CN111153830A - Multifunctional composite material, polyether, and preparation method and application thereof - Google Patents
Multifunctional composite material, polyether, and preparation method and application thereof Download PDFInfo
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- CN111153830A CN111153830A CN202010007090.2A CN202010007090A CN111153830A CN 111153830 A CN111153830 A CN 111153830A CN 202010007090 A CN202010007090 A CN 202010007090A CN 111153830 A CN111153830 A CN 111153830A
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- polyether
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- diazonium salt
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 59
- 229920000570 polyether Polymers 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000012954 diazonium Substances 0.000 claims description 32
- 150000001989 diazonium salts Chemical class 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 28
- -1 3, 5-disubstituted-4-aminophenol Chemical class 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000009413 insulation Methods 0.000 claims 1
- 239000004753 textile Substances 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 8
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000007306 functionalization reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- YHQVBHFKCBFNEG-UHFFFAOYSA-N 4-amino-3,5-difluorophenol Chemical compound NC1=C(F)C=C(O)C=C1F YHQVBHFKCBFNEG-UHFFFAOYSA-N 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- KQOIBXZRCYFZSO-UHFFFAOYSA-N 3,5-difluoroaniline Chemical compound NC1=CC(F)=CC(F)=C1 KQOIBXZRCYFZSO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000007777 multifunctional material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- WNRGWPVJGDABME-UHFFFAOYSA-N 3,5-Dimethoxyaniline Chemical compound COC1=CC(N)=CC(OC)=C1 WNRGWPVJGDABME-UHFFFAOYSA-N 0.000 description 2
- RVNUUWJGSOHMRR-UHFFFAOYSA-N 3,5-dibromoaniline Chemical compound NC1=CC(Br)=CC(Br)=C1 RVNUUWJGSOHMRR-UHFFFAOYSA-N 0.000 description 2
- UJGIEAXELCZTOF-UHFFFAOYSA-N 4-amino-3,5-dibromophenol Chemical compound NC1=C(Br)C=C(O)C=C1Br UJGIEAXELCZTOF-UHFFFAOYSA-N 0.000 description 2
- NCJAKCZENDBSCU-UHFFFAOYSA-N 4-amino-3,5-dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1N NCJAKCZENDBSCU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/85—Chemically modified polymers by azo compounds
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2669—Non-metals or compounds thereof
- C08G65/2675—Phosphorus or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
Abstract
The invention discloses a multifunctional composite material, polyether, and a preparation method and application thereof, and belongs to the field of composite materials. The invention mainly relates to preparation of a multifunctional nano complex, and polyether with different structures is synthesized by using the novel initiator, and the polyether has photoresponse performance, heat preservation performance and enhanced mechanical performance, and has wide application value in the field of intelligent materials in the future.
Description
Technical Field
The invention relates to a multifunctional composite material, polyether, and a preparation method and application thereof, and belongs to the field of composite materials.
Background
The graphite flake layer material is used as a traditional two-dimensional material, has the characteristics of high specific surface area, light weight, excellent electronic conductivity, good chemical and thermodynamic stability and the like, and has wide application prospect in the field of polymer performance enhancement.
The functionalization of graphite flake materials is a hotspot of research in recent years, and various materials such as organic functional molecules, inorganic nano particles, polymers and the like are compounded with the graphite flake materials through methods such as non-covalent bonds, covalent bonds and the like. Generally speaking, the compounding of polyether polyol and graphite flake layer material is generally a blending (simple blending or supermolecular action) doping method, which is simple and efficient, but has the problems of uneven doping, phase separation and the like. Secondly, the polyether glycol can be compounded with the graphite sheet material by a covalent grafting method, and the problems of low grafting degree, distribution on the edge of the graphite sheet material and the like generally exist. Aiming at the problems, the novel multifunctional molecule is designed and synthesized, so that the molecules are uniformly distributed on the surface of a graphite sheet material, and then in-situ polymerization is carried out to obtain a polyether product. The polyether product has good light responsiveness, and simultaneously has higher strength and near infrared light absorption characteristic due to even compounding with the graphite flake layer material. Downstream products produced based on the polyether have great application value in the fields of photoresponse, heat preservation, high-strength materials and the like.
