CN112706480A - Preparation method of polyurethane electronic and electrical insulating material - Google Patents
Preparation method of polyurethane electronic and electrical insulating material Download PDFInfo
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/558—Impact strength, toughness
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- C—CHEMISTRY; METALLURGY
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention discloses a preparation method of a polyurethane electronic electrical insulating material, which comprises the following steps of preparing raw materials of polymerized fluororubber, polyurethane emulsion and a characteristic auxiliary coating, wherein the polymerized fluororubber consists of fluorine-containing monomer molecules, water, an auxiliary agent, a dispersing agent, a neutralization buffering agent, an initiator and a chain transfer agent, the characteristic auxiliary coating comprises a cold-resistant toughness coating, an elastic coating and a wear-resistant coating, the cold-resistant toughness coating is a polyimide toughness film, the elastic coating is an elastic coating, the wear-resistant coating is a wear-resistant coating, and the raw materials are processed to obtain a finished product. According to the preparation method of the polyurethane electronic electrical insulating material, the fluororubber is used as a main body, the polyurethane emulsion which is self-emulsified by adopting an acetone method and the modified fluororubber are polymerized with each other to form the modified fluororubber, so that the whole polyurethane electronic electrical insulating material has better corrosion resistance, can adapt to high-temperature and low-temperature environments, improves the cold and heat resistance of the polyurethane electronic electrical insulating material to the utmost, and greatly improves the working applicability of the whole polyurethane electronic electrical insulating material.
Description
Technical Field
The invention relates to the technical field of polyurethane insulating materials, in particular to a preparation method of a polyurethane electronic electrical insulating material.
Background
The polyurethane is a high molecular compound, can be used as a preparation material for preparing materials for producing electronic and electrical products or equipment, and has a thermoplastic linear structure as a whole.
The existing polyurethane electronic and electric insulating material is mostly a traditional insulating material prepared by adopting polyurethane as a main body, does not have better applicability in the application work of electronic and electric products or equipment, is difficult to adapt to high-temperature and low-temperature environments, limits the whole working range to a certain degree, has more general toughness, easily causes the fractured use condition in long-term use, does not have better elasticity, wear resistance and corrosion resistance, correspondingly receives the limitation of a certain degree in the service life of the whole, has poorer flame retardant property in normal use, further has poorer use safety of the whole, easily causes work accidents in the application work of the electronic and electric products or equipment, and has larger use risk.
Disclosure of Invention
The invention aims to provide a preparation method of a polyurethane electronic and electric insulating material, which aims to solve the problems of poor applicability, relatively common elasticity, wear resistance and corrosion resistance, short overall service life, poor flame retardance, easy initiation of use accidents and relatively high overall use risk in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a polyurethane electronic electrical insulating material comprises the following raw materials of polymerized fluororubber, polyurethane emulsion and a characteristic auxiliary coating, wherein the polymerized fluororubber comprises fluorine-containing monomer molecules, water, an auxiliary agent, a dispersing agent, a neutralization buffering agent, an initiator and a chain transfer agent, the polyurethane emulsion comprises polyether or polyester dihydric alcohol, isocyanate, acetone, N-methyl glycol and an ionizing reagent, the characteristic auxiliary coating comprises a cold-resistant tough coating, an elastic coating and a wear-resistant coating, the cold-resistant tough coating is a polyimide tough film, the elastic coating is an elastic coating, the wear-resistant coating is a wear-resistant coating, and the raw materials are processed by the following steps to obtain a finished product:
