CN112126393B - Phase-change heat storage pouring sealant and preparation method thereof - Google Patents
Phase-change heat storage pouring sealant and preparation method thereof Download PDFInfo
- Publication number
- CN112126393B CN112126393B CN202011039996.9A CN202011039996A CN112126393B CN 112126393 B CN112126393 B CN 112126393B CN 202011039996 A CN202011039996 A CN 202011039996A CN 112126393 B CN112126393 B CN 112126393B
- Authority
- CN
- China
- Prior art keywords
- phase
- parts
- change
- component
- heat
- 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
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention belongs to the technical field of pouring sealant, and particularly relates to phase-change heat storage pouring sealant and a preparation method thereof. The invention provides a phase-change heat storage pouring sealant which comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy resin, 30-50 parts of modified powder and 5-10 parts of diluent; the preparation raw materials of the component B comprise: 20-25 parts of anhydride curing agent and 1-3 parts of accelerator. The phase-change heat-storage pouring sealant is prepared from the heat-conducting filler with a certain particle size range, the self-made phase-change microcapsules and the epoxy resin, and the obtained phase-change heat-storage pouring sealant is strong in heat-conducting capacity and good in temperature regulation performance through mutual cooperation of the components.
Description
Technical Field
The invention belongs to the technical field of pouring sealant, and particularly relates to phase-change heat storage pouring sealant and a preparation method thereof.
Background
Epoxy resin is a thermosetting resin, has high chemical stability and corrosion resistance, good adhesive property, high mechanical strength and strong electrical insulation property, and is widely applied in industry, especially in aerospace industry. The pouring sealant is also called electronic glue, and along with the increasing popularization of electronic products, the pouring sealant plays a more important role in the daily life of people. When the traditional pouring sealant is actually applied to electronic chip packaging, local uneven heating is easy to occur due to poor heat conduction capability, and the service life of an electronic component is seriously influenced.
Chinese patent CN 105860893A discloses a method for improving heat conduction and high and low temperature change resistance of a pouring sealant by using a mica sheet, which can enable a cured substance of the pouring sealant to be used for a long time under the conditions of high temperature and low temperature. But because the compatibility between the mica sheet and the matrix resin is poor, microcracks are easy to generate after long-term use, and the normal use of equipment is influenced.
The Phase Change Microcapsules (PCMs) are a novel intelligent material which can absorb and emit a large amount of heat when being mutually converted from a solid state and a liquid state, and meanwhile, the temperature of the phase change material is not changed. Due to the characteristics, the solar heat collector is widely applied to the fields of solar energy, industrial waste heat recovery, cold accumulation air conditioning, aerospace and the like. At present, a pouring sealant which can well regulate and control the temperature change of the pouring sealant, has strong heat storage capacity and excellent performance is needed to be provided.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a phase change heat storage pouring sealant, which comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy resin, 30-50 parts of modified powder and 5-10 parts of diluent; the preparation raw materials of the component B comprise: 20-25 parts of anhydride curing agent and 1-3 parts of accelerator.
As a preferable technical scheme, the modified powder comprises, by weight, 15-25 parts of heat-conducting filler, 15-25 parts of phase-change microcapsule and 0.1-0.4 part of modifier.
As a preferable technical solution, the heat conductive filler is at least one selected from the group consisting of aluminum oxide, boron nitride, silicon nitride, aluminum hydroxide, calcium carbonate, aluminum powder, and zinc oxide.
As a preferable technical scheme, the average particle size of the heat conduction filler comprises at least one of 0.2-1, 1-10, 10-30, 30-50, 50-100, 100-200 and 200-300 microns.
As a preferable technical scheme, the phase change point of the phase change microcapsule is 20-60 ℃, the enthalpy value is 160-240J/g, and the average particle size comprises at least one of 1-5, 5-10, 10-30 and 30-60 micrometers.
As a preferred technical scheme, the preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on heat-conducting powder; s2, preparing phase-change microcapsule emulsion; s3, adding the heat-conducting powder obtained in the step S1 into the phase-change microcapsule emulsion obtained in the step S2, stirring for 1-2 hours, and performing post-treatment to obtain the phase-change microcapsule.
As a preferable technical scheme, the gas for plasma pretreatment is oxygen and/or air, and the pretreatment time is 10-40 min.
As a preferred technical scheme, the phase-change microcapsule emulsion is prepared from the following raw materials: 200-300 parts of phase-change material, 5-15 parts of surfactant, 0.01-0.1 part of auxiliary agent, 500-700 parts of water and 40-80 parts of melamine resin prepolymer.
The second aspect of the invention provides a preparation method of the phase-change heat storage pouring sealant, which comprises the following steps:
(1) preparing a component A: weighing epoxy resin, modified powder and diluent, fully stirring and uniformly mixing in a reaction kettle, taking out, and placing in a vacuum box for deaeration for 1-3h to obtain a component A;
(2) preparing a component B: weighing the curing agent and the accelerator, putting into a reaction kettle, fully stirring and uniformly mixing, and defoaming in a vacuum box for 1-3h to obtain the component B.