Disclosure of Invention
In order to expand the application of polyether products in the fields of photoresponse, heat insulation materials and high-mechanical-strength materials, the multifunctional composite material is synthesized and applied to polyether synthesis.
According to a first aspect of the present invention, there is provided a multifunctional composite material having the following structural formula:
wherein ,R2Each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
According to a second aspect of the present invention, there is provided a polyether having the formula:
wherein ,
m is an integer of 0 to 200, n is an integer of 0 to 100, and m and n cannot be 0 at the same time; preferably, m is an integer of 0-150, n is an integer of 20-80 or m is an integer of 20-150, n is an integer of 0-80 or m is an integer of 20-150, and n is an integer of 20-80;
R2each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
According to a third aspect of the present invention, the present invention further provides a method for preparing the above multifunctional composite material, comprising the steps of:
(A) reacting a3, 5-disubstituted-4-aminophenylalkyl alcohol of formula (I) (e.g., selected from 3, 5-disubstituted-4-aminophenol, 3, 5-disubstituted-4-aminobenzene)Phenol methanol, 3, 5-disubstituted-4-aminophenylethanol, etc.) in HCl solution (e.g., at a concentration of 10-38%) with NaNO2Reacting to generate a diazonium salt solution, and reacting with 3, 5-disubstituted aniline of a formula (II) to obtain a product AZO-1 of a formula (III);
(B) preparing a product AZO-1 of a formula (III) into a diazonium salt solution, and then reacting the diazonium salt solution with a graphite sheet material of a formula (IV) to obtain the multifunctional composite material of a formula (V);
in the above formulae, R2Each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
In step (A), preferably, 3, 5-disubstituted-4-aminobenzylalcohol, hydrochloric acid, NaNO2The molar ratio to the 3, 5-disubstituted aniline is 1:2.0-8:1-2.5:1-2.0, preferably 1:2.5-4:1.05-1.15: 1-1.1.
In step (A), preferably, a3, 5-disubstituted-4 aminophenylalkyl alcohol (e.g., selected from 3, 5-disubstituted-4 aminophenol, 3, 5-disubstituted-4 aminophenol methanol, 3, 5-disubstituted-4 aminophenylethanol, etc.) of formula (I) is reacted with NaNO in HCl solution2The reaction is stirred and reacted for 30-60min at the temperature of 0-5 ℃; the reaction of the diazonium salt solution with the 3, 5-disubstituted aniline of formula (II) is carried out at 0-5 ℃ and pH 5-7 for 6-8h, preferably in a solvent such as a water/acetone mixed solution with a volume ratio of 5: 1.
Further, in the step (A), the two substituents at the 3, 5-positions in the 3, 5-disubstituted-4-aminobenzylalcohol are each independently selected from the group consisting of F, Cl, Br, CH3、OCH3、CF3、OCF3。
Further, in the preparation of the diazonium salt solution of step (B), AZO-1 and NaNO are used2Reacting in hydrochloric acid solution (concentration 10-38%), AZO-1, NaNO2The molar ratio of the diazonium salt to the hydrochloric acid is 1:1.05-2:2-6, and the prepared diazonium salt solution and the graphite flake layer material are reacted for 2-24 hours at the temperature of 0-50 ℃. The mass ratio of the diazonium salt to the graphite platelet material is not particularly limited and may be 20-1000:1, preferably 100-400: 1. The graphite flake layer material contains one or more of crystalline flake graphite, expanded graphite, graphene oxide, reduced graphene oxide and the like, and preferably, the reduced graphene oxide.
According to a fourth aspect of the present invention, there is provided a method for preparing the above polyether, comprising the steps of:
(C) introducing ethylene oxide and/or propylene oxide in the presence of the above multifunctional composite to react to obtain a polyether of formula (VI):
wherein ,
m is an integer of 0 to 200, n is an integer of 0 to 100, and m and n cannot be 0 at the same time; preferably, m is an integer of 0-150, n is an integer of 20-80 or m is an integer of 20-150, n is an integer of 0-80 or m is an integer of 20-150, and n is an integer of 20-80;
R2each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
The molecular weight of the polyether related to the invention is 5000-.
