kinematic viscosity is 10000mm2500g of hydroxyl-terminated polydimethylsiloxane having a molar mass/s of 64000g/mol was put into a three-necked flask equipped with stirring, 1000g of a toluene solution having a weight-average molecular weight of 5714g/mol and a number-average molecular weight of 2153g/mol and containing 67% of methyl M/Q silicone resin in terms of solid content was put into the flask, the molar ratio M/Q was 1.1, and the mixture was stirred at room temperature for 5 hours,
(2) then 175.5 g of kinematic viscosity 50mm are added2And (2) uniformly mixing the dimethyl silicone oil/s, heating to 80 ℃, removing toluene under-0.1 Mpa vacuum, condensing, recovering and recycling.
(3) And cooling the reactant to 40 ℃, adding 120g of methylvinyl di (N-methylacetamido) silane, and mixing and stirring uniformly under the protection of nitrogen to prepare the solvent-free silicone sensitive adhesive precursor. Secret keySealing and packaging, the viscosity of the finished product is 3200mm2/s。
(4) And (3) adding silane coupling agent kh-792 and lithium octoate into the pressure-sensitive adhesive precursor prepared in the step (3), adding 2g of silane coupling agent and 1.5g of coupling catalyst into 100g of the pressure-sensitive adhesive precursor, and uniformly mixing to obtain the solvent-free silicone pressure-sensitive adhesive.
And (3) performance testing:
the test was carried out according to the test method of example 1,
results the following test results: flexibility, winding the fiber rapidly for 8 meters, and breaking the fiber for 0 time; wettability, and total immersion time is 16 seconds; bonding, taking 3 samples, respectively stretching along opposite angles, and ensuring that the mica layer is not separated from the cloth base; blocking resistance, 5 sheets tested, from 1 layer of 5 layers can be naturally released, no sound, no glue migration on the surface.
Comparative example 1
Comparative example 1 provides a prior art binder prepared by the following steps:
(1) 1000g of methyl M/Q silicone resin toluene solution with weight average molecular weight of 10300g/mol and number average molecular weight of 3783g/mol and solid content of 67% and with M/Q molar ratio of 0.7-1.0 is added into a three-neck flask with a stirrer, and then 520g of hydroxyl-terminated polydimethylsiloxane crude rubber with solid content of 30% and viscosity of 35000mpa.s is added.
(2) 5.3g of a 10 wt.% aqueous solution of sodium hydroxide was added and mixed well.
(3) Heating and refluxing for 6 hours, removing partial toluene and oligomers, neutralizing with phosphoric acid to pH 7, supplementing toluene to adjust the solid content to 60%, and obtaining the uncrosslinked toluene solution silicone pressure-sensitive adhesive with viscosity of 48000 mpa.s.
(4) And (3) taking 1g of the adhesive prepared in the step (3), adding 2g of toluene for dilution, then adding 0.015g of benzoyl peroxide, adding 2g of toluene and 0.015g of benzoyl peroxide according to the proportion of 1g of pressure sensitive adhesive, and uniformly mixing to obtain the toluene solution silicone pressure sensitive adhesive.
And (3) performance testing:
the same glue was applied as in example 1, the vulcanization temperature was increased from 100 ℃ to 165 ℃ and vulcanization was carried out for 1 min. The same test method as in example 1 was used, and the test results were: flexibility, winding the fiber rapidly for 5 m, and breaking the fiber for 0 time; wettability, and the total immersion time is 25 seconds; the adhesion property is that 3 pieces of samples are taken and respectively stretched along opposite angles, 1 piece is qualified, 1 piece has a point cloud mother layer to be separated from the cloth substrate, and 1 piece has a separated area, which is particularly obvious under a magnifier; and (3) the adhesion resistance is that 5 sheets are tested, and the 3 layers and the 4 layers cannot be naturally separated from each other, and when the second sheet and the fourth sheet are opened, the second sheet and the fourth sheet are both provided with sound, glue migrates to the surface of the test piece, and the hand feeling is harsh. In addition, the diluent toluene is high in volatilization amount and heavy in smell.
Comparative example 2
Comparative example 2 provides a prior art binder prepared by the following steps:
(1) 500g of methyl M/Q silicone 67% toluene solution with weight average molecular weight of 7300g/mol and number average molecular weight of 2640M/Q molar ratio of 0.7-1.0 is added into a three-neck flask with a stirrer, and then 900g of raw polydimethylsiloxane with solid content of 30% and viscosity of 26000mpa.s is added.
(2) 6g of 10 wt.% aqueous solution of sodium hydroxide was added and mixed well.
