CN111153830B - Multifunctional composite material, polyether, preparation method and application thereof - Google Patents
Multifunctional composite material, polyether, preparation method and application thereof Download PDFInfo
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 63
- 229920000570 polyether Polymers 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 229910002804 graphite Inorganic materials 0.000 claims description 35
- 239000010439 graphite Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 33
- 239000012954 diazonium Substances 0.000 claims description 31
- 150000001989 diazonium salts Chemical class 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- -1 3, 5-disubstituted aniline Chemical class 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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 7
- 230000008569 process Effects 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 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
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 125000003884 phenylalkyl group Chemical group 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 9
- 230000004298 light response Effects 0.000 abstract description 6
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003599 detergent Substances 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
- 230000001276 controlling effect 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
- 230000035484 reaction time Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 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
- 230000032683 aging Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 239000007777 multifunctional material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000007789 sealing 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
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-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
- 238000013329 compounding Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 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
- 239000011734 sodium Substances 0.000 description 2
- 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
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process 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
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 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
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 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
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a multifunctional composite material, polyether, a preparation method and application thereof, and belongs to the field of composite materials. The invention mainly relates to the preparation of a multifunctional nano-composite, and polyether with different structures is synthesized by utilizing the novel initiator, and the polyether has light response 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, a preparation method and application thereof, and belongs to the field of composite materials.
Background
As a traditional two-dimensional material, the graphite sheet material has the characteristics of high specific surface area, light weight, excellent electron conductivity, good chemical and thermodynamic stability and the like, and has wide application prospect in the field of polymer performance enhancement.
Functionalization of graphite flake materials is a hot point of research in recent years, and various materials such as organic functional molecules, inorganic nanoparticles, polymers and the like are compounded with the graphite flake materials by non-covalent bonds, covalent bonds and the like. In general, the compounding of polyether polyol and graphite flake material is generally a method of doping by blending (simple blending or supermolecular action), which is simple and efficient, but has the problems of uneven doping, phase separation and the like. Secondly, polyether polyol can be compounded with the graphite sheet material by a covalent grafting method, and the problems that the grafting degree is low, the polyether polyol is distributed at the edge of the graphite sheet material and the like generally exist. Aiming at the problems, the novel multifunctional molecule is designed and synthesized to realize uniform distribution of molecules on the surface of the graphite sheet material, so that the polyether product is obtained through in-situ polymerization. The polyether product has good light response, and has high intensity and near infrared light absorption property due to uniform composition with the graphite sheet material. The downstream product produced based on the polyether has 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-insulating 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 ,R2 Each independently selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 ；
R 3 Each independently selected from the group consisting of single bond (-), -CH 2 -、-CH 2 CH 2 -。
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 from 0 to 150, n is an integer from 20 to 80 or m is an integer from 20 to 150, n is an integer from 0 to 80 or m is an integer from 20 to 150, n is an integer from 20 to 80;
R 2 each independently selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 ；
R 3 Each independently selected from the group consisting of single bond (-), -CH 2 -、-CH 2 CH 2 -。
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) 3, 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-aminophenol, etc.) is reacted with NaNO in HCl solution (e.g., at a concentration of 10-38%) 2 Reacting to generate diazonium salt solution, and then reacting with 3, 5-disubstituted aniline shown in a formula (II) to obtain a product AZO-1 shown in a formula (III);
(B) Preparing a product AZO-1 of the formula (III) into diazonium salt solution, and then reacting with a graphite sheet material of the formula (IV) to obtain a multifunctional composite material of the formula (V);
in the above formulae, R 2 Each independently selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 ；
R 3 Each independently selected from the group consisting of single bond (-), -CH 2 -、-CH 2 CH 2 -。
In step (A), preferably, 3, 5-disubstituted-4-amino phenylalkyl alcohols, hydrochloric acid, naNO 2 The molar ratio of the catalyst 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, 3, 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 aminophenol ethanol, etc.) is reacted with NaNO in HCl solution 2 Stirring and reacting for 30-60min at 0-5 ℃; the reaction of the diazonium salt solution with the 3, 5-disubstituted anilines of formula (II) is carried out at 0-5℃and pH 5-7 for 6-8 hours, preferably in a solvent such as a water/acetone mixture in a volume ratio of 5:1.
Further, in step (A), the two substituents at the 3,5 positions in the 3, 5-disubstituted-4-amino phenylalkyl alcohol are each independently selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 。
Further, AZO-1 and NaNO in the preparation of diazonium salt solution in step (B) 2 Reacting in hydrochloric acid solution (concentration 10-38%) to obtain AZO-1, naNO 2 The molar ratio of the diazonium salt solution to the hydrochloric acid is 1:1.05-2:2-6, and the prepared diazonium salt solution and graphite sheet material are subjected to 2-24h at the temperature of 0-50 ℃. The mass ratio of diazonium salt to graphite platelet material is not particularly limited and may be 20-1000:1, preferably 100-400:1. The graphite flake material comprises one or more of crystalline flake graphite, expanded graphite, graphene oxide, reduced graphene oxide and the like, preferably reduced graphene oxide.