Further, the reaction of step (C) is carried out in the presence of a catalyst. Suitable catalysts include NaOH, KOH, Na, NaH, CHO3Na、CHO3K. One or more of a bimetallic catalyst, an alkaline earth metal catalyst, a phosphazene catalyst, a lewis acid catalyst, and the like, preferably selected from the group consisting of alkali metal catalysts and phosphazene catalysts. With respect to the catalystThe amount of the initiator to be used is generally 0.01 to 1.0 wt%, preferably 0.05 to 0.3 wt%, based on the total weight of the initiator and one or both of ethylene oxide and propylene oxide to be added to the reaction. The reaction temperature is 80-160 ℃, preferably 120-130 ℃. The reaction pressure is in the range of-0.1 MPa to 0.6MPa, and the pressure is preferably controlled to be not higher than 0.3 MPa. With regard to the block sequence pattern of the block polyether, the design is made by changing the order of EO and/or PO feeding reaction. With respect to the synthesis of random copolyethers, copolyethers can be obtained by adding EO and PO in different mass ratios simultaneously. The molecular weight of the polyether related to the invention is 5000-. The mass ratio of the multifunctional composite material to the ethylene oxide and/or propylene oxide may be 1:10 to 100, preferably 1:20 to 40. The polyether of the invention comprises polyoxyethylene ether, polyoxypropylene ether, block polyether and random copolyether.
In a preferred embodiment, exemplified by the starting 3, 5-difluoro-4-aminophenol, the process comprises: synthesis of photoresponsive molecules: one mole of 3, 5-difluoro-4-aminophenol was weighed out and dissolved in 2.5-4 moles of HCl solution, denoted as a. Weighing 1.05-1.15 mol of NaNO2Dissolving in deionized water, adding NaNO while stirring in ice bath2Slowly add dropwise to a. Keeping the temperature at 0-5 ℃, and stirring for reaction for 30-60min to obtain a diazonium salt solution B. Weighing 1-1.1 mol of 3, 5-difluoroaniline, dissolving in a mixed solution of water and acetone with a volume ratio of 5:1 at 0-5 ℃, slowly and dropwise adding the solution B into the solution, and using saturated NaHCO3Adjusting the pH value of the aqueous solution to 5-7, and reacting for 6-8 h. And after the reaction, recrystallizing by using ethanol/water (volume ratio is 1:1) to obtain the product AZO-1.
Preparing a multifunctional composite material: 1mol of AZO-1 and 1.1mol of NaNO were weighed2The mixture was added to a flask containing 500m L deionized water, followed by 3-4 equivalents of hydrochloric acid and placed in an ice bath for 1 hour to obtain diazonium salt solution C. And slowly dripping the C into 500m L aqueous solution of graphite sheet material (3mg/m L), reacting for 4 hours at 0-5 ℃, and reacting for 12-20 hours at room temperature. The product is passed throughDeionized water, acetone and DMF are repeatedly washed and filtered (PTFE film) to remove unreacted AZO-1 and diazonium salt, and the product is repeatedly reacted with diazonium salt solution twice by the functionalization method to improve the grafting density. Vacuum drying to obtain the final product. (UV-Vis: 450nm tan-to-cis; 290nm π - π conjugation.)