(3) Heating and refluxing for 6 hours, removing partial toluene and oligomer, neutralizing with phosphoric acid to pH 7, and adjusting the solid content to 60% with toluene to obtain uncrosslinked mica binder with viscosity of about 31000 mpa.s.
(4) And (3) taking 1g of the adhesive prepared in the step (3), adding 2g of toluene for dilution, then adding 0.015g of benzoyl peroxide, adding 2g of toluene and 0.015g of benzoyl peroxide according to the proportion of 1g of pressure-sensitive adhesive, and uniformly mixing to obtain the mica adhesive.
And (3) testing results: flexibility, winding the fiber rapidly for 8 meters, and breaking the fiber for 0 time; wettability, total immersion time 21 seconds; the adhesion property is that 3 pieces of samples are taken and respectively stretched along opposite angles, 1 piece of mica paper with one point is separated from the cloth base, 2 pieces are qualified, and the adhesion property is particularly obvious under a magnifying glass; the anti-blocking property is that 5 pieces of the rubber composition can not be naturally separated from 1 layer of the rubber composition and 5 layers of the rubber composition are all slightly migrated, and the surface of the rubber composition feels astringent. In addition, the volatile amount of the diluent is heavy in odor.
Comparative example 3
Comparative example 3 provides a prior art binder prepared by the following steps:
(1) in a three-neck flask equipped with a stirrer, 67% of C is added to a methyl M/Q silicone resin with 6519g/mol of weight average molecular weight and 2013g/mol of number average molecular weight, wherein the M/Q molar ratio is 0.7-1.05-C201000g of isoalkane solution, and then 520g of raw rubber of 18000mpa.s hydroxyl-terminated polydimethylsiloxane with the solid content of 30 percent.
(2) 5.5g of a 10 wt.% aqueous solution of sodium hydroxide was added and mixed well.
(3) Heating and refluxing for 8 hours, removing partial toluene and oligomer, neutralizing to pH 7 with phosphoric acid, and adjusting the solid content to 60% with toluene to obtain the non-crosslinked mica binder with viscosity of 26000 mpa.s.
(4) And (3) taking 1g of the adhesive prepared in the step (3), adding 2g of toluene for dilution, then adding 0.015g of benzoyl peroxide, adding 2g of toluene and 0.015g of benzoyl peroxide according to the proportion of 1g of pressure-sensitive adhesive, and uniformly mixing to obtain the mica adhesive.
And (3) testing results: flexibility, winding the fiber rapidly for 5 m, and breaking the fiber for 0 time; wettability, the total immersion time is 19 seconds, and the process requirements are basically met; the adhesiveness is that 3 pieces of samples are taken and respectively stretched along opposite angles, 1 piece is released at one point, 2 pieces are qualified, and the magnifying glass is particularly prominent; blocking resistance, 5 sheets tested, naturally released from 1 to 3 layers, no glue migration, 4 to 5 blocking, surface glue migration. In addition, toluene is highly volatile and smells unpleasant.
The invention is characterized in that the finished product does not contain solvent, optionally uses a small amount of solvent as mica paper impregnating compound, can be coated to manufacture mica paper adhesive tape, does not use sulfur and aromatic solvent to pollute human body and environment, introduces chain extender during the manufacture of pressure sensitive adhesive, leads the pressure sensitive adhesive to be cured while chain extending, and the prior art represented by a comparative example needs benzoyl peroxide as curing agent, needs a large amount of toluene to be diluted and then coated, and the curing temperature needs more than 160 ℃.
The adhesive material has low viscosity, can be coated without being diluted by a solvent, is stable in storage, avoids the problem of pollution of toluene and xylene solvents to industrial workers and the atmospheric environment, is vulcanized without BPO (bisphenol A oxide), can be quickly cured at a temperature of below 120 ℃ by utilizing moisture in the air, does not use tin catalysts, avoids suspected suspicion of endocrine disorders of tin, and is more environment-friendly and healthier. Compared with the use of raw rubber of terminal hydroxyl polydimethylsiloxane, the use of the terminal hydroxyl polydimethylsiloxane has the advantages that the early-stage synthesis reaction process is simple, the neutralization process is omitted, a large amount of methylbenzene is not used for diluting products during later-stage rubber preparation, the vulcanization temperature is low, the energy consumption is reduced, the solvent pollution and the recycling trouble are avoided, the product bonding effect after vulcanization is good, and the product is not easy to back-stick.
