CN111138843A - 一种石墨烯基聚氨酯多孔纳米材料及其制备方法 - Google Patents

一种石墨烯基聚氨酯多孔纳米材料及其制备方法 Download PDF

Info

Publication number
CN111138843A
CN111138843A CN201911409609.3A CN201911409609A CN111138843A CN 111138843 A CN111138843 A CN 111138843A CN 201911409609 A CN201911409609 A CN 201911409609A CN 111138843 A CN111138843 A CN 111138843A
Authority
CN
China
Prior art keywords
graphene
based polyurethane
polyurethane porous
component
resin
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.)
Pending
Application number
CN201911409609.3A
Other languages
English (en)
Inventor
蒋璐瑶
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Suzhou Tongli Optoelectronics Co ltd
Original Assignee
Suzhou Tongli Optoelectronics Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Suzhou Tongli Optoelectronics Co ltd filed Critical Suzhou Tongli Optoelectronics Co ltd
Priority to CN201911409609.3A priority Critical patent/CN111138843A/zh
Publication of CN111138843A publication Critical patent/CN111138843A/zh
Priority to PCT/CN2020/114657 priority patent/WO2021135378A1/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2427/04—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 chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2431/00—Characterised by the use of 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 an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2431/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2431/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
    • C08J2493/04—Rosin
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种石墨烯基聚氨酯多孔纳米材料及其制备方法，由A组份和B组份按照1‑2:1的质量比例混合后构成，A组份包括以下各组分：聚醚多元醇、聚酯多元醇、扩链剂、石墨烯、抗结构化剂、弱补强剂、发泡剂和稀释剂；B组份包括以下各组分：增粘树脂及增粘剂、异氰酸酯、石墨烯、抗结构化剂、弱补强剂、匀泡剂和功能型添加剂。本发明制得的石墨烯基聚氨酯多孔纳米材料具有多孔性、相对密度小的优点。