In the third aspect of the invention, the use method of the phase-change heat-storage pouring sealant is improved, and the prepared component A and the component B are mixed, poured and packaged, and cured.
Has the advantages that: the phase-change heat-storage pouring sealant is prepared from the heat-conducting filler with a certain particle size range, the self-made phase-change microcapsules and the epoxy resin, and the obtained phase-change heat-storage pouring sealant is strong in heat-conducting capacity and good in temperature regulation performance through mutual cooperation of the components.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the problems, the invention provides a phase change heat storage pouring sealant which comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy resin, 30-50 parts of modified powder and 5-10 parts of diluent; the preparation raw materials of the component B comprise: 20-25 parts of anhydride curing agent and 1-3 parts of accelerator.
Component A
The epoxy resin comprises at least one of bisphenol A epoxy resin, novolac epoxy resin and aliphatic epoxy resin; the type of the epoxy resin comprises one or more of NPCN-701, NPPN-631, NPPN-638S, NPPN-431, EPN1179 and EPN 1180; the manufacturers of EPN1179 and EPN1180 are Hensmai USA.
The modified powder comprises, by weight, 15-25 parts of a heat-conducting filler, 15-25 parts of a phase-change microcapsule and 0.1-0.4 part of a modifier.
The heat-conducting filler is selected from at least one of aluminum oxide, boron nitride, silicon nitride, aluminum hydroxide, aluminum powder, zinc oxide and calcium carbonate; preferably, the average particle size of the heat-conducting filler is at least one of 0.2-1, 1-10, 10-30, 30-50, 50-100, 100-200 and 200-300 micrometers.
The phase change point of the phase change microcapsule is 20-60 ℃, the enthalpy value is 160-240J/g, and the average particle size comprises at least one of 1-5, 5-10, 10-30 and 30-60 micrometers;
the preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on heat-conducting powder; s2, preparing phase-change microcapsule emulsion; s3, adding the heat-conducting powder obtained in the step S1 into the phase-change microcapsule emulsion obtained in the step S2, stirring for 1-2 hours, and performing post-treatment to obtain the phase-change microcapsule.
The heat conducting powder is selected from at least one of boron nitride nanosheets, graphene nanosheets, nano aluminum oxide, graphene oxide nanosheets, nano zinc oxide and nano calcium carbonate;
the heat-conducting powder can be prepared by self or purchased, and the purchase manufacturers have no special limitation.
The gas for plasma pretreatment is oxygen and/or air, and the pretreatment time is 10-40 min. Active groups are introduced to the surface of the heat-conducting powder by carrying out plasma pretreatment on the heat-conducting powder.
The phase-change microcapsule emulsion is prepared from the following raw materials: 200-300 parts of phase-change material, 5-15 parts of surfactant, 0.01-0.1 part of auxiliary agent, 500-700 parts of water and 40-80 parts of melamine resin prepolymer. The preparation method of the phase-change microcapsule emulsion comprises the following steps: (1) melting the phase change material to prepare an oil phase; (2) adding a surfactant and an auxiliary agent into water, dissolving, and preparing a water phase; (3) adding the oil phase into the water phase while stirring, and uniformly stirring to obtain microemulsion; (4) adding the melamine resin prepolymer into the microemulsion, uniformly stirring, adjusting the pH to 4-5, reacting for 30-60 min, slowly heating to 70 +/-10 ℃, and continuously reacting for 3-5 hours to obtain the phase-change microcapsule emulsion.
Preferably, the preparation of the phase-change microcapsule emulsion comprises the following steps:
(1) melting the phase change material to prepare an oil phase; (2) adding a surfactant and an auxiliary agent into water, dissolving, and preparing a water phase; (3) adding the oil phase into the water phase while stirring, and uniformly stirring to obtain microemulsion; (4) adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 150-250 rpm; and adjusting the pH value to 4-5, reacting for 30-60 min, slowly heating to 70 +/-10 ℃, and continuously reacting for 3-5 hours to obtain the phase-change microcapsule emulsion.
The heat conducting powder accounts for 5-15 parts by weight.
Preferably, the phase change material is long-chain alkane; further preferably, the chemical formula of the phase-change material is CnH2n+2Wherein n is more than or equal to 18; more preferably, 22 ≧ n ≧ 18; the phase-change material has the advantages of good chemical stability, no corrosion, no toxicity, low supercooling degree in the cooling crystallization process and higher latent heat value. In the present application, the phase change material is paraffin.
Preferably, the surfactant is an anionic surfactant and/or a block copolymer. The anionic surfactant is a sodium sulfate surfactant and/or a sodium sulfonate surfactant; sodium sulfate surfactants include, for example, sodium lauryl sulfate, sodium 2-ethylhexyl sulfate; the sodium sulfonate surfactant can be exemplified by sodium polystyrene sulfonate, sodium dodecyldiphenyl sulfonate, sodium alpha-olefin sulfonate, sodium dodecylbenzene sulfonate, sodium long-chain carboxylate polyoxyethylene sulfonate, disodium sulfosuccinate alkyl polyoxyethylene ether monoester sulfonate; the block copolymer comprises at least one of ethylene-maleic anhydride copolymer and styrene-maleic anhydride copolymer.