Polyether synthesis: the synthesis route of the polyether is different from that of the traditional polyether synthesis process, firstly, DMF is used for carrying out ultrasonic dispersion on the multifunctional composite material, dispersion liquid is added into a reaction kettle to be used as an initiator for reaction, and after the reaction, the solvent DMF is removed under high temperature and reduced pressure. Other conditions with reference to conventional polyether synthesis, the starter, the type of catalyst, the amount of catalyst used, the starter/EO/PO molar mass ratio, the reaction temperature, the reaction pressure can be reasonably determined by the person skilled in the art according to the teaching of the present invention in combination with the prior art. Suitable catalysts include NaOH, KOH, Na, NaH, CHO3Na、CHO3K. Bimetallic catalysts, alkaline earth metal catalysts, phosphazene catalysts, lewis acid catalysts, and the like, with alkali metal catalysts and phosphazene catalysts being preferred. The amount of the catalyst is usually 0.01 to 1.0 wt%, preferably 0.05 to 0.3 wt%, based on the total weight of the initiator, ethylene oxide and/or propylene oxide to be added to the reaction. The reaction temperature is 80-160 ℃, preferably 120-130 ℃. The reaction pressure is in the range of-0.1 MPa to 0.6MPa, and the pressure is preferably controlled to be not higher than 0.3 MPa. With regard to the block sequence pattern of the block polyether, the design is made by changing the order of EO and/or PO feeding reaction. With respect to the synthesis of random copolyethers, copolyethers can be obtained by adding EO and PO in different mass ratios simultaneously.
wherein ,
and m and n are not 0 at the same time; preferably, m is0 to 150, n is an integer of 20 to 80 or m is an integer of 20 to 150, n is an integer of 0 to 80 or m is an integer of 20 to 150, and n is an integer of 20 to 80.
The specific method for preparing the multifunctional composite material comprises the following key parts:
the synthesis of the photoresponse molecule is azobenzene molecule, wherein para-position of the molecule is amino and hydroxyl substituent respectively, and four ortho-position substituents are F, Cl, Br and CH3、OCH3、CF3 and OCF3One kind of (1). The reaction adopts diazotization coupling reaction, the reaction solution adopts water/acetone mixed solution with the volume ratio of 5:1, and the addition of a small amount of acetone can improve the solubility of reactants and enhance the compatibility of two phases. The mixed solvent used in the present invention is exemplified by water/acetone, but is not limited to water/acetone, NMP, DMF, tetrahydrofuran, and the like, and may be selected according to the characteristics of the reactants.
In this embodiment, the multifunctional composite material of the present invention is synthesized by a diazonium salt radical reaction at room temperature, which is relatively mild. Meanwhile, the diazotization free radical reaction is to utilize free radicals generated by amino diazotization of azobenzene to react with carbon-carbon double bonds on the surface of the graphite sheet material, so that azobenzene is covalently grafted on the surface of the graphite sheet material instead of the edge. The graft ratio can be improved by repeating the reaction.
In this embodiment, the synthesis of the polyether of the multifunctional composite material of the present invention firstly uses DMF as the dispersing initiator, the dispersion liquid as the initiator is used for polyether synthesis, and the DMF solvent is removed by high temperature (120-140 ℃) vacuum pumping after the reaction. The solvent used in the present invention is DMF, but is not limited to DMF, NMP, DMAC, and other solvents that can disperse the multifunctional composite material and do not react with EO and PO can be used. In the polyether synthesis process, the synthesis of high-quality polyether is realized mainly by controlling conditions such as reaction temperature, catalyst and the like, and the catalyst is preferably a phosphazene catalyst.
The invention further provides the application of the multifunctional composite material in polyether synthesis, polymer modification, heat insulation materials, coating additives, the photoelectric field, the photovoltaic field and the like.
The invention further provides the application of the polyether in the fields of washing, pharmacy, spinning, cosmetics and the like.
Compared with the prior art, the invention has the following advantages:
1. the molecules used for grafting are azobenzene molecules with an adjacent position four-substituted and opposite position push-pull electronic structure, the molecules can realize visible light response, and the damage of ultraviolet light to the environment is avoided.
2. According to the multifunctional composite material, azobenzene molecules are uniformly grafted on the surface of the graphite flake layer instead of being grafted on the edge, so that polyether is polymerized on the surface of the graphite flake layer, and the molecular-level uniform compounding of the polyether and the graphite flake layer is realized. By regulating and controlling the grafting rate of azobenzene molecules on the surface of a graphite sheet and the polymerization degree of polyether, the composite material with different graphite sheet/polyether ratios can be obtained.