Description

一种石墨烯基聚氨酯多孔纳米材料及其制备方法
技术领域
本发明属于聚氨酯材料技术领域，涉及一种石墨烯基聚氨酯多孔纳米材料及其制备方法。
背景技术
聚氨酯由有机二异氰酸酯或多异氰酸酯与二羟基或多羟基化合物加聚而成，全称为聚氨基甲酸酯，是主链上含有重复氨基甲酸酯基团和侧链上含有醚基、酯基、脲基或者缩二脲基等引进基团的大分子化合物的统称。石墨烯是一种性能先进的二维平面纳米材料，通过化学气相沉积法和化学还原法可以实现工业化生产，二维石墨烯是碳质材料的基本组成单元，可以将它卷曲成零维的富勒烯和一维的碳纳米管，也可以将它重叠堆积成三维的石墨。石墨烯包含以下特性：一，目前发现最薄的材料，单层石墨烯厚度只有0.335nm，相当于碳原子的直径；二，比表面积庞大，石墨烯的比表面积达到2600m2/g以上，是一种性能优异的储能材料；三，导电性强，石墨烯中电子几乎没有质量，电子运动速度大大超过金属导体和其他半导体中电子运动速度，可作为理想的导电材料；四，导热性强，石墨烯的热导率达到5000W/mk以上，超过金、银、铜和铝等金属材料，可作为理想的导热材料。聚氨酯和石墨烯，一个应用广泛的高分子材料，一个革命性的无机材料，均在材料行业中不可估量。
基于石墨烯的聚合物复合材料是石墨烯迈向实际应用的一个重要方向，石墨烯微片具有一定含氧官能团，易于进行功能化，不仅增加其与高分子基体结合力，而且可以提高其溶解性，赋予石墨烯新的性质。近年来，结合石墨烯和聚氨酯的研究以及围绕石墨烯/聚氨酯的新兴产品、工艺和应用炙手可热，经过科研工作者的不断探索和刻苦专研，石墨烯/聚氨酯复合材料层出不穷，石墨烯/聚氨酯复合材料的应用也越来越广泛。但是，石墨烯/聚氨酯在人们日常生活中应用的深度和广度还未达到该领域科研工作者的预期，主要原因有以下两点：1，石墨烯/聚氨酯复合材料作为前沿材料，研发主体以高校和研究机构为主，偏重于基础科学而非实用技术，高端生产工艺不成熟，尚无法实现低成本，而下游应用主体缺乏积极性，难以形成规模化产业；2，石墨烯/聚氨酯复合材料本身还存在一定的技术难题需要较长时间去攻克，例如石墨烯结构容易破坏、自生容易团聚和石墨烯跟聚氨酯相容性差等缺陷。中国在石墨烯机理和制备技术等方面取得了一定成绩，但应用研究和产业布局尚处于研发阶段，石墨烯与高分子材料结合的理论基础以及各项性能指标随着应用领域的拓展也逐步的提高和完善。初步应用研究显示了石墨烯基复合材料优异的性能和独特的优势，因此应继续深入开展应用研究，结合低成本和高质量生产技术，拓宽和丰富下游应用产业链的空间。
发明内容
本发明的目的在于提供一种石墨烯基聚氨酯多孔纳米材料及制备方法。
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种石墨烯基聚氨酯多孔纳米材料，所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照1-2:1的质量比例混合后构成：
所述A组份包括以下质量百分比的原料组分：
Figure BDA0002349611670000021
所述B组份包括以下质量百分比的原料组分：
Figure BDA0002349611670000022
Figure BDA0002349611670000031
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、聚四亚甲基醚二醇中的至少一种。
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇、端羟基苯酐聚酯多元醇和聚己内酯多元醇中的至少一种。
优选的技术方案为：所述扩链剂为EG、1,2-PG、1,4-BD、DEG、HD、HER、HQEE、甘油、TMP、二乙醇胺、三乙醇胺、MOCA中的至少一种。
优选的技术方案为：所述石墨烯为单层石墨烯、双层石墨烯和少层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.05g/cm3以内，振实密度为0.05～0.1g/cm3。
优选的技术方案为：所述抗结构化剂为羟基硅油、二苯基硅二醇、烷氧基低分子聚硅氧烷、六甲基二硅氨烷、环状三硅氨烷和含硼硅氧烷类化合物中的至少一种。
优选的技术方案为：所述弱补强剂为碳酸钙、滑石粉、气相法白炭黑、富勒烯、碳纳米管和沉淀法白炭黑中的至少一种。
优选的技术方案为：所述发泡剂为碳酸氢钠、氧化锌、碳酸氢铵、明矾、偶氮二甲酰胺、尿素、N,N-二亚硝基五次甲基四胺、苯甲酸、二苯磺酰肼醚、乙二胺、二偶氮氨基苯、二苯胍、对甲苯磺酰肼和偶氮二异丁腈中的至少一种。
优选的技术方案为：所述稀释剂为水、甲苯、二甲苯和石油醚中的至少一种。
优选的技术方案为：所述增粘树脂及增粘剂为苯乙烯-甲基丙烯酸甲酯树脂、松香树脂、甲基MQ硅树脂、萜烯树脂、萜烯酚醛树脂、端硅烷基聚醚树脂、端硅烷基聚氨基甲酸酯树脂、聚乙酸乙烯酯、3-氨丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-异氰酸丙基三乙氧基硅烷中的至少一种。