Preferably, the auxiliary agent is selected from at least one of animal glue, gelatin, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives and polyacrylate.
The shape and the size of the phase-change microcapsule are controlled by selecting the surfactant, but when the content of the surfactant is low, the phase-change material cannot be well dispersed, and the capsule with a regular shape is difficult to form; when the content of the surfactant is more, the surface of the capsule is rough; the applicant finds that by adding a small amount of auxiliary agents, the oil phase is promoted to form independent and uniform liquid drops in the water phase, and the three-dimensional space feeling of the microcapsule is increased.
Preferably, the melamine resin prepolymer is at least one selected from melamine-formaldehyde prepolymer, methylated melamine-formaldehyde prepolymer, urea-formaldehyde prepolymer and cyclic urea prepolymer.
In the step (4), the pH regulator is not particularly limited, can regulate the pH to 4-5, and does not influence the purpose of the invention; examples of the pH adjuster include citric acid, acetic acid, hydrochloric acid, potassium dihydrogen phosphate, and sodium dihydrogen phosphate.
In the step (4), preferably, after reacting for 30-60 min, uniformly heating to 70 +/-10 ℃ in 90-150 min; more preferably, after the reaction is carried out for 30-60 min, the temperature is uniformly increased to 70 +/-10 ℃ within 110-130 min; reacting for 30-60 min, namely adjusting the pH to 4-5 and calculating the reaction time; the applicant finds that the phase-change microcapsule with bright surface and high temperature resistance can be obtained by controlling a certain heating speed; if the temperature rising speed is too high, the obtained microcapsules have rough surfaces, and if the temperature rising speed is too low, the high temperature resistance of the phase change microcapsules is influenced.
In the step (4), preferably, after the pH is adjusted to 4-5, the stirring speed is reduced by 5-15rpm every 1 hour until the reaction is finished to obtain the phase-change microcapsule emulsion. The applicant also unexpectedly finds that the phase-change microcapsule with excellent performance can be obtained by controlling the stirring speed; too fast a reduction in the rotational speed is detrimental to the thorough mixing of the various substances and the uniform mixing with the shell material; too slow a reduction in rotational speed results in poor encapsulation of the newly formed shell material on the surface of the core material, which results in microcapsules that are susceptible to rupture and heat resistance that is severely compromised.
In step S3, the post-treatment step is not particularly limited, and is intended to remove liquid to obtain dried phase-change microcapsules. In the present application, the post-processing includes: dehydrating and drying.
The drying temperature is 0-100 ℃, and preferably 30-80 ℃.
The invention prepares the heat-conducting powder with a large number of negative ion groups deposited on the surface by pretreating the heat-conducting powder by using a plasma technology. The heat-conducting powder is added into the phase-change microcapsule microemulsion prepared from the melamine shell material, under the mutual attraction of negative charges on the surface of the powder and positive charges on the surface of the melamine resin shell material, the heat-conducting powder is tightly adsorbed on the surface of the microcapsule in situ to form a heat-conducting layer consisting of the heat-conducting powder, and the heat-conducting powder is added at the later stage of the phase-change microcapsule, so that the high heat resistance and the high heat conductivity of the phase-change microcapsule are improved.
The modifier is a silane coupling agent and/or a titanate coupling agent;
the silane coupling agent is at least one selected from SH6040, A-171, vinyl trimethoxy silane, KH-560, KH-550, (3,4 epoxy cyclohexyl) -ethyl trimethoxy silane and octyl triethoxy silane.
The titanate coupling agent is selected from at least one of titanium isopropoxide tristearate, titanium isopropoxide trioleate, titanium isopropoxide tri (dioctyl pyrophosphato acyloxy) titanate, titanium isopropoxide tri (ethylenediamine-N-ethoxy) titanate and tetra-neoalkoxy bis (didecyl phosphorous acyloxy) titanate.
The preparation method of the modified powder comprises the following steps: uniformly mixing the heat-conducting filler, the phase-change microcapsule and the modifier by using high-speed mixing equipment, and then drying for later use.
The drying temperature and the mixing equipment are not particularly limited.