3. The polyether product synthesized based on the novel initiator belongs to a functional product and has multiple functions. The existence of the graphite flake material can enhance the near infrared light absorption characteristic of polyether, and the graphite flake material is used for a heat insulation material; meanwhile, the high strength and flexibility of the graphite sheet material can improve the mechanical strength of polyether downstream products. The existence of azobenzene molecules can realize the photoresponse performance, which is beneficial to realizing the remote control of the polyether performance.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Synthesis of 2,2 ', 6,6 ' -tetrafluoro-4-amino-4 ' -hydroxy azobenzene (AZO-1) 10mol of 3, 5-difluoro-4-aminophenol (1450g) are weighed out and dissolved in 25mol of HCl solution (38% strength) and are designated A1. Weighing 10mol of NaNO2(690g) Dissolving in 5000mL deionized water, and adding NaNO while stirring in ice bath2Slowly add dropwise to a 1. Keeping the temperature at 0-5 ℃, stirring and reacting for 30min to obtain a diazonium salt solution B1, and weighing 10mol of 3, 5-difluoroAniline (1290g) was dissolved in 5000mL of a 0-5 ℃ water/acetone mixture at a volume ratio of 5:1, and solution B1 was slowly added dropwise to the solution using saturated NaHCO3The pH of the aqueous solution was adjusted to about 6 and the reaction time was 6 h. And after the reaction, recrystallizing by using ethanol/water (volume ratio is 1:1) to obtain the product AZO-1.19F NMR(376MHz,DMSO-d6):δ＝-121.33(s,4F；Ar-F)。HRMS-ESI:m/z:285.0522(calcd.for[M+H]+,285.0525)。
2. Multifunctional composite material: 1mol AZO-1(285g) and 1.1mol NaNO were weighed2(69g) Into a flask containing 5000mL of deionized water, followed by addition of 3mol of hydrochloric acid (38% strength aqueous hydrochloric acid solution) was placed in an ice bath and reacted for 1 hour to obtain a diazonium salt solution C1. Then, slowly dripping the C1 into 500mL of aqueous solution of graphite sheet material (5mg/m L), reacting for 4 hours at 0-5 ℃, and reacting for 12 hours at room temperature. The product is repeatedly washed by deionized water, acetone and DMF, and filtered (PTFE film) to remove unreacted AZO-1 and diazonium salt, and the product is repeatedly reacted with diazonium salt solution twice by the above-mentioned functionalization method to improve the grafting density. Vacuum drying to obtain the final product. (UV-Vis: 450nm tan-to-cis; 290nm π - π conjugation).
3. And (3) polyether synthesis: firstly, carrying out ultrasonic dispersion on 2g of multifunctional composite material by using 150mL of DMF, adding the dispersion into a 0.5L reaction kettle with a stirring device, a heating sleeve and an internal water-cooling coil, adding 0.05 wt% of phosphazene catalyst, and sealing the reaction kettle. Replacing with nitrogen for three times, starting stirring, heating to 90 ℃, dehydrating under-0.1 MPa, and then heating to 130 ℃. Then slowly introducing ethylene oxide, keeping the reaction pressure less than 0.3MPa by controlling the feeding speed, stopping feeding when the total amount of the introduced ethylene oxide is 20g, carrying out an aging reaction at 130 ℃ for 3 hours, and carrying out demonomerization at-0.1 MPa; cooling to room temperature to obtain the polyether. GPC measurement: mw 5000g/mol, PDI 1.32.