优选的技术方案为：所述异氰酸酯为苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。
优选的技术方案为：所述匀泡剂为低粘度二甲基硅油、端烯丙基聚醚、甲基纤维素醚、羟乙基纤维素、羟甲基甲基纤维素、羟内基甲基纤维素和月桂酰二乙醉胺中的至少一种。
优选的技术方案为：所述功能型添加剂为聚氯乙烯、聚乙酸乙烯酯、聚酰胺、聚甲基丙烯酸甲酯、聚苯乙烯和聚异丁烯等热塑性树脂；二丁基锡二月桂酸酯、辛酸亚锡、双吗啉基二乙基醚和N,N-二甲基环已胺、三苯基膦酸酯、十溴二苯醚、八溴二苯醚、四溴双酚A、2，4，6-三溴苯酚、双(2，3-二烷丙基)醚和三氧化二锑和五氧化二锑等阻燃剂至少一种。
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯基聚氨酯多孔纳米材料的方法：
所述A组份的制备方法包括以下步骤：
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；
所述B组份的制备方法包括以下步骤：
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。
优选的技术方案为：负压条件为真空度为-0.08～-0.1MPa。
由于上述技术方案运用，本发明与现有技术相比具有的优点是：
1、本发明制得的石墨烯基聚氨酯多孔纳米材料具有多孔性、相对密度小、比强度高的优点
2、本发明制得的石墨烯基聚氨酯多孔纳米材料，阻燃级别达到UL94-VO，耐化学溶剂、耐紫外旋光和耐撕裂扯断，作业温幅大(-60℃至135℃)，在－10℃～150℃之间经过千百万次的曲挠不会断裂，压缩后迅速回弹，即使在恶劣环境下作业也能保持原有的高弹性，广泛应用于密封减震、微波吸收、电磁屏蔽和散热保护等轻量化应用场景。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。
实施例1：一种石墨烯基聚氨酯多孔纳米材料及制备方法
一种石墨烯基聚氨酯多孔纳米材料，由重量比1.5:1的组份A和组份B合成。
所述的A组份包括以下各组分：聚醚多元醇、聚酯多元醇、扩链剂、石墨烯、抗结构化剂、弱补强剂、发泡剂和稀释剂，其中各成分重量百分数如下：聚醚多元醇36％、聚酯多元醇30％、扩链剂5％、石墨烯20％、抗结构化剂1％、弱补强剂1％、发泡剂5％和稀释剂2％。
所述的B组份包括以下各组分：增粘树脂及增粘剂、异氰酸酯、石墨烯、抗结构化剂、弱补强剂、匀泡剂和功能型添加剂，其中各成分重量百分数如下：增粘树脂及增粘剂20％、异氰酸酯38％、石墨烯30％、抗结构化剂1％、弱补强剂1％、匀泡剂5％和功能型添加剂5％。
所述的聚醚多元醇包括：
a)聚氧化丙烯二醇(其中，羟值/[mgKOH/g]在20-50以内，分子量在2000～6000以内，25℃时粘度在500～5000mpa·s以内，酸值/[mgKOH/g]≤0.05)；
b)聚氧化丙烯三醇(其中，羟值/[mgKOH/g]在20-100以内，分子量在1000～4000以内，25℃时粘度在100～2000mpa·s以内，酸值/[mgKOH/g]≤0.05)；
c)聚四亚甲基醚二醇(其中，羟值/[mgKOH/g]在30-200以内，分子量在500～4000以内，25℃时粘度在100～2000mpa·s以内，酸值/[mgKOH/g]≤0.05)；中的一种或几种。
所述的聚酯多元醇包括：
a)己二酸系聚酯多元醇(其中，羟值/[mgKOH/g]在30-300以内，分子量在200～4000以内，60℃时粘度在50～1500mpa·s以内，酸值/[mgKOH/g]≤0.05)；
b)端羟基苯酐聚酯多元醇(其中，羟值/[mgKOH/g]在100-300以内，分子量在1000～2000以内，60℃时粘度在100～2000mpa·s以内，酸值/[mgKOH/g]≤0.1)；
c)聚己内酯多元醇(其中，羟值/[mgKOH/g]在50-150以内，分子量在500～3000以内，60℃时粘度在50～2000mpa·s以内，酸值/[mgKOH/g]≤0.1)；中的一种或几种。
所述的扩链剂为EG、1,2-PG、1,4-BD、DEG、HD、HER、HQEE、甘油、TMP、二乙醇胺、三乙醇胺、MOCA中的一种或几种。
所述的石墨烯为单层石墨烯、双层石墨烯和少层石墨烯中的一种或几种，上述石墨烯松装密度控制在0.01～0.05g/cm3以内，振实密度为0.05～0.1g/cm3以内。
所述抗结构化剂为羟基硅油、二苯基硅二醇、烷氧基低分子聚硅氧烷、六甲基二硅氨烷、环状三硅氨烷和含硼硅氧烷类化合物中的至少一种。
所述的弱补强剂为碳酸钙、滑石粉、气相法白炭黑、富勒烯、碳纳米管和沉淀法白炭黑中一种或几种。