Preferably, the diluent is a reactive diluent; the diluent is at least one selected from propylene oxide propylene ether, butyl glycidyl ether, glycerol epoxy resin, epichlorohydrin, propoxyglycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
In order to better achieve the aim of the invention, the component A also comprises at least one of a defoaming agent, a leveling agent, a flame retardant and an ultraviolet resistant agent; in the application, the component A comprises 0.5-1 part of defoaming agent and 2-4 parts of flame retardant; the defoaming agent is selected from one or more of alcohols, polyethers and polyether modified polysiloxane defoaming agents; the flame retardant is an organic flame retardant and/or an inorganic flame retardant; the inorganic flame retardant includes antimony trioxide, aluminum hydroxide, magnesium hydroxide; examples of the organic flame retardant include at least one of tributyl phosphate, tris (2-ethylhexyl) phosphate, tris (2-chloroethyl) phosphate, tris (2, 3-dichloropropyl) phosphate, tris (2, 3-dibromopropyl) phosphate, tolylene diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, and 2-ethylhexyl diphenyl phosphate.
B component
The anhydride curing agent is at least one selected from maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, polyazelaic anhydride, polysebacic anhydride, elaeostearic anhydride and diphenyl ether tetracid dianhydride.
The anhydride curing agent can also be replaced by amine curing agents and imidazole curing agents.
The accelerator is an amine accelerator and/or an alcohol accelerator; preferably, the accelerator is an amine accelerator; the accelerator is one or more selected from DMP-30, DMP-10, tertiary amine accelerators and quaternary ammonium salt accelerators.
The second aspect of the invention provides a preparation method of the phase-change heat storage pouring sealant, which comprises the following steps:
(1) preparing a component A: weighing epoxy resin, modified powder and diluent, fully stirring and uniformly mixing in a reaction kettle, taking out, and placing in a vacuum box for deaeration for 1-3h to obtain a component A;
(2) preparing a component B: weighing the curing agent and the accelerator, putting into a reaction kettle, fully stirring and uniformly mixing, and defoaming in a vacuum box for 1-3h to obtain the component B.
The third aspect of the invention provides a use method of the phase-change heat storage pouring sealant, which comprises the following steps: and mixing the prepared component A and the component B, and curing.
The curing temperature includes, but is not limited to, 40-70 ℃ and 70-150 ℃, and the curing temperature can be first-stage curing or second-stage curing.
In some preferred embodiments, curing is carried out at 110-.
In the application method, the mixing is performed at 20-30 ℃, and the stirring speed includes at least one of 50-200 r/min, 200-500 r/min, 500-1000 r/min, 1000-1500 r/min, and 1500-2500 r/min.
Preferably, the weight ratio of the component A to the component B is 6: 2-3.
The phase-change heat-storage pouring sealant is prepared from the heat-conducting filler with a certain particle size range, the self-made phase-change microcapsules and the epoxy resin, and the obtained phase-change heat-storage pouring sealant is strong in heat-conducting capacity and good in temperature regulation performance through mutual cooperation of the components.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
The phase-change heat storage pouring sealant comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 30 parts of epoxy resin (the type of the epoxy resin is EPN1180, and the manufacturer is American Henshimei), 50 parts of modified powder, 10 parts of diluent, 0.8 part of defoaming agent (the type is B-0997, and the manufacturer is Federal), and 3 parts of flame retardant magnesium hydroxide; the preparation raw materials of the component B comprise: 25 parts of anhydride curing agent maleic anhydride and 3 parts of accelerator (model number DMP-30, the Chinese name is 2, 4, 6-tri (dimethylaminomethyl) phenol).
The modified powder comprises, by weight, 25 parts of a heat-conducting filler, 25 parts of a phase-change microcapsule and 0.4 part of a modifier. The heat conducting filler is alumina with the average grain diameter of 5 microns; the modifier is a silane coupling agent with the model of KH 560.
The preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on 15 parts by weight of heat-conducting powder graphene nanosheets;
s2, preparing phase-change microcapsule emulsion;
s3, adding the heat-conducting powder obtained in the step S1 into the phase-change microcapsule emulsion obtained in the step S2, stirring for 1 hour, and performing post-treatment to obtain the phase-change microcapsule.
The gas subjected to plasma pretreatment is oxygen, and the pretreatment time is 20 min; the graphene nano-sheet is purchased from Nanjing Xiancheng nanomaterial science and technology Limited, with a product number of 10078.
The phase-change microcapsule emulsion is prepared from the following raw materials: 300 parts of phase-change material paraffin, 15 parts of surfactant lauryl sodium sulfate, 0.1 part of auxiliary agent polyvinylpyrrolidone, 700 parts of water and 80 parts of melamine resin prepolymer. The paraffin is purchased from Guangzhou Zhongjia new material science and technology limited, the product number is ZJ-37, and the phase transition temperature is 37 ℃; the melamine resin prepolymer is melamine-formaldehyde prepolymer, and the preparation method of the melamine-formaldehyde prepolymer comprises the following steps: adding 1 part by weight of melamine and 3 parts by weight of formaldehyde aqueous solution with the concentration of 37 wt% into 3 parts by weight of water, stirring uniformly, adjusting the pH to 10 by using triethanolamine, and reacting for 30min at 70 ℃ to obtain the melamine-formaldehyde prepolymer.