the method comprises the following steps: forming an elastic polymer by fluorine-containing monomer molecules, adopting an aerosol emulsion polymerization mode, taking water as a medium, carrying a polymerization reaction and uniformly loading the polymer in the water, taking low-concentration ammonium perfluorooctanoate as a dispersing agent to form a polymer emulsion, carrying out the polymerization reaction in a liquid phase, taking acid generated by the neutralization reaction as a neutralization buffering agent, maintaining the colloid stability, the reaction speed stability and the latex concentration stability, controlling the pH to be 5-6, and then taking (NH) S20 as an initiator to decompose an active group to initiate the polymerization reaction, wherein the decomposition speed is higher than 85 ℃, the decomposition speed is 0.5h below 90 ℃, the decomposition speed is 30%, the decomposition speed is 50% within 1h, the decomposition speed is 75% within 2h, and the decomposition speed is 90% within 3 h; (NH) S20 decomposes at more than 40 ℃, decomposes at 85 ℃ rapidly, and finally takes diethyl malonate as a chain transfer agent to reduce the molecular weight of a copolymer, thereby reducing the Mooney viscosity, and has the more important function of generating a nonionic end group at the end of a molecular chain, so that the vulcanization performance is excellent, the processing fluidity is good, alloy corrosion cannot be caused, and the polymerized fluororubber is prepared by emulsion polymerization;
step two: a stable PU emulsion is prepared by a self-emulsifying method, polyether or polyester diol and isocyanate are prepared into a prepolymer, a proper amount of acetone is added to reduce the viscosity, then N-methyldiethanolamine is used for chain extension, acetone is added to reduce the viscosity, and then an ionizing reagent is added to stir and ionize. Dispersing ionized PU into a medium containing 80% of acetone and 20% of water, and finally evaporating the acetone to obtain water emulsion type polyurethane with the particle size of 0.03-100 mu m;
step three: preparing a polyimide flexible film, synthesizing polyamic acid, dissolving diaminodiphenyl ether in a solvent dimethylacetamide under the protection of nitrogen, adding small amount of dry pyromellitic dianhydride while stirring, adding pyromellitic dianhydride, filtering the prepared polyamic acid under the protection of dry nitrogen, defoaming, preparing, casting, preparing polyamic acid solution, preparing photosensitive film base, casting the mixture to a stainless steel circulating endless belt running below the stainless steel circulating endless belt through a gap of a casting nozzle, drying and forming the mixture into a gel-like film with self-supporting property, performing heat treatment, rolling to obtain a primary finished product of the polyimide tough film, stretching, the polyimide film prepared by the casting method has poor performance, the performance of the stretched film can be greatly improved, and then a high-performance polyimide tough film finished product is obtained by cooling, edge cutting and rolling;
step four: adding the prepared polymerized fluororubber and polyurethane emulsion into a polymerization kettle, heating for a second polymerization reaction, adding an adaptive solvent to fuse the polymerized fluororubber and the polyurethane emulsion, adding mixed acetone with a proper proportion to reduce viscosity, evaporating the acetone, and adding a proper amount of curing agent to obtain polyurethane fluororubber;
step five: cooling and molding the prepared polyurethane fluororubber, then performing covering operation of an auxiliary coating, respectively and uniformly coating an elastic coating and a wear-resistant coating on the outer surface of the polyurethane fluororubber, covering the outermost part of the polyurethane fluororubber with the prepared polyimide tough film, and performing heating plasticity on the whole body as required after the whole body is fused and molded to obtain the polyurethane electronic electrical insulating material;
preferably, the preparation of the polyurethane emulsion adopts an acetone method to prepare a high-viscosity prepolymer containing NCO end groups, then acetone is added to reduce the viscosity, then hydrophilic monomers are used for chain extension, water is added under high-speed stirring, the prepolymer is dispersed in the water through strong shearing action, and after emulsification, the prepolymer is decompressed, distilled and recovered with solvent, thus obtaining the PU water dispersion system.
Preferably, the polymerization reaction of the polymerized fluororubber is performed by using diethyl malonate as a chain transfer agent, the diethyl malonate is a molecular weight regulator, and the diethyl malonate can eliminate reacted monomers from free radicals, so that the polymerization speed is reduced, the molecular weight is reduced, and the reaction speed is reduced.
Preferably, isopentane as a chain transfer agent in the polymerization reaction of the polymerized fluororubber is used for transferring an active center rather than eliminating a free radical, and the influence on the polymerization speed is small, but the chain transfer constant is particularly large, so that the molecular weight and the molecular weight distribution of the polymer can be changed drastically.
Preferably, the method for preparing the water-based PU by adopting the acetone method in the polyurethane emulsion has the advantages of easily controlled reaction, good repeatability, easily controlled emulsion particle size and high emulsion quality.