所述的发泡剂为碳酸氢钠、氧化锌、碳酸氢铵、明矾、偶氮二甲酰胺、尿素、N,N-二亚硝基五次甲基四胺、苯甲酸、二苯磺酰肼醚、乙二胺、二偶氮氨基苯、二苯胍、对甲苯磺酰肼和偶氮二异丁腈中的一种或几种。
所述的稀释剂为水、甲苯、二甲苯和石油醚中的一种或几种。
所述的增粘树脂及增粘剂为苯乙烯-甲基丙烯酸甲酯树脂、松香树脂、甲基MQ硅树脂、萜烯树脂、萜烯酚醛树脂、端硅烷基聚醚树脂、端硅烷基聚氨基甲酸酯树脂、聚乙酸乙烯酯、3-氨丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-异氰酸丙基三乙氧基硅烷中的一种或几种。
所述的异氰酸酯包括：甲苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的一种或几种；其中-NCO含量/％在20-50％以内，分子量在50-500以内。
所述的匀泡剂为低粘度二甲基硅油、端烯丙基聚醚、甲基纤维素醚、羟乙基纤维素、羟甲基甲基纤维素、羟内基甲基纤维素和月桂酰二乙醉胺中的一种或几种。
所述的功能型添加剂包括：聚氯乙烯、聚乙酸乙烯酯、聚酰胺、聚甲基丙烯酸甲酯、聚苯乙烯和聚异丁烯等热塑性树脂；二丁基锡二月桂酸酯、辛酸亚锡、双吗啉基二乙基醚和N,N-二甲基环已胺等催化剂；三苯基膦酸酯、十溴二苯醚、八溴二苯醚、四溴双酚A、2，4，6-三溴苯酚、双(2，3-二烷丙基)醚和三氧化二锑和五氧化二锑等阻燃剂中的一种或几种。
石墨烯基聚氨酯多孔纳米材料制备方法，包括以下步骤：
所述的A组份制备方法包括以下步骤：
A)将聚醚多元醇、聚酯多元醇加到反应釜里，在高温和负压的条件下，高速搅拌1.5小时，至分散均匀；
B)在常温和低速搅拌的条件下，加入扩链剂、抗结构化剂和稀释剂，在负压条件下高速搅拌1.5小时，至分散均匀；
C)在低速搅拌的条件下，加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，高速搅拌至分散均匀；
所述的B组份制备方法包括以下步骤：
A)将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到反应釜里，在中温和负压的条件下，高速搅拌1.5小时，至分散均匀；
B)在常温和低速搅拌的条件下，加入石墨烯、弱补强剂和匀泡剂,在负压条件下高速搅拌1.5小时，至分散均匀；
使用时，按比例将A组份和B组份混合均匀即可。
高速搅拌为40～60r/min，低速搅拌为10～20r/min，高温为110～130℃，中温为70～90℃，常温是室温。负压条件为真空度为-0.08～-0.1Mpa。本实施例：高速搅拌为50r/min，低速搅拌为15r/min，高温为120℃，中温为70～90℃，常温是室温。负压条件为真空度为-0.089Mpa。
实施例2：一种石墨烯基聚氨酯多孔纳米材料及制备方法
一种石墨烯基聚氨酯多孔纳米材料，所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照1:1的质量比例混合后构成：
所述A组份包括以下质量百分比的原料组分：
Figure BDA0002349611670000081
所述B组份包括以下质量百分比的原料组分：
Figure BDA0002349611670000082
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇。
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇。
优选的技术方案为：所述扩链剂为EG。
优选的技术方案为：所述石墨烯为单层石墨烯。
优选的技术方案为：所述抗结构化剂为羟基硅油。
优选的技术方案为：所述弱补强剂为碳酸钙。
优选的技术方案为：所述发泡剂为氧化锌。
优选的技术方案为：所述稀释剂为甲苯。
优选的技术方案为：所述增粘树脂及增粘剂为松香树脂。
优选的技术方案为：所述异氰酸酯为六亚甲基二异氰酸酯。
优选的技术方案为：所述匀泡剂为端烯丙基聚醚、甲基纤维素醚。
优选的技术方案为：所述功能型添加剂为聚氯乙烯。
为实现上述目的及其他相关目的，本发明提供的技术方案是：一种制备石墨烯基聚氨酯多孔纳米材料的方法：
所述A组份的制备方法包括以下步骤：
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；
所述B组份的制备方法包括以下步骤：
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。
优选的技术方案为：负压条件为真空度为-0.08MPa。
实施例3：一种石墨烯基聚氨酯多孔纳米材料及制备方法
一种石墨烯基聚氨酯多孔纳米材料，所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照2:1的质量比例混合后构成：