The preparation method of the phase-change microcapsule emulsion comprises the following steps:
(1) melting the phase change material to prepare an oil phase;
(2) adding a surfactant and an auxiliary agent into water, dissolving, and preparing a water phase;
(3) adding the oil phase into the water phase while stirring, and uniformly stirring to obtain microemulsion;
(4) adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 200 rpm; adding citric acid to adjust the pH value to 4, then reducing the stirring speed by 5rpm every 1h, reacting for 40min, uniformly heating to 70 ℃ in 110min, and continuing to react for 5h to obtain the phase-change microcapsule emulsion.
The post-treatment refers to dehydration and drying at 30 ℃.
The preparation method of the modified powder comprises the following steps: uniformly mixing the heat-conducting filler, the phase-change microcapsule and the modifier by using high-speed mixing equipment, and then drying for later use.
The preparation method of the phase-change heat storage pouring sealant comprises the following steps:
(1) preparing a component A: weighing epoxy resin, modified powder and diluent, fully stirring and uniformly mixing in a reaction kettle, taking out and placing in a vacuum box for deaeration for 2 hours to obtain a component A;
(2) preparing a component B: weighing the curing agent and the accelerator, putting into a reaction kettle, fully stirring and uniformly mixing, and putting into a vacuum box for defoaming for 2 hours to prepare the component B.
Example 2
The phase-change heat storage pouring sealant comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 20 parts of epoxy resin (the type of the epoxy resin is EPN1180, and the manufacturer is American Henshimei), 30 parts of modified powder, 5 parts of diluent, 0.8 part of defoaming agent (the type is B-0997, and the manufacturer is Federal), and 3 parts of flame retardant magnesium hydroxide; the preparation raw materials of the component B comprise: 20 parts of anhydride curing agent maleic anhydride and 1 part of accelerator (the model is DMP-30, and the name of the accelerator is 2, 4, 6-tri (dimethylaminomethyl) phenol).
The modified powder comprises the following raw materials, by weight, 15 parts of heat-conducting filler, 15 parts of phase-change microcapsule and 0.1 part of modifier. The heat conducting filler is alumina with the average grain diameter of 3 microns; the modifier is a silane coupling agent with the model of KH 560.
The preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on 5 parts by weight of heat-conducting powder graphene nanosheets;
s2, preparing phase-change microcapsule emulsion;
s3, adding the heat-conducting powder obtained in the step S1 into the phase-change microcapsule emulsion obtained in the step S2, stirring for 1 hour, and performing post-treatment to obtain the phase-change microcapsule.
The gas subjected to plasma pretreatment is oxygen, and the pretreatment time is 20 min; the graphene nano-sheet is purchased from Nanjing Xiancheng nanomaterial science and technology Limited, with a product number of 10078.
The phase-change microcapsule emulsion is prepared from the following raw materials: 200 parts of phase-change material paraffin, 5 parts of surfactant lauryl sodium sulfate, 0.01 part of auxiliary agent polyvinylpyrrolidone, 500 parts of water and 40 parts of melamine resin prepolymer. The paraffin is purchased from Guangzhou Zhongjia new material science and technology limited, the product number is ZJ-37, and the phase transition temperature is 37 ℃; the melamine resin prepolymer is melamine-formaldehyde prepolymer, and the preparation method of the melamine-formaldehyde prepolymer comprises the following steps: adding 1 part by weight of melamine and 3 parts by weight of formaldehyde aqueous solution with the concentration of 37 wt% into 3 parts by weight of water, stirring uniformly, adjusting the pH to 10 by using triethanolamine, and reacting for 30min at 70 ℃ to obtain the melamine-formaldehyde prepolymer.
The preparation method of the phase-change microcapsule emulsion comprises the following steps:
(1) melting the phase change material to prepare an oil phase;
(2) adding a surfactant and an auxiliary agent into water, dissolving, and preparing a water phase;
(3) adding the oil phase into the water phase while stirring, and uniformly stirring to obtain microemulsion;
(4) adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 250 rpm; adding citric acid to adjust the pH value to 4, then reducing the stirring speed by 15rpm every 1h, reacting for 40min, uniformly heating to 70 ℃ in 150min, and continuing to react for 3h to obtain the phase-change microcapsule emulsion.
The post-treatment refers to dehydration and drying at 30 ℃.
The preparation method of the modified powder is the same as that of the embodiment 1;
the preparation method of the phase-change heat storage pouring sealant is the same as that of the embodiment 1.
Example 3
The phase-change heat storage pouring sealant comprises a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 25 parts of epoxy resin (the type of the epoxy resin is EPN1180, and the manufacturer is American Hensman), 40 parts of modified powder, 7 parts of diluent, 0.8 part of defoaming agent (the type is B-0997, and the manufacturer is Federal), and 3 parts of flame retardant magnesium hydroxide; the preparation raw materials of the component B comprise: 23 parts of anhydride curing agent maleic anhydride and 2 parts of accelerator (model number DMP-30, the Chinese name is 2, 4, 6-tri (dimethylaminomethyl) phenol).