The invention has the beneficial effects that: the preparation method of the polyurethane electronic electrical insulating material adopts fluororubber as a main body, adopts acetone method to perform self-emulsification, and adopts the mutual polymerization of the urethane emulsion and the modified fluororubber to form the modified fluororubber, so that the whole body has better corrosion resistance, can adapt to high-temperature and low-temperature environments, improves the cold and heat resistance of the whole body to the utmost extent, greatly improves the working applicability of the whole body, obviously improves the self structure toughness and the cold resistance of the obtained finished product by externally covering the prepared polyimide toughness film, simultaneously respectively and uniformly coats the whole body with the coating used by the elastic coating and the wear-resistant coating, greatly enhances the plasticity of the whole body on the basis of not changing the whole basic performance of the polyurethane electronic electrical insulating material, and can perform the shaping according to the working production requirements of electronic and electrical products, the flame-retardant rubber can be used as a lead material of electronic and electrical products or equipment, has better elasticity and wear resistance, correspondingly has better flame retardant property, and fundamentally improves the overall use safety of the electronic and electrical products or equipment in use.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The preparation method of the polyurethane electronic and electric insulating material comprises the following steps:
the method comprises the following steps: forming an elastic polymer by fluorine-containing monomer molecules, adopting an aerosol emulsion polymerization mode, taking water as a medium, carrying a polymerization reaction and uniformly loading the polymer in the water, taking low-concentration ammonium perfluorooctanoate as a dispersing agent to form a polymer emulsion, carrying out the polymerization reaction in a liquid phase, taking acid generated by the neutralization reaction as a neutralization buffering agent, maintaining the colloid stability, the reaction speed stability and the latex concentration stability, controlling the pH to be 5-6, and then taking (NH) S20 as an initiator to decompose an active group to initiate the polymerization reaction, wherein the decomposition speed is higher than 85 ℃, the decomposition speed is 0.5h below 90 ℃, the decomposition speed is 30%, the decomposition speed is 50% within 1h, the decomposition speed is 75% within 2h, and the decomposition speed is 90% within 3 h; (NH) S20 decomposes at more than 40 ℃, decomposes at 85 ℃ rapidly, and finally takes diethyl malonate as a chain transfer agent to reduce the molecular weight of a copolymer, thereby reducing the Mooney viscosity, and has the more important function of generating a nonionic end group at the end of a molecular chain, so that the vulcanization performance is excellent, the processing fluidity is good, alloy corrosion cannot be caused, and the polymerized fluororubber is prepared by emulsion polymerization;
step two: a stable PU emulsion is prepared by a self-emulsifying method, polyether or polyester diol and isocyanate are prepared into a prepolymer, a proper amount of acetone is added to reduce the viscosity, then N-methyldiethanolamine is used for chain extension, acetone is added to reduce the viscosity, and then an ionizing reagent is added to stir and ionize. Dispersing ionized PU into a medium containing 80% of acetone and 20% of water, and finally evaporating the acetone to obtain water emulsion type polyurethane with the particle size of 0.03-100 mu m;
step three: preparing a polyimide flexible film, synthesizing polyamic acid, dissolving diaminodiphenyl ether in a solvent dimethylacetamide under the protection of nitrogen, adding small amount of dry pyromellitic dianhydride while stirring, adding pyromellitic dianhydride, filtering the prepared polyamic acid under the protection of dry nitrogen, defoaming, preparing, casting, preparing polyamic acid solution, preparing photosensitive film base, casting the mixture to a stainless steel circulating endless belt running below the stainless steel circulating endless belt through a gap of a casting nozzle, drying and forming the mixture into a gel-like film with self-supporting property, performing heat treatment, rolling to obtain a primary finished product of the polyimide tough film, stretching, the polyimide film prepared by the casting method has poor performance, the performance of the stretched film can be greatly improved, and then a high-performance polyimide tough film finished product is obtained by cooling, edge cutting and rolling;
step four: adding the prepared polymerized fluororubber and polyurethane emulsion into a polymerization kettle, heating for a second polymerization reaction, adding an adaptive solvent to fuse the polymerized fluororubber and the polyurethane emulsion, adding mixed acetone with a proper proportion to reduce viscosity, evaporating the acetone, and adding a proper amount of curing agent to obtain polyurethane fluororubber;
step five: cooling and molding the prepared polyurethane fluororubber, then performing covering operation of an auxiliary coating, respectively and uniformly coating an elastic coating and a wear-resistant coating on the outer surface of the polyurethane fluororubber, covering the outermost part of the polyurethane fluororubber with the prepared polyimide tough film, and performing heating plasticity on the whole body as required after the whole body is fused and molded to obtain the polyurethane electronic electrical insulating material;