所述A组份包括以下质量百分比的原料组分：
Figure BDA0002349611670000091
所述B组份包括以下质量百分比的原料组分：
Figure BDA0002349611670000092
Figure BDA0002349611670000101
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇按照1：1的质量比例构成的混合物。
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇、端羟基苯酐聚酯多元醇按照1：1的质量比例构成的混合物。
优选的技术方案为：所述扩链剂为甘油、二乙醇胺、三乙醇胺按照1：1：1的质量比例构成的混合物。
优选的技术方案为：所述石墨烯为单层石墨烯、双层石墨烯和少层石墨烯按照1：1的质量比例构成的混合物；所述石墨烯松装密度为0.01g/cm3以内，振实密度为0.05g/cm3。
优选的技术方案为：所述抗结构化剂为羟基硅油、二苯基硅二醇按照1：1的质量比例构成的混合物。
优选的技术方案为：所述弱补强剂为滑石粉、气相法白炭黑按照1：1的质量比例构成的混合物。
优选的技术方案为：所述发泡剂为偶氮二甲酰胺、尿素按照1：1的质量比例构成的混合物。
优选的技术方案为：所述稀释剂为二甲苯和石油醚按照1：1的质量比例构成的混合物。
优选的技术方案为：所述增粘树脂及增粘剂为甲基MQ硅树脂、萜烯树脂按照1：1的质量比例构成的混合物。
优选的技术方案为：所述异氰酸酯为苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯按照1：1：1的质量比例构成的混合物。
优选的技术方案为：所述匀泡剂为羟乙基纤维素、羟甲基甲基纤维素按照1：1的质量比例构成的混合物。
优选的技术方案为：所述功能型添加剂为辛酸亚锡、双吗啉基二乙基醚按照1：1的质量比例构成的混合物。
制备石墨烯基聚氨酯多孔纳米材料的方法：
所述A组份的制备方法包括以下步骤：
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；
所述B组份的制备方法包括以下步骤：
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。
优选的技术方案为：负压条件为真空度为-0.1MPa。
实施例4：一种石墨烯基聚氨酯多孔纳米材料及制备方法
其它实施方式同实施例3，不同之处在于：
优选的技术方案为：所述聚醚多元醇为聚四亚甲基醚二醇。
优选的技术方案为：所述聚酯多元醇为聚己内酯多元醇。
优选的技术方案为：所述扩链剂为MOCA。
优选的技术方案为：所述石墨烯为双层石墨烯；所述石墨烯松装密度为0.01g/cm3以内，振实密度为0.05g/cm3。
优选的技术方案为：所述抗结构化剂为六甲基二硅氨烷。
优选的技术方案为：所述弱补强剂为富勒烯。
优选的技术方案为：所述发泡剂为氧化锌和偶氮二异丁腈按照1：1的质量比例构成的混合物。
优选的技术方案为：所述稀释剂为水、。
优选的技术方案为：所述增粘树脂及增粘剂为聚乙酸乙烯酯和γ-巯丙基三甲氧基硅烷按照1：1的质量比例构成的混合物。
优选的技术方案为：所述异氰酸酯为赖氨酸二异氰酸酯。
优选的技术方案为：所述匀泡剂为羟甲基甲基纤维素。
优选的技术方案为：所述功能型添加剂为辛酸亚锡和十溴二苯醚按照1：1的质量比例构成的混合物。
实施例5：一种石墨烯基聚氨酯多孔纳米材料及制备方法
其它实施方式同实施例3，不同之处在于：
优选的技术方案为：所述聚醚多元醇为聚氧化丙烯二醇和聚四亚甲基醚二醇按照1：1的质量比例构成的混合物。
优选的技术方案为：所述聚酯多元醇为己二酸系聚酯多元醇。
优选的技术方案为：所述扩链剂为1,2-PG、1,4-BD按照1：1的质量比例构成的混合物。
优选的技术方案为：所述石墨烯为少层石墨烯；所述石墨烯松装密度为0.05g/cm3以内，振实密度为0.1g/cm3。
优选的技术方案为：所述抗结构化剂为环状三硅氨烷。
优选的技术方案为：所述弱补强剂为沉淀法白炭黑。
优选的技术方案为：所述发泡剂为苯甲酸、二苯磺酰肼醚按照1：1的质量比例构成的混合物。
优选的技术方案为：所述稀释剂为石油醚。
优选的技术方案为：所述增粘树脂及增粘剂为端硅烷基聚氨基甲酸酯树脂。
优选的技术方案为：所述异氰酸酯为二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯按照1：1的质量比例构成的混合物。
优选的技术方案为：所述匀泡剂为月桂酰二乙醉胺。
优选的技术方案为：所述功能型添加剂为双吗啉基二乙基醚和四溴双酚A、2，4，6-三溴苯酚按照1：1的质量比例构成的混合物。
以上所述者仅为用以解释本发明之较佳实施例，并非企图具以对本发明做任何形式上之限制，是以，凡有在相同之发明精神下所作有关本发明之任何修饰或变更，皆仍应包括在本发明意图保护之范畴。