The modified powder comprises 20 parts of heat-conducting filler, 20 parts of phase-change microcapsule and 0.3 part of modifier. The heat-conducting filler is alumina with the average grain diameter of 4 microns; the modifier is a silane coupling agent with the model of KH 560.
The preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on 10 parts by weight of heat-conducting powder graphene nanosheets;
s2, preparing phase-change microcapsule emulsion;
s3, adding the heat-conducting powder obtained in the step S1 into the phase-change microcapsule emulsion obtained in the step S2, stirring for 1-2 hours, and performing post-treatment to obtain the phase-change microcapsule.
The gas subjected to plasma pretreatment is oxygen, and the pretreatment time is 20 min; the graphene nano-sheet is purchased from Nanjing Xiancheng nanomaterial science and technology Limited, with a product number of 10078.
The phase-change microcapsule emulsion is prepared from the following raw materials: 250 parts of phase-change material paraffin, 10 parts of surfactant lauryl sodium sulfate, 0.05 part of auxiliary agent polyvinylpyrrolidone, 600 parts of water and 60 parts of melamine resin prepolymer. The paraffin is purchased from Guangzhou Zhongjia new material science and technology limited, the product number is ZJ-37, and the phase transition temperature is 37 ℃; the melamine resin prepolymer is melamine-formaldehyde prepolymer, and the preparation method of the melamine-formaldehyde prepolymer comprises the following steps: adding 1 part by weight of melamine and 3 parts by weight of formaldehyde aqueous solution with the concentration of 37 wt% into 3 parts by weight of water, stirring uniformly, adjusting the pH to 10 by using triethanolamine, and reacting for 30min at 70 ℃ to obtain the melamine-formaldehyde prepolymer.
The preparation method of the phase-change microcapsule emulsion comprises the following steps:
(1) melting the phase change material to prepare an oil phase;
(2) adding a surfactant and an auxiliary agent into water, dissolving, and preparing a water phase;
(3) adding the oil phase into the water phase while stirring, and uniformly stirring to obtain microemulsion;
(4) adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 200 rpm; adding citric acid to adjust the pH value to 4, then reducing the stirring speed by 10rpm every 1h, reacting for 40min, uniformly heating to 70 ℃ in 120min, and continuously reacting for 4h to obtain the phase-change microcapsule emulsion.
The post-treatment refers to dehydration and drying at 30 ℃.
The preparation method of the modified powder is the same as that of the embodiment 1;
the preparation method of the phase-change heat storage pouring sealant is the same as that of the embodiment 1.
Comparative example 1
The specific implementation manner of the phase-change heat storage pouring sealant is the same as that in example 3, the difference is that in the preparation method of the rubber microcapsule: the heat conducting powder graphene nanosheets are not subjected to plasma pretreatment.
Comparative example 2
The specific implementation manner of the phase-change heat storage pouring sealant is the same as that in example 3, and the difference is that the preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on 10 parts by weight of heat-conducting powder graphene nanosheets;
s2, phase change microcapsule preparation:
(1) melting the phase change material to prepare an oil phase;
(2) adding a surfactant and an auxiliary agent into water, dissolving, and preparing a water phase;
(3) adding the oil phase into the water phase while stirring, and uniformly stirring to obtain microemulsion;
(4) adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 250 rpm; and adding citric acid to adjust the pH value to 4, adding the heat-conducting powder obtained in the step S1, reducing the stirring speed by 15rpm every 1 hour, reacting for 40min, uniformly heating to 70 ℃ within 150min, and continuously reacting for 3 hours to obtain the phase-change microcapsule emulsion.
And S3, carrying out post-treatment on the phase change microcapsule emulsion to obtain the phase change microcapsule.
Comparative example 3
The specific implementation manner of the phase-change heat storage pouring sealant is the same as that in example 3, and the difference is that the preparation method of the phase-change microcapsule comprises the following steps: in the step (4), adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 200 rpm; adding citric acid to adjust the pH value to 4, then reducing the stirring speed by 10rpm every 1h, reacting for 40min, uniformly heating to 70 ℃ in 40min, and continuously reacting for 4h to obtain the phase-change microcapsule emulsion.
Comparative example 4
The specific implementation manner of the phase-change heat storage pouring sealant is the same as that in example 3, and the difference is that the preparation method of the phase-change microcapsule comprises the following steps: in the step (4), adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 200 rpm; adding citric acid to adjust the pH value to 4, then reducing the stirring speed by 10rpm every 1h, reacting for 40min, uniformly heating to 70 ℃ in 200min, and continuously reacting for 4h to obtain the phase-change microcapsule emulsion.
Comparative example 5
The specific implementation manner of the phase-change heat storage pouring sealant is the same as that in example 3, and the difference is that the preparation method of the phase-change microcapsule comprises the following steps: in the step (4), adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 200 rpm; adding citric acid to adjust the pH value to 4, then reducing the stirring speed by 30rpm every 1h, reacting for 40min, uniformly heating to 70 ℃ in 120min, and continuously reacting for 4h to obtain the phase-change microcapsule emulsion.