according to the preparation method of the polyurethane electronic electrical insulating material obtained by the first embodiment, the polyurethane electronic electrical insulating material prepared by the method has good insulating property, strong plasticity, certain elasticity and high wear resistance, and strong integral corrosion resistance;
example two
The preparation method of the polyurethane electronic and electric insulating material comprises the following steps:
the method comprises the following steps: forming an elastic polymer by fluorine-containing monomer molecules, adopting an aerosol emulsion polymerization mode, taking water as a medium, carrying a polymerization reaction and uniformly loading the polymer in the water, taking low-concentration ammonium perfluorooctanoate as a dispersing agent to form a polymer emulsion, carrying out the polymerization reaction in a liquid phase, taking acid generated by the neutralization reaction as a neutralization buffering agent, maintaining the colloid stability, the reaction speed stability and the latex concentration stability, controlling the pH to be 5-6, and then taking (NH) S20 as an initiator to decompose an active group to initiate the polymerization reaction, wherein the decomposition speed is higher than 85 ℃, the decomposition speed is 0.5h below 90 ℃, the decomposition speed is 30%, the decomposition speed is 50% within 1h, the decomposition speed is 75% within 2h, and the decomposition speed is 90% within 3 h; (NH) S20 decomposes at more than 40 ℃, decomposes at 85 ℃ rapidly, and finally takes diethyl malonate as a chain transfer agent to reduce the molecular weight of a copolymer, thereby reducing the Mooney viscosity, and has the more important function of generating a nonionic end group at the end of a molecular chain, so that the vulcanization performance is excellent, the processing fluidity is good, alloy corrosion cannot be caused, and the polymerized fluororubber is prepared by emulsion polymerization;
step two: a stable PU emulsion is prepared by a self-emulsifying method, polyether or polyester diol and isocyanate are prepared into a prepolymer, a proper amount of acetone is added to reduce the viscosity, then N-methyldiethanolamine is used for chain extension, acetone is added to reduce the viscosity, and then an ionizing reagent is added to stir and ionize. Dispersing ionized PU into a medium containing 60% of acetone and 40% of water, and finally evaporating the acetone to obtain water emulsion type polyurethane;
step three: preparing a polyimide flexible film, synthesizing polyamic acid, dissolving diaminodiphenyl ether in a solvent dimethylacetamide under the protection of nitrogen, adding small amount of dry pyromellitic dianhydride while stirring, adding pyromellitic dianhydride, filtering the prepared polyamic acid under the protection of dry nitrogen, defoaming, preparing, casting, preparing polyamic acid solution, preparing photosensitive film base, casting the mixture to a stainless steel circulating endless belt running below the stainless steel circulating endless belt through a gap of a casting nozzle, drying and forming the mixture into a gel-like film with self-supporting property, performing heat treatment, rolling to obtain a primary finished product of the polyimide tough film, stretching, the polyimide film prepared by the casting method has poor performance, the performance of the stretched film can be greatly improved, and then a high-performance polyimide tough film finished product is obtained by cooling, edge cutting and rolling;
step four: adding the prepared polymerized fluororubber and polyurethane emulsion into a polymerization kettle, heating for a second polymerization reaction, adding an adaptive solvent to fuse the polymerized fluororubber and the polyurethane emulsion, adding mixed acetone with a proper proportion to reduce viscosity, evaporating the acetone, and adding a proper amount of curing agent to obtain polyurethane fluororubber;
step five: cooling and molding the prepared polyurethane fluororubber, then performing covering operation of an auxiliary coating, respectively and uniformly coating an elastic coating and a wear-resistant coating on the outer surface of the polyurethane fluororubber, covering the outermost part of the polyurethane fluororubber with the prepared polyimide tough film, and performing heating plasticity on the whole body as required after the whole body is fused and molded to obtain the polyurethane electronic electrical insulating material;
according to the second embodiment, a preparation method of the polyurethane electronic and electric insulating material can not be obtained;
EXAMPLE III
The preparation method of the polyurethane electronic and electric insulating material comprises the following steps:
the method comprises the following steps: forming an elastic polymer by fluorine-containing monomer molecules, adopting an aerosol emulsion polymerization mode, taking water as a medium, carrying a polymerization reaction and uniformly loading the polymer in the water, taking low-concentration ammonium perfluorooctanoate as a dispersing agent to form a polymer emulsion, carrying out the polymerization reaction in a liquid phase, taking acid generated by the neutralization reaction as a neutralization buffering agent, maintaining the colloid stability, the reaction speed stability and the latex concentration stability, controlling the pH to be 5-6, and then taking (NH) S20 as an initiator to decompose an active group to initiate the polymerization reaction, wherein the decomposition speed is higher than 85 ℃, the decomposition speed is 0.5h below 90 ℃, the decomposition speed is 30%, the decomposition speed is 50% within 1h, the decomposition speed is 75% within 2h, and the decomposition speed is 90% within 3 h; (NH) S20 decomposes at more than 40 ℃, decomposes at 85 ℃ rapidly, and finally takes diethyl malonate as a chain transfer agent to reduce the molecular weight of a copolymer, thereby reducing the Mooney viscosity, and has the more important function of generating a nonionic end group at the end of a molecular chain, so that the vulcanization performance is excellent, the processing fluidity is good, alloy corrosion cannot be caused, and the polymerized fluororubber is prepared by emulsion polymerization;
step two: a stable PU emulsion is prepared by a self-emulsifying method, polyether or polyester diol and isocyanate are prepared into a prepolymer, a proper amount of acetone is added to reduce the viscosity, then N-methyldiethanolamine is used for chain extension, acetone is added to reduce the viscosity, and then an ionizing reagent is added to stir and ionize. Dispersing ionized PU into a medium containing 20% of acetone and 80% of water, and finally evaporating the acetone to obtain water emulsion type polyurethane;
step three: preparing a polyimide flexible film, synthesizing polyamic acid, dissolving diaminodiphenyl ether in a solvent dimethylacetamide under the protection of nitrogen, adding small amount of dry pyromellitic dianhydride while stirring, adding pyromellitic dianhydride, filtering the prepared polyamic acid under the protection of dry nitrogen, defoaming, preparing, casting, preparing polyamic acid solution, preparing photosensitive film base, casting the mixture to a stainless steel circulating endless belt running below the stainless steel circulating endless belt through a gap of a casting nozzle, drying and forming the mixture into a gel-like film with self-supporting property, performing heat treatment, rolling to obtain a primary finished product of the polyimide tough film, stretching, the polyimide film prepared by the casting method has poor performance, the performance of the stretched film can be greatly improved, and then a high-performance polyimide tough film finished product is obtained by cooling, edge cutting and rolling;
step four: adding the prepared polymerized fluororubber and polyurethane emulsion into a polymerization kettle, heating for a second polymerization reaction, adding an adaptive solvent to fuse the polymerized fluororubber and the polyurethane emulsion, adding mixed acetone with a proper proportion to reduce viscosity, evaporating the acetone, and adding a proper amount of curing agent to obtain polyurethane fluororubber;
step five: cooling and molding the prepared polyurethane fluororubber, then performing covering operation of an auxiliary coating, respectively and uniformly coating an elastic coating and a wear-resistant coating on the outer surface of the polyurethane fluororubber, covering the outermost part of the polyurethane fluororubber with the prepared polyimide tough film, and performing heating plasticity on the whole body as required after the whole body is fused and molded to obtain the polyurethane electronic electrical insulating material;
according to the third embodiment, a preparation method of the polyurethane electronic and electric insulating material can not be obtained;
preferably, the preparation of the polyurethane emulsion adopts an acetone method to prepare a high-viscosity prepolymer containing NCO end groups, then acetone is added to reduce the viscosity, then hydrophilic monomers are used for chain extension, water is added under high-speed stirring, the prepolymer is dispersed in the water through strong shearing action, and a PU (polyurethane) water dispersion system can be prepared by recovering a solvent through reduced pressure distillation after emulsification;
preferably, the polymerization reaction of the polymerized fluororubber takes diethyl malonate as a chain transfer agent, the diethyl malonate is a molecular weight telomerization agent, and the diethyl malonate can enable the reacted monomers to disappear from radicals, so that the polymerization speed is reduced, the molecular weight is reduced, the reaction speed is reduced, the prepared polymerized fluororubber can perform stable repolymerization reaction with polyurethane emulsion more quickly, and the overall preparation speed can be greatly improved;
preferably, isopentane as a chain transfer agent in the polymerization reaction for polymerizing the fluororubber is used for transferring an active center rather than eliminating a free radical, so that the influence on the polymerization speed is small, but the chain transfer constant is particularly large, so that the molecular weight and the molecular weight distribution of the polymer can be changed violently, and the influence of other reagents on the overall reaction is reduced;