Claims (15)

1.一种石墨烯基聚氨酯多孔纳米材料，其特征在于：所述石墨烯基聚氨酯多孔纳米材料由A组份和B组份按照1-2:1的质量比例混合后构成：
所述A组份包括以下质量百分比的原料组分：
Figure FDA0002349611660000011
所述B组份包括以下质量百分比的原料组分：
Figure FDA0002349611660000012
2.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述聚醚多元醇为聚氧化丙烯二醇、聚氧化丙烯三醇、聚四亚甲基醚二醇中的至少一种。
3.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述聚酯多元醇为己二酸系聚酯多元醇、端羟基苯酐聚酯多元醇和聚己内酯多元醇中的至少一种。
4.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述扩链剂为EG、1,2-PG、1,4-BD、DEG、HD、HER、HQEE、甘油、TMP、二乙醇胺、三乙醇胺、MOCA中的至少一种。
5.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述石墨烯为单层石墨烯、双层石墨烯和少层石墨烯中的至少一种；所述石墨烯松装密度为0.01-0.05g/cm3以内，振实密度为0.05～0.1g/cm3。
6.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述抗结构化剂为羟基硅油、二苯基硅二醇、烷氧基低分子聚硅氧烷、六甲基二硅氨烷、环状三硅氨烷和含硼硅氧烷类化合物中的至少一种。
7.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述弱补强剂为碳酸钙、滑石粉、气相法白炭黑、富勒烯、碳纳米管和沉淀法白炭黑中的至少一种。
8.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述发泡剂为碳酸氢钠、氧化锌、碳酸氢铵、明矾、偶氮二甲酰胺、尿素、N,N-二亚硝基五次甲基四胺、苯甲酸、二苯磺酰肼醚、乙二胺、二偶氮氨基苯、二苯胍、对甲苯磺酰肼和偶氮二异丁腈中的至少一种。
9.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述稀释剂为水、甲苯、二甲苯和石油醚中的至少一种。
10.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述增粘树脂及增粘剂为苯乙烯-甲基丙烯酸甲酯树脂、松香树脂、甲基MQ硅树脂、萜烯树脂、萜烯酚醛树脂、端硅烷基聚醚树脂、端硅烷基聚氨基甲酸酯树脂、聚乙酸乙烯酯、3-氨丙基三乙氧基硅烷、γ-巯丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和γ-异氰酸丙基三乙氧基硅烷中的至少一种。
11.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述异氰酸酯为苯二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。
12.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述匀泡剂为低粘度二甲基硅油、端烯丙基聚醚、甲基纤维素醚、羟乙基纤维素、羟甲基甲基纤维素、羟内基甲基纤维素和月桂酰二乙醉胺中的至少一种。
13.根据权利要求1所述的石墨烯基聚氨酯多孔纳米材料，其特征在于：所述功能型添加剂为聚氯乙烯、聚乙酸乙烯酯、聚酰胺、聚甲基丙烯酸甲酯、聚苯乙烯和聚异丁烯等热塑性树脂；二丁基锡二月桂酸酯、辛酸亚锡、双吗啉基二乙基醚和N,N-二甲基环已胺、三苯基膦酸酯、十溴二苯醚、八溴二苯醚、四溴双酚A、2，4，6-三溴苯酚、双(2，3-二烷丙基)醚和三氧化二锑和五氧化二锑等阻燃剂至少一种。
14.一种制备权利要求1-13任一所述的石墨烯基聚氨酯多孔纳米材料的方法：其特征在于：
所述A组份的制备方法包括以下步骤：
步骤1：将聚醚多元醇、聚酯多元醇加到A反应釜里，搅拌至分散均匀；
步骤2：向A反应釜加入扩链剂、抗结构化剂和稀释剂，在负压条件下搅拌至分散均匀；
步骤3：向A反应釜加入加入石墨烯、弱补强剂和发泡剂，然后在负压条件下，搅拌至分散均匀，得到A组份；
所述B组份的制备方法包括以下步骤：
步骤1：将增粘树脂及增粘剂、异氰酸酯、抗结构化剂、匀泡剂和功能型添加剂，加到B反应釜里，在负压条件下，搅拌至分散均匀；
步骤2：向B反应釜加入石墨烯、弱补强剂和匀泡剂，在负压条件下搅拌至分散均匀，得到B组份。
15.根据权利要求14所述的方法，其特征在于：负压条件为真空度为-0.08～-0.1MPa。
CN201911409609.3A 2019-12-31 2019-12-31 一种石墨烯基聚氨酯多孔纳米材料及其制备方法 Pending CN111138843A (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201911409609.3A CN111138843A (zh) 2019-12-31 2019-12-31 一种石墨烯基聚氨酯多孔纳米材料及其制备方法
PCT/CN2020/114657 WO2021135378A1 (zh) 2019-12-31 2020-09-11 一种石墨烯基聚氨酯多孔纳米材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911409609.3A CN111138843A (zh) 2019-12-31 2019-12-31 一种石墨烯基聚氨酯多孔纳米材料及其制备方法