Example 2
Synthesis of 2,2 ', 6,6 ' -tetrabromo-4-amino-4 ' -hydroxyazobenzene (AZO-2) 10mol of 3, 5-dibromo-4-aminophenol (2670g) were weighed out and dissolved in 30mol of HCl solution (38% strength) and recorded as A2. Weighing 11mol of NaNO2(759g) Dissolving in deionized water, adding NaNO while stirring in ice bath2Slowly add dropwise to a 2. Keeping the temperature at 0-5 ℃, and stirring for reaction for 45min to obtain a diazonium salt solution B2. 10mol of 3, 5-dibromoaniline (2510g) are weighed out and dissolved in a 5:1 volume ratio water/acetone mixed solution at 0-5 ℃, and solution B2 is slowly added dropwise to the solution, saturated NaHCO is used3The pH of the aqueous solution was adjusted to about 6.5 and the reaction time was 7 h. After the reaction, the product AZO-2 is obtained by recrystallization with ethanol/water (volume ratio 1: 1). HRMS-ESI: M/z:528.7279(calcd. for [ M + H ]]+,528.7282)。
2. Multifunctional composite material: 1mol of AZO-2 and 1.1mol of NaNO are weighed2Into a flask containing 500mL of deionized water, followed by addition of 3.5mol of hydrochloric acid (38% in concentration) was placed in an ice bath and reacted for 1 hour to obtain a diazonium salt solution C2. Then slowly dripping C2 into 500mL of graphite sheet material (5mg/m L) aqueous solution, reacting for 4h at 0-5 ℃, and reacting for 16h at room temperature. The product is repeatedly washed by deionized water, acetone and DMF, and filtered (PTFE film) to remove unreacted AZO-2 and diazonium salt, and the product is repeatedly reacted with diazonium salt solution twice by the above-mentioned functionalization method to improve the grafting density. Vacuum drying to obtain the final product. (UV-Vis: 440nm tan-to-cis; 290nm π - π conjugation).
3. And (3) polyether synthesis: firstly, 2g of multifunctional composite material is subjected to ultrasonic dispersion by using 150mL of DMF, the dispersion is added into a 0.5L reaction kettle with a stirring device, a heating sleeve and an internal water-cooling coil pipe, 0.1% of sodium methoxide catalyst is added, and the reaction kettle is sealed. Replacing with nitrogen for three times, starting stirring, heating to 90 ℃, dehydrating under-0.1 MPa, and then heating to 120 ℃. Then slowly introducing propylene oxide, keeping the reaction pressure less than 0.3MPa by controlling the feeding speed, stopping feeding when the total amount of the propylene oxide introduced is 40g, carrying out an aging reaction at 120 ℃ for 3 hours, and carrying out demonomerization at-0.1 MPa; cooling to room temperature to obtain the polyether. GPC measurement: mw 14023g/mol, PDI 1.34.
Example 3
Synthesis of 2,2 ', 6,6 ' -tetramethoxy-4-amino-4 ' -hydroxy-azobenzene (AZO-3) 10mol of 3, 5-dimethoxy-4-aminophenol (1690g) are weighed out and dissolved in 40mol of HCl (38% strength) solution and are designated A3. Weighing 21molNaNO2(1449g) Dissolved in deionized waterNaNO is added into water under ice-bath stirring2Slowly add dropwise to a 3. Keeping the temperature at 0-5 ℃, and stirring for reaction for 60min to obtain a diazonium salt solution B3. 18mol of 3, 5-dimethoxyaniline (2754g) are weighed out and dissolved in a 5:1 volume ratio water/acetone mixture at 0-5 ℃, solution B3 is slowly added dropwise to this solution, saturated NaHCO is used3Adjusting the pH value of the aqueous solution to 5-7, and reacting for 8 h. And after the reaction, recrystallizing by using ethanol/water (volume ratio is 1:1) to obtain the product AZO-3. HRMS-ESI: M/z:333.1324(calcd. for [ M + H ]]+,333.1325)。
2. Multifunctional composite material: 1mol of AZO-3 and 1.18mol of NaNO are weighed2The mixture was added to a flask containing 500mL of deionized water, followed by addition of 4mol of hydrochloric acid, and the mixture was placed in an ice bath to react for 1 hour to obtain a diazonium salt solution C3. Then, slowly dripping C3 into 500mL of graphite sheet material (2mg/m L) aqueous solution, reacting for 4 hours at 0-5 ℃, and reacting for 20 hours at room temperature. The product is repeatedly washed by deionized water, acetone and DMF, and filtered (PTFE film) to remove unreacted AZO-3 and diazonium salt, and the product is repeatedly reacted twice by the above functionalization method to improve the grafting density. Vacuum drying to obtain the final product. (UV-Vis: 430nm tan-to-cis; 285nm π - π conjugation.)