preferably, the method for preparing the water-based PU by adopting the acetone method in the polyurethane emulsion has the advantages of easily controlled reaction, good repeatability, easily controlled emulsion particle size and high emulsion quality, optimizes the preparation process of the electronic and electric insulating material to the greatest extent, can enable the whole to be more conveniently controlled, and does not increase the risk of the whole preparation.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and those skilled in the art can make simple modifications or equivalent substitutions on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. A preparation method of a polyurethane electronic electric insulating material comprises the following raw materials of polymerized fluororubber, polyurethane emulsion and a characteristic auxiliary coating, and is characterized in that: the polymerized fluororubber comprises fluorine-containing monomer molecules, water, an auxiliary agent, a dispersing agent, a neutralization buffering agent, an initiator and a chain transfer agent, the polyurethane emulsion comprises polyether or polyester dihydric alcohol, isocyanate, acetone, N-methyl diethanol and an ionizing reagent, the characteristic auxiliary coating comprises a cold-resistant tough coating, an elastic coating and a wear-resistant coating, the cold-resistant tough coating is a polyimide tough film, the elastic coating is an elastic coating, the wear-resistant coating is a wear-resistant coating, and the raw materials are processed by the following steps to obtain a finished product:
the method comprises the following steps: an elastic polymer is formed by fluorine-containing monomer molecules, an aerosol emulsion polymerization mode is adopted, water is used as a medium, a carrying polymerization reaction and a carrying polymer are uniformly contained in the elastic polymer, low-concentration ammonium perfluorooctanoate is used as a dispersing agent to form a polymer emulsion, the polymerization reaction is carried out in a liquid phase, acid generated by the neutralization reaction is used as a neutralization buffering agent, the colloid stability, the reaction speed stability and the latex concentration stability are maintained, the pH is controlled to be 5-6, then (NH) S20 is used as an initiator, an active group is decomposed to initiate the polymerization reaction, the decomposition speed is higher than 85 ℃, the decomposition speed is lower than 90 ℃, the decomposition speed is 0.5h for 30%, the decomposition speed is 50% in 1h, the decomposition speed is 75%; (NH) S20 decomposes at a temperature of above 40 ℃, decomposes at a temperature of 85 ℃ rapidly, and finally takes diethyl malonate as a chain transfer agent to reduce the molecular weight of the copolymer, so as to reduce the Mooney viscosity, and has the more important function of generating a nonionic end group at the end of a molecular chain, so that the vulcanization performance is excellent, the processing fluidity is good, alloy corrosion cannot be caused, and the polymerized fluororubber is prepared by emulsion polymerization;
step two: a stable PU emulsion is prepared by a self-emulsifying method, polyether or polyester diol and isocyanate are prepared into a prepolymer, a proper amount of acetone is added to reduce the viscosity, then N-methyldiethanolamine is used for chain extension, acetone is added to reduce the viscosity, and then an ionizing reagent is added to stir and ionize. Dispersing ionized PU into a medium containing 80% of acetone and 20% of water, and finally evaporating the acetone to obtain water emulsion type polyurethane with the particle size of 0.03-100 mu m;
step three: preparing a polyimide flexible film, synthesizing polyamic acid, dissolving diaminodiphenyl ether in a solvent dimethylacetamide under the protection of nitrogen, adding small amount of dry pyromellitic dianhydride while stirring, adding pyromellitic dianhydride, filtering the prepared polyamic acid under the protection of dry nitrogen, defoaming, preparing, casting, preparing polyamic acid solution, preparing photosensitive film base, casting the mixture to a stainless steel circulating endless belt running below the stainless steel circulating endless belt through a gap of a casting nozzle, drying and forming the mixture into a gel-like film with self-supporting property, performing heat treatment, rolling to obtain a primary finished product of the polyimide tough film, stretching, the polyimide film prepared by the tape casting method has poor performance, the performance of the stretched film can be greatly improved, and then a high-performance polyimide tough film finished product is obtained through cooling, edge cutting and rolling;
step four: adding the prepared polymerized fluororubber and polyurethane emulsion into a polymerization kettle, heating for a second polymerization reaction, adding an adaptive solvent to fuse the polymerized fluororubber and the polyurethane emulsion, adding mixed acetone with a proper proportion to reduce viscosity, evaporating the acetone, and adding a proper amount of curing agent to obtain polyurethane fluororubber;
step five: and cooling and molding the prepared polyurethane fluororubber, then performing covering operation of an auxiliary coating, respectively and uniformly coating an elastic coating and a wear-resistant coating on the outer surface of the polyurethane fluororubber, covering the outermost part of the polyurethane fluororubber with the prepared polyimide tough film, and performing heating plasticity on the whole body as required after the whole body is fused and molded to obtain the polyurethane electronic electric insulating material.