Publications (1)

Publication Number Publication Date
CN111138843A true CN111138843A (zh) 2020-05-12

Family

ID=70522460

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911409609.3A Pending CN111138843A (zh) 2019-12-31 2019-12-31 一种石墨烯基聚氨酯多孔纳米材料及其制备方法

Country Status (2)

Country Link
CN (1) CN111138843A (zh)
WO (1) WO2021135378A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021135378A1 (zh) * 2019-12-31 2021-07-08 苏州桐力光电股份有限公司 一种石墨烯基聚氨酯多孔纳米材料及其制备方法
CN113600132A (zh) * 2021-08-31 2021-11-05 南通大学 一种吸附用的插层石墨烯共混聚氨酯开孔海绵的制备方法
CN115181412A (zh) * 2022-08-25 2022-10-14 足力健老龄产业发展有限公司北京分公司 一种石墨烯鞋垫及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432671A (zh) * 2016-09-21 2017-02-22 江苏盖姆纳米材料科技有限公司 一种碳基海绵及泡沫材料的制备方法
CN106832189A (zh) * 2017-01-24 2017-06-13 南京科孚纳米技术有限公司 一种石墨烯聚氨酯复合材料的制备方法
CN107722230A (zh) * 2017-10-16 2018-02-23 北京北排科技有限公司 一种无机填料改性聚氨酯泡沫材料及其制备方法
CN108569692A (zh) * 2017-03-10 2018-09-25 中国石油化工股份有限公司 改性石墨烯及其制备方法以及聚氨酯泡沫材料及其制备方法和应用
CN108774306A (zh) * 2018-06-29 2018-11-09 南京红宝丽新材料有限公司 一种匀质的不燃型聚氨酯泡沫隔热保温材料及其制备方法
CN109553743A (zh) * 2017-09-25 2019-04-02 北京工商大学 一种无机填料填充耐高温泡沫材料及其制备方法
CN109942877A (zh) * 2019-03-21 2019-06-28 北京理工大学 一种电磁屏蔽型聚氨酯轻量化材料的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104844781B (zh) * 2015-05-29 2018-03-23 杨秀莲 一种石墨烯化学改性硬质聚氨酯泡沫
EP3538611B1 (en) * 2016-11-09 2023-08-02 Basf Se Polyurethane comprising graphene nano structure
CN106832887A (zh) * 2017-02-21 2017-06-13 东莞市雄林新材料科技股份有限公司 一种多次发泡tpu复合材料及其制备方法
CN111138843A (zh) * 2019-12-31 2020-05-12 苏州桐力光电股份有限公司 一种石墨烯基聚氨酯多孔纳米材料及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432671A (zh) * 2016-09-21 2017-02-22 江苏盖姆纳米材料科技有限公司 一种碳基海绵及泡沫材料的制备方法
CN106832189A (zh) * 2017-01-24 2017-06-13 南京科孚纳米技术有限公司 一种石墨烯聚氨酯复合材料的制备方法
CN108569692A (zh) * 2017-03-10 2018-09-25 中国石油化工股份有限公司 改性石墨烯及其制备方法以及聚氨酯泡沫材料及其制备方法和应用
CN109553743A (zh) * 2017-09-25 2019-04-02 北京工商大学 一种无机填料填充耐高温泡沫材料及其制备方法
CN107722230A (zh) * 2017-10-16 2018-02-23 北京北排科技有限公司 一种无机填料改性聚氨酯泡沫材料及其制备方法
CN108774306A (zh) * 2018-06-29 2018-11-09 南京红宝丽新材料有限公司 一种匀质的不燃型聚氨酯泡沫隔热保温材料及其制备方法
CN109942877A (zh) * 2019-03-21 2019-06-28 北京理工大学 一种电磁屏蔽型聚氨酯轻量化材料的制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021135378A1 (zh) * 2019-12-31 2021-07-08 苏州桐力光电股份有限公司 一种石墨烯基聚氨酯多孔纳米材料及其制备方法
CN113600132A (zh) * 2021-08-31 2021-11-05 南通大学 一种吸附用的插层石墨烯共混聚氨酯开孔海绵的制备方法
CN113600132B (zh) * 2021-08-31 2023-09-15 南通大学 一种吸附用的插层石墨烯共混聚氨酯开孔海绵的制备方法
CN115181412A (zh) * 2022-08-25 2022-10-14 足力健老龄产业发展有限公司北京分公司 一种石墨烯鞋垫及其制备方法