3. And (3) polyether synthesis: first, 2g of the multifunctional composite material was ultrasonically dispersed using 150mL of DMF, the dispersion was added to a 0.5L reaction vessel equipped with a stirring, heating mantle and an internal water-cooled coil, 0.1% potassium hydroxide catalyst was added, and the reaction vessel was sealed. Replacing with nitrogen for three times, starting stirring, heating to 90 ℃, dehydrating under-0.1 MPa, and then heating to 125 ℃. Then slowly introducing an ethylene oxide/propylene oxide mixed solution, keeping the reaction pressure less than 0.3MPa by controlling the feeding speed, stopping feeding when 50g of epoxyalkane is introduced, carrying out an aging reaction for 3 hours at 125 ℃, and carrying out demonomerization at-0.1 MPa; cooling to room temperature to obtain the polyether. GPC measurement: mw13654g/mol, PDI 1.36.
Application example 1
Polymer modification applications: a multifunctional composite was prepared as in example 1. The multifunctional material is added into DMF solution of polyurethane elastomer according to the addition amount of 0.5 percent, and the solution is placed in a vacuum oven for vacuum drying for 48 hours at the temperature of 140 ℃ to obtain the multifunctional material modified polyurethane elastomer. The modified polymer was irradiated with near infrared light, and the polymer was allowed to undergo a temperature rise of 10 ℃. The comparative test was a polymer without added multifunctional material and the temperature rise was only 1 ℃. Thus, the modified polymer can be used as a heat-insulating coating.
Application example 2
The application of the polyether comprises the following steps: the polyether was prepared as in example 1. The polyether was added to a commercial laundry detergent in an amount of 0.3% to prepare a novel detergent. 5g of the compounded detergent is dissolved in a closed glass container filled with 500ml of water, and the mixture is vigorously shaken for 3min to generate a large amount of foam. A commercial laundry detergent without the addition of the above polyether was used as a comparative experiment under the same conditions. The comparison shows that the foam height is 5-6cm lower than that of the laundry detergent without the polyether after 0.3 percent of polyether is added, and the foam height of the laundry detergent with the polyether is further reduced by 3-5cm after visible light irradiation. Therefore, the novel washing liquid added with polyether has the advantages of low foam and photoresponse defoaming.
Claims (10)
1. A multifunctional composite having the following structural formula:
wherein ,R2Each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
2. A polyether having the following structural formula:
wherein ,
m is an integer of 0-200, n is an integer of 0-100, and m and n are not 0 at the same time; preferably, m is an integer of 0-150, n is an integer of 20-80 or m is an integer of 20-150, n is an integer of 0-80 or m is an integer of 20-150, and n is an integer of 20-80;
R2each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
3. A method of preparing the multifunctional composite of claim 1 comprising the steps of:
(A) reacting a3, 5-disubstituted-4-aminophenylalkyl alcohol of formula (I) (e.g., selected from 3, 5-disubstituted-4-aminophenol, 3, 5-disubstituted-4-aminophenol methanol, 3, 5-disubstituted-4-aminophenylethanol, etc.) with NaNO in HCl solution (e.g., at a concentration of 10-38%)2Reacting to generate a diazonium salt solution, and reacting with 3, 5-disubstituted aniline of a formula (II) to obtain a product AZO-1 of a formula (III);
(B) preparing a product AZO-1 of a formula (III) into a diazonium salt solution, and then reacting the diazonium salt solution with a graphite sheet material of a formula (IV) to obtain the multifunctional composite material of a formula (V);
in the above formulae, R2Each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
4. The method for producing according to claim 3, which isIn the step (A), 3, 5-disubstituted-4-aminobenzylalcohol, hydrochloric acid, NaNO2The molar ratio to the 3, 5-disubstituted aniline is 1:2.0-8:1-2.5:1-2.0, preferably 1:2.5-4:1.05-1.15: 1-1.1; and/or
The two substituents at the 3, 5-position in the 3, 5-disubstituted-4-aminophenylalkyl alcohol are each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3。
5. The process according to claim 3 or 4, wherein in step (A), the 3, 5-disubstituted-4 aminobenzylalcohol of formula (I) is reacted with NaNO in HCl solution2The reaction is stirred and reacted for 30-60min at the temperature of 0-5 ℃; the reaction of the diazonium salt solution with the 3, 5-disubstituted aniline of formula (II) is carried out at 0-5 ℃ and pH 5-7 for 6-8h, preferably in a solvent such as a water/acetone mixed solution with a volume ratio of 5: 1.