Claims (10)
1. A mica tape comprises a solvent-free silicone pressure sensitive adhesive as a binder;
the silicone pressure-sensitive adhesive comprises the following raw materials in parts by mass:
300-600 parts of hydroxyl-terminated polydimethylsiloxane, 40-150 parts of vulcanized chain extender, 400-800 parts of methyl M/Q silicone resin, 0-150 parts of viscosity regulator, 10-50 parts of silane coupling agent and 10-50 parts of coupling catalyst; the viscosity of the hydroxyl-terminated polydimethylsiloxane is 100-10000mm2S; the M/Q molar ratio of the methyl M/Q silicon resin is 0.7-1.2; the weight-average molecular weight is 4600-8000g/mol, and the number-average molecular weight is 2000-4000 g/mol;
the silane coupling agent is selected from one or more of gamma-methacryloxypropyltrimethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, aminopropyltrimethoxysilane and isocyanatopropyltriethoxysilane;
the coupling catalyst is selected from one or more of lithium octoate, strontium octoate, zirconate, tetraoctyl orthotitanate, tetraethyl titanate and tetrabutyl titanate;
the vulcanization chain extender is selected from one or two of amidosilane and aminoxysilane.
2. The mica tape of claim 1, wherein the amidosilane is selected from one or more of methylvinyldi (N-methylacetamido) silane, dimethyldi (N-acetamido) silane, and methylvinyldi (epsilon-caproylamido) silane;
the aminoxysilane is a linear aminoxy-containing polysiloxane crosslinking agent.
3. The mica tape of claim 1, wherein the viscosity modifier is selected from one or more of dimethicone, MDT silicone oil, and MDM silicone oil, and the kinematic viscosity of the viscosity modifier is 20-200mm2/s。
4. The mica tape of any one of claims 1 to 3, wherein the solvent-free silicone pressure sensitive adhesive is prepared by a process comprising the steps of:
(1) mixing and stirring hydroxyl-terminated polydimethylsiloxane and methyl M/Q silicon resin solution to obtain a mixed solution;
(2) adding a viscosity regulator into the mixed solution obtained in the step (1), uniformly mixing, and then carrying out reduced pressure distillation operation;
(3) adding a vulcanized chain extender into the reaction vessel, and mixing and stirring uniformly under the protection of inert atmosphere gas;
(4) and (4) adding a silane coupling agent and a coupling catalyst into the mixture obtained in the step (3) to obtain the silicone pressure-sensitive adhesive.
5. The mica tape of claim 4, wherein the solvent of the methyl M/Q silicone solution is selected from toluene, xylene, C5-C20Isoparaffin, C5-C15One or more of the olefins of (a), MDT silicone oil and ethyl acetate.
6. The mica tape of claim 4, wherein in step (1), the methyl M/Q silicone solution has a solid content of 60-70%; the mixing and stirring time is 3-5 hours.
7. The mica tape according to claim 4, wherein in the step (2), in the distillation under reduced pressure operation, the pressure in the vessel is-0.1 MPa and the temperature is 70 to 80 ℃.
8. The mica tape of claim 4, wherein the reaction temperature of step (3) is 20-40 ℃.
9. A method of making the mica tape of any one of claims 1 to 3, comprising the steps of:
(a) coating the silicone pressure-sensitive adhesive on a mica tape base material, wherein the mica tape base material is selected from one or more of glass fiber cloth, non-woven fabric and nylon;
(b) and completely bonding the mica tape substrate and the mica paper through the silicone pressure sensitive adhesive to obtain the mica tape.