Comparative example 6
The specific implementation manner of the phase-change heat storage pouring sealant is the same as that in example 3, and the difference is that the preparation method of the phase-change microcapsule comprises the following steps: in the step (4), adding the melamine resin prepolymer into the microemulsion and uniformly stirring at the stirring speed of 200 rpm; adding citric acid to adjust the pH value to 4, reacting for 40min, uniformly heating to 70 ℃ within 120min, and continuously reacting for 4 hours to obtain the phase-change microcapsule emulsion.
Performance testing
The prepared A component and B component (the weight ratio of the A component to the B component is 6: 4) in the examples and the comparative examples are mixed, cured at 120 ℃ for 3 hours and then cured at 140 ℃ for 12 hours for performance test, and the results are shown in tables 1 and 2.
Coefficient of thermal conductivity: testing by using a thermal conductivity meter;
TABLE 1
TABLE 2
| Test items | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Viscosity (cP, 25 ℃ C.) | 4456 | 4458 | 4457 | 4563 |
| Coefficient of thermal conductivity (W/m.K) | 0.69 | 0.71 | 0.74 | 0.45 |
| Elongation at Break (%) | 88 | 90 | 91 | 75 |
| DSC (enthalpy J/g) | 25 | 30 | 22 | 32 |
| Water absorption (%) | 0.04 | 0.02 | 0.05 | 0.03 |
| Hardness (Shao A) | 85 | 86 | 86 | 82 |
| Breakdown strength (kV/mm) | ≥10 | ≥10 | ≥10 | ≥10 |
| Flame retardant rating | V0 | V0 | V0 | V0 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (7)
1. The phase change heat storage pouring sealant is characterized by comprising a component A and a component B, wherein the component A is prepared from the following raw materials in parts by weight: 20-30 parts of epoxy resin, 30-50 parts of modified powder and 5-10 parts of diluent; the preparation raw materials of the component B comprise: 20-25 parts of anhydride curing agent and 1-3 parts of accelerator;
the modified powder comprises the following raw materials, by weight, 15-25 parts of heat-conducting filler, 15-25 parts of phase-change microcapsule and 0.1-0.4 part of modifier;
the preparation method of the phase-change microcapsule comprises the following steps:
s1, carrying out plasma pretreatment on heat-conducting powder; s2, preparing phase-change microcapsule emulsion; s3, adding the heat-conducting powder obtained in the step S1 into the phase-change microcapsule emulsion obtained in the step S2, stirring for 1-2 hours, and performing post-treatment to obtain a phase-change microcapsule;
the phase-change microcapsule emulsion is prepared from the following raw materials: 200-300 parts of phase-change material, 5-15 parts of surfactant, 0.01-0.1 part of auxiliary agent, 500-700 parts of water and 40-80 parts of melamine resin prepolymer.
2. The phase-change heat-storage pouring sealant according to claim 1, wherein the heat-conducting filler is at least one selected from the group consisting of aluminum oxide, boron nitride, silicon nitride, aluminum hydroxide, calcium carbonate, aluminum powder, and zinc oxide.
3. The phase change heat storage pouring sealant of claim 2, wherein the average particle size of the heat conductive filler is at least one of 0.2-1, 1-10, 10-30, 30-50, 50-100, 100-200, and 200-300 μm.
4. The phase change heat storage pouring sealant as claimed in claim 1, wherein the phase change microcapsule has a phase change point of 20-60 ℃, an enthalpy of 160-240J/g, and an average particle size of at least one of 1-5, 5-10, 10-30, and 30-60 μm.
5. The phase-change heat-storage pouring sealant as claimed in claim 1, wherein the gas of the plasma pretreatment is oxygen and/or air, and the pretreatment time is 10-40 min.
6. The preparation method of the phase-change heat-storage pouring sealant as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) preparing a component A: weighing epoxy resin, modified powder and diluent, fully stirring and uniformly mixing in a reaction kettle, taking out, and placing in a vacuum box for deaeration for 1-3h to obtain a component A;
(2) preparing a component B: weighing the anhydride curing agent and the accelerant, putting into a reaction kettle, fully stirring and uniformly mixing, and defoaming in a vacuum box for 1-3 hours to obtain the component B.