6. The production method according to any one of claims 3 to 5, wherein AZO-1 is reacted with NaNO in the production of the diazonium salt solution of step (B)2Reacting in hydrochloric acid solution (concentration 10-38%), AZO-1, NaNO2The molar ratio of the diazonium salt to the hydrochloric acid is 1:1.05-2:2-6, and the prepared diazonium salt solution and the graphite flake layer material are reacted for 2-24 hours at the temperature of 0-50 ℃; and/or the presence of a gas in the gas,
the mass ratio of the diazonium salt to the graphite flake layer material is 20-1000:1, preferably 100-400: 1; and/or
The graphite flake layer material is selected from one or more of crystalline flake graphite, expanded graphite, graphene oxide and reduced graphene oxide, and preferably the reduced graphene oxide.
7. A process for preparing the polyether of claim 2 comprising the steps of:
(C) introducing ethylene oxide and/or propylene oxide in the presence of the multifunctional composite of claim 1 to react to obtain a polyether of formula (VI):
wherein ,
m is an integer of 0-200, n is an integer of 0-100, and m and n are not 0 at the same time; preferably, m is an integer of 0-150, n is an integer of 20-80 or m is an integer of 20-150, n is an integer of 0-80 or m is an integer of 20-150, and n is an integer of 20-80;
R2each independently selected from F, Cl, Br, CH3、OCH3、CF3、OCF3；
R3Each independently selected from the group consisting of a single bond (-), -CH2-、-CH2CH2-。
8. The method of claim 7, wherein the reaction of step (C) is carried out in the presence of a catalyst comprising NaOH, KOH, Na, NaH, CHO3Na、CHO3K. One or more of a bimetallic catalyst, an alkaline earth metal catalyst, a phosphazene catalyst, a lewis acid catalyst, and the like, preferably selected from the group consisting of alkali metal catalysts and phosphazene catalysts; and/or
The mass ratio of the multifunctional composite material to the ethylene oxide and/or the propylene oxide is 1:10-100, preferably 1: 20-40.
9. Use of the multifunctional composite of claim 1 in polyether synthesis, polymer modification, insulation, coating additives, the photovoltaic field, or the photovoltaic field.
10. Use of the polyether of claim 2 in the fields of detergency, pharmacy, textile, or cosmetics.
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| CN104844781A (en) * | 2015-05-29 | 2015-08-19 | 杨秀莲 | Graphene chemically-modified hard polyurethane foam |
| CN105542584A (en) * | 2016-01-29 | 2016-05-04 | 天津大学 | Thermal-inductive fluorocarbon function coating containing azobenzene/carbon-hybrid material and preparation method of thermal-inductive fluorocarbon function coating |
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| CN103980703A (en) * | 2014-06-04 | 2014-08-13 | 福州大学 | Flocculent-polyaniline-coated graphene composite material and preparation method and application thereof |
| CN104844781A (en) * | 2015-05-29 | 2015-08-19 | 杨秀莲 | Graphene chemically-modified hard polyurethane foam |
| CN105542584A (en) * | 2016-01-29 | 2016-05-04 | 天津大学 | Thermal-inductive fluorocarbon function coating containing azobenzene/carbon-hybrid material and preparation method of thermal-inductive fluorocarbon function coating |
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