10. The method of preparing mica tape as claimed in claim 9, wherein the side of the mica paper in contact with the silicone pressure sensitive adhesive in step (b) is coated with an organic solvent;
the organic solvent is selected from toluene, xylene and C5-C20Isoalkane of (C)5-C15One or more of the olefins and ethyl acetate of (a);
and (c) after the base material and the mica paper are completely attached through the silicone pressure-sensitive adhesive in the step (b), vulcanizing at 90-120 ℃ for 30-60 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910363583.7A CN110283566B (en) | 2019-04-30 | 2019-04-30 | Solvent-free silicone pressure-sensitive adhesive and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910363583.7A CN110283566B (en) | 2019-04-30 | 2019-04-30 | Solvent-free silicone pressure-sensitive adhesive and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110283566A CN110283566A (en) | 2019-09-27 |
| CN110283566B true CN110283566B (en) | 2021-07-09 |
Family
ID=68001433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910363583.7A Active CN110283566B (en) | 2019-04-30 | 2019-04-30 | Solvent-free silicone pressure-sensitive adhesive and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283566B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112289528B (en) * | 2020-09-23 | 2023-05-05 | 湖北平安电工实业有限公司 | Method for manufacturing calcined mica tape and calcined mica tape |
| CN112712948A (en) * | 2020-12-29 | 2021-04-27 | 晟大科技(南通)有限公司 | Preparation method of solvent-free mica tape |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05239433A (en) * | 1992-02-25 | 1993-09-17 | Toray Dow Corning Silicone Co Ltd | Moisture-curable self-adhesive silicone composition |
| CN101333426A (en) * | 2008-07-22 | 2008-12-31 | 株洲时代新材料科技股份有限公司 | Low resin mica tape organosilicon adhesive and method for preparing same |
| CN103409103A (en) * | 2013-05-20 | 2013-11-27 | 广东信翼新材料股份有限公司 | Environment-friendly high-temperature-resistant organic silicon pressure-sensitive adhesive and preparation method thereof |
| CN104428372A (en) * | 2012-07-18 | 2015-03-18 | 道康宁公司 | Organosiloxane compositions |
| CN105038689A (en) * | 2015-07-03 | 2015-11-11 | 黑龙江省科学院石油化学研究院 | Solvent-free room temperature cross-linked organic silicon pressure-sensitive adhesive, and preparation method thereof |
-
2019
- 2019-04-30 CN CN201910363583.7A patent/CN110283566B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05239433A (en) * | 1992-02-25 | 1993-09-17 | Toray Dow Corning Silicone Co Ltd | Moisture-curable self-adhesive silicone composition |
| CN101333426A (en) * | 2008-07-22 | 2008-12-31 | 株洲时代新材料科技股份有限公司 | Low resin mica tape organosilicon adhesive and method for preparing same |
| CN104428372A (en) * | 2012-07-18 | 2015-03-18 | 道康宁公司 | Organosiloxane compositions |
| CN103409103A (en) * | 2013-05-20 | 2013-11-27 | 广东信翼新材料股份有限公司 | Environment-friendly high-temperature-resistant organic silicon pressure-sensitive adhesive and preparation method thereof |
| CN105038689A (en) * | 2015-07-03 | 2015-11-11 | 黑龙江省科学院石油化学研究院 | Solvent-free room temperature cross-linked organic silicon pressure-sensitive adhesive, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 有机硅粘合剂在耐火云母带上的应用;高群等;《中国胶粘剂》;20030930(第05期);第56-60页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110283566A (en) | 2019-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111417692B (en) | Anti-graffiti coating compositions | |
| CN110283566B (en) | Solvent-free silicone pressure-sensitive adhesive and preparation and application thereof | |
| US2736721A (en) | Optionally | |
| CN109251691B (en) | Silica gel protection film | |
| CN107312471A (en) | A kind of antistatic protection film and its manufacture method | |
| CN104152104A (en) | Self-adhesive organic silicon press-sensitive adhesive and preparation method thereof | |
| CN105960443B (en) | The manufacturing method of polyorganosiloxane adhesive composite, adhesive tape and adhesive tape | |
| CN110494528A (en) | The method for preparing silicone pressure sensitive adhesive | |
| CN108484803B (en) | Silane-terminated polymer and moisture-cured adhesive composition prepared from same | |
| JP2017511417A (en) | Curable silicone composition | |
| CN107236144A (en) | It is a kind of to be used to process mould release membrance combination of battery grade lithium band and preparation method thereof | |
| JP2007515560A6 (en) | Adhesive bonding process of silicone coated fibrous support | |
| JP2007515560A (en) | Adhesive bonding process of silicone coated fibrous support | |
| CN107641466B (en) | Organic silicon solvent-free impregnating varnish and preparation method thereof | |
| JPH0718185A (en) | Silicone composition for release agent | |
| CN105745294A (en) | Surface-protecting adhesive sheet, and method for using surface-protecting adhesive sheet | |
| CN113667310B (en) | Liquid silicone rubber and preparation method and application thereof | |
| CN112289528A (en) | Method for manufacturing calcined mica tape and calcined mica tape | |
| CN111051449B (en) | Polysiloxane composition | |
| CN116478656A (en) | Quick-curing solvent-free organosilicon adhesive, manufacturing process and application | |
| JP3719796B2 (en) | Adhesive material | |
| CN114907767B (en) | Antibacterial silicone rubber coating and preparation method thereof | |
| CN105745296A (en) | Pressure-sensitive adhesive composition and process for manufacturing pressure-sensitive adhesive sheet | |
| CN207159127U (en) | A kind of mould release membrance combination for being used to process battery grade lithium band and the lithium band composite membrane prepared by it | |
| CN108265558B (en) | Release agent composition comprising hydroxyl-terminated silicone resin and use of the silicone resin |
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 |