7. The use method of the phase-change heat-storage pouring sealant as claimed in any one of claims 1 to 5, wherein the prepared component A and component B are mixed, poured into an encapsulated object, and cured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011039996.9A CN112126393B (en) | 2020-09-28 | 2020-09-28 | Phase-change heat storage pouring sealant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011039996.9A CN112126393B (en) | 2020-09-28 | 2020-09-28 | Phase-change heat storage pouring sealant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112126393A CN112126393A (en) | 2020-12-25 |
| CN112126393B true CN112126393B (en) | 2021-07-20 |
Family
ID=73843099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011039996.9A Active CN112126393B (en) | 2020-09-28 | 2020-09-28 | Phase-change heat storage pouring sealant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112126393B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113265209B (en) * | 2021-05-25 | 2022-12-09 | 广东力王新材料有限公司 | Phase change energy storage adhesive tape and preparation method thereof |
| CN115725182B (en) * | 2022-12-26 | 2023-12-12 | 华南理工大学 | Silicon rubber composite material containing phase-change nanocapsules/boron nitride hybrid filler, preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977857A (en) * | 2011-09-06 | 2013-03-20 | 比亚迪股份有限公司 | Phase-change energy storage microcapsules and preparation method thereof |
| CN103087665A (en) * | 2013-01-31 | 2013-05-08 | 合肥工业大学 | High-heat-conductivity insulation low-viscosity epoxy resin pouring sealant and preparation method thereof |
| CN107815286A (en) * | 2017-11-03 | 2018-03-20 | 航天特种材料及工艺技术研究所 | A kind of heat conduction embedding silica gel based on phase-change microcapsule and preparation method thereof |
| CN111139008A (en) * | 2020-01-09 | 2020-05-12 | 上海汉司实业有限公司 | Pouring sealant, preparation method thereof, solar inverter and electronic component |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9480960B2 (en) * | 2014-12-01 | 2016-11-01 | National Chung Shan Institute Of Science And Technology | Process for preparing phase change microcapsule having thermally conductive shell |
-
2020
- 2020-09-28 CN CN202011039996.9A patent/CN112126393B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977857A (en) * | 2011-09-06 | 2013-03-20 | 比亚迪股份有限公司 | Phase-change energy storage microcapsules and preparation method thereof |
| CN103087665A (en) * | 2013-01-31 | 2013-05-08 | 合肥工业大学 | High-heat-conductivity insulation low-viscosity epoxy resin pouring sealant and preparation method thereof |
| CN107815286A (en) * | 2017-11-03 | 2018-03-20 | 航天特种材料及工艺技术研究所 | A kind of heat conduction embedding silica gel based on phase-change microcapsule and preparation method thereof |
| CN111139008A (en) * | 2020-01-09 | 2020-05-12 | 上海汉司实业有限公司 | Pouring sealant, preparation method thereof, solar inverter and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112126393A (en) | 2020-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112126393B (en) | Phase-change heat storage pouring sealant and preparation method thereof | |
| CN101255299B (en) | Environment protection heat-proof acrylic resin insulation paint | |
| CN101693795A (en) | Pasty heat-insulating elastic putty | |
| CN113388306B (en) | Coating composition and preparation method and application thereof | |
| CN113205932B (en) | Low-temperature-resistant anti-pollution-flashover ceramic insulator and manufacturing process thereof | |
| CN102618016B (en) | Light-transparent heat insulating film, its preparation method and application | |
| CN104530782A (en) | Phosphate coating solution and preparation method thereof | |
| CN111153608B (en) | Organic-inorganic hybrid film-forming microcapsule type high-temperature self-repairing basalt fiber water-based impregnating compound and preparation method thereof | |
| CN112694772A (en) | High-temperature-resistant inorganic hole sealing agent for thermal spraying coating and preparation method thereof | |
| CN110482559B (en) | Aluminum modified acidic silica sol and preparation method and application thereof | |
| CN112121738B (en) | Preparation method of functionalized microcapsule and functionalized microcapsule prepared by preparation method | |
| CN104031355A (en) | Epoxy resin composition cured and modified by carboxyl-containing polyether nitrile sulphone ketone copolymer as well as preparation method and application of epoxy resin composition | |
| Chen et al. | Review on Porous Ceramic‐Based Form‐Stable Phase Change Materials: Preparation, Enhance Thermal Conductivity, and Application | |
| CN113337231A (en) | Epoxy composite material with heterostructure and preparation method thereof | |
| CN109851996A (en) | A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material | |
| CN113355055A (en) | Microcapsule with high phase change enthalpy and preparation method thereof | |
| CN111204998B (en) | Organic-inorganic hybrid high-temperature-resistant basalt fiber impregnating compound and preparation method thereof | |
| CN105315845A (en) | High-strength water-resistant corrosion-resistant epoxy resin powder coating | |
| CN112391148A (en) | High-thermal-conductivity and high-enthalpy composite phase change microcapsule and preparation method thereof | |
| CN115196982B (en) | Boiler lining heat-insulating material and preparation method thereof | |
| CN103897577A (en) | Glass paint and preparation method thereof | |
| CN112724933A (en) | Microcapsule phase change energy storage material and preparation method thereof | |
| CN113511821B (en) | Basalt fiber impregnating compound for electronic fabric and preparation method thereof | |
| CN105862426B (en) | A kind of enhanced carbon fiber sizing agent of nanoscale twins molybdenum disulfide and preparation method thereof | |
| CN107352921B (en) | Preparation and application of quick-film-forming energy-saving environment-friendly machine-sprayed finish-decoration mortar |
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 |