Also Published As

Publication number Publication date
WO2021135378A1 (zh) 2021-07-08

Similar Documents

Publication Publication Date Title
CN111138843A (zh) 一种石墨烯基聚氨酯多孔纳米材料及其制备方法
Lu et al. Enhanced thermal conductivity of polyurethane/wood powder composite phase change materials via incorporating low loading of graphene oxide nanosheets for solar thermal energy storage
US7758783B2 (en) Continious production of exfoliated graphite composite compositions and flow field plates
EP3617141B1 (en) Paper ball-like graphene microsphere, composite material thereof, and preparation method therefor
US5565497A (en) Dispersant for filled, rigid cellular polymers
Li et al. Engineering of high-density thin-layer graphite foam-based composite architectures with superior compressibility and excellent electromagnetic interference shielding performance
US8728679B2 (en) Laminated exfoliated graphite composite-metal compositions for fuel cell flow field plate or bipolar plate applications
US20080277628A1 (en) Exfoliated graphite composite compositions for fuel cell flow field plates
US10894397B2 (en) Process for producing graphene foam laminate based sealing materials
CN105097066A (zh) 官能性石墨烯-橡胶纳米复合材料
US20230257623A1 (en) Precursor for super-hydrophobic composite coating and preparation method therefor
EP2417176A1 (de) Hydroxygruppen umfassende kohlenstoffnanoröhren, verfahren zu deren herstellung und diese kohlenstoffnanoröhren umfassende polyurethanpolymere
Zhang et al. High dimensional stability and low viscous response solid propellant binder based on graphene oxide nanosheets and dual cross-linked polyurethane
CN1976807B (zh) 树脂浸渍的柔性石墨制品
EP2871207A1 (en) Polyurethane foam nanocomposite and a method of its obtaining
JP2008001866A (ja) ポリウレタンシートおよびその製造方法
CN114395160B (zh) 一种石墨烯改性聚氨酯复合材料及其制备方法
JP3142587B2 (ja) 炭素質組成物、燃料電池用炭素材およびその製造方法
Xu et al. Graphene and boron nitride foams for smart functional applications
CN110028779B (zh) 一种汽车电池用隔热材料及其制备工艺
CN113387702A (zh) 一种高导热石墨烯复合散热膜及其制备方法
Zhang Largely improved mechanical properties of polyurethane nanocomposites via in situ polymerization with low loading of graphene oxide
Li et al. Construction of polyurethane-imide/graphene oxide nanocomposite foam with gradient structure and its thermal mechanical stability
KR20190118386A (ko) 탄소나노튜브가 고르게 분산된 폼 소재 및 그 제조방법
CN108676198B (zh) 表面改性氧化石墨烯及其复合材料的制备方法

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20200512

RJ01 Rejection of invention patent application after publication