2. The method for preparing the polyurethane electronic and electric insulating material according to claim 1, wherein the method comprises the following steps: the preparation method of the polyurethane emulsion comprises the steps of firstly preparing a high-viscosity prepolymer containing NCO end groups by an acetone method, then adding acetone to reduce viscosity, then using hydrophilic monomers to carry out chain extension, adding water under high-speed stirring, dispersing the prepolymer in the water through a strong shearing action, emulsifying, and then carrying out reduced pressure distillation to recover a solvent to obtain the PU water dispersion system.
3. The method for preparing the polyurethane electronic and electric insulating material according to claim 1, wherein the method comprises the following steps: the polymerization reaction of the polymerized fluororubber takes diethyl malonate as a chain transfer agent, the diethyl malonate is a molecular weight telomer agent, and the diethyl malonate can eliminate free radicals of monomers to reduce the polymerization speed, the molecular weight and the reaction speed.
4. The method for preparing the polyurethane electronic and electric insulating material according to claim 1, wherein the method comprises the following steps: in the polymerization reaction of the polymerized fluororubber, isopentane is used as a chain transfer agent, the transfer of an active center is required instead of the disappearance of free radicals, the influence on the polymerization speed is small, but the molecular weight and the molecular weight distribution of the polymer can be changed violently due to the extremely large chain transfer constant.
5. The method for preparing the polyurethane electronic and electric insulating material according to claim 1, wherein the method comprises the following steps: the method for preparing the water-based PU by adopting the acetone method in the polyurethane emulsion has the advantages of easy control of reaction, good repeatability, easy control of emulsion particle size and high emulsion quality.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454144A (en) * | 2000-08-11 | 2003-11-05 | 因德斯普罗伊恩公司 | Compacted material comprising a polyurethane elastomer and rubber, method for obtaining said material and applications thereof |
| CN102443090A (en) * | 2011-10-25 | 2012-05-09 | 中昊晨光化工研究院 | Synthetic method for fluororubber |
| CN103087291A (en) * | 2013-02-01 | 2013-05-08 | 陕西科技大学 | Preparation method of high solid content waterborne polyurethane |
| CN103665238A (en) * | 2013-12-11 | 2014-03-26 | 中昊晨光化工研究院有限公司 | Synthesis method of fluororubber with wide molecular weight distribution |
| CN105330878A (en) * | 2015-11-25 | 2016-02-17 | 南京理工大学 | Preparation method of fluororesin-containing modified polyimide film |
| JP2018062142A (en) * | 2016-10-14 | 2018-04-19 | 宇部興産株式会社 | Laminate and aqueous coating agent |
| CN108727706A (en) * | 2017-04-21 | 2018-11-02 | 高永健 | Electric power overhaul tool radiation protection insulating materials and preparation method thereof |
-
2020
- 2020-12-02 CN CN202011394651.5A patent/CN112706480B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454144A (en) * | 2000-08-11 | 2003-11-05 | 因德斯普罗伊恩公司 | Compacted material comprising a polyurethane elastomer and rubber, method for obtaining said material and applications thereof |
| CN102443090A (en) * | 2011-10-25 | 2012-05-09 | 中昊晨光化工研究院 | Synthetic method for fluororubber |
| CN103087291A (en) * | 2013-02-01 | 2013-05-08 | 陕西科技大学 | Preparation method of high solid content waterborne polyurethane |
| CN103665238A (en) * | 2013-12-11 | 2014-03-26 | 中昊晨光化工研究院有限公司 | Synthesis method of fluororubber with wide molecular weight distribution |
| CN105330878A (en) * | 2015-11-25 | 2016-02-17 | 南京理工大学 | Preparation method of fluororesin-containing modified polyimide film |
| JP2018062142A (en) * | 2016-10-14 | 2018-04-19 | 宇部興産株式会社 | Laminate and aqueous coating agent |
| CN108727706A (en) * | 2017-04-21 | 2018-11-02 | 高永健 | Electric power overhaul tool radiation protection insulating materials and preparation method thereof |
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