According to a fourth aspect of the present invention, there is provided a process for the preparation of the polyether described above, comprising the steps of:
(C) Introducing ethylene oxide and/or propylene oxide in the presence of the multifunctional composite material to react to obtain 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 from 0 to 150, n is an integer from 20 to 80 or m is an integer from 20 to 150, n is an integer from 0 to 80 or m is an integer from 20 to 150, n is an integer from 20 to 80;
R 2 each independently selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 ；
R 3 Each independently selected from the group consisting of single bond (-), -CH 2 -、-CH 2 CH 2 -。
The molecular weight of the polyether is 5000-20000g/mol.
Further, the reaction of step (C) is carried out in the presence of a catalyst. Suitable catalysts include NaOH, KOH, na, naH, CHO 3 Na、CHO 3 K. One or more of a bimetallic catalyst, an alkaline earth metal catalyst, a phosphazene catalyst, a lewis acid catalyst, etc., is preferably selected from an alkali metal catalyst and a phosphazene catalyst. The amount of the catalyst to be used is generally 0.01 to 1.0wt%, preferably 0.05 to 0.3wt%, based on the total weight of the initiator and one or both of ethylene oxide and propylene oxide fed into 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, preferably the control pressure is not higher than 0.3MPa. With regard to the block sequence pattern of the block polyether, the design is carried out by changing the order of EO and/or PO introduction reactions. 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 is 5000-20000g/mol. The mass ratio of the multifunctional composite to ethylene oxide and/or propylene oxide may be 1:10-100, preferably 1:20-40. The polyether of the invention comprises polyoxyethylene ether, polyoxypropylene ether, block polyether and random copolyether.
In a preferred embodiment, taking 3, 5-difluoro-4-aminophenol starting material as an example,the method comprises the following steps: synthesis of light-responsive molecules: one mole of 3, 5-difluoro-4-aminophenol was weighed and dissolved in 2.5-4 moles of HCl solution, designated a. Weighing 1.05-1.15 mol of NaNO 2 Dissolving in deionized water, stirring with ice bath to obtain NaNO 2 Slowly drop-wise into A. Keeping the temperature at 0-5 ℃, and stirring and reacting for 30-60min to obtain diazonium salt solution B. 1-1.1 mol of 3, 5-difluoroaniline is weighed and dissolved in a mixed solution of water and acetone with the volume ratio of 5:1 at the temperature of 0-5 ℃, and the solution B is slowly dripped into the solution, and saturated NaHCO is used 3 The pH of the aqueous solution is regulated to 5-7, and the reaction time is 6-8h. And (3) recrystallizing by using ethanol/water (volume ratio is 1:1) after the reaction to obtain the AZO-1 product.
Preparation of the multifunctional composite material: weighing 1 mole of AZO-1 and 1.1 mole of NaNO 2 Into a flask containing 500m L deionized water, 3-4 equivalents of hydrochloric acid was then added, and the mixture was placed in an ice bath to react for 1 hour to obtain diazonium salt solution C. Then, the C is slowly dripped into 500m L graphite flake material (3 mg/m L) water solution to react for 4 hours at 0-5 ℃ and for 12-20 hours at room temperature. The product is repeatedly washed by deionized water, acetone and DMF, filtered (PTFE film) to remove unreacted AZO-1 and diazonium salt, and then the product is repeatedly reacted with diazonium salt solution twice by the functionalization method to improve grafting density. And vacuum drying to obtain the final product. (UV-Vis: 450nm tan-to-cis; 290nm pi-pi conjugation.)
Polyether synthesis: the synthetic route of polyether is different from the traditional polyether synthetic process, DMF is firstly used for carrying out ultrasonic dispersion on the multifunctional composite material, the dispersion liquid is added into a reaction kettle to be used as an initiator for reaction, and the solvent DMF is removed under high temperature and reduced pressure after the reaction. Other conditions refer to conventional polyether synthesis, and those skilled in the art will incorporate the present technology in light of the teachings of the present inventionThe method can reasonably determine the initiator, the catalyst type, the catalyst dosage, the molar ratio of the initiator to EO/PO, the reaction temperature and the reaction pressure. Suitable catalysts include NaOH, KOH, na, naH, CHO 3 Na、CHO 3 K. Bimetallic catalysts, alkaline earth metal catalysts, phosphazene catalysts, lewis acid catalysts, and the like, alkali metal catalysts and phosphazene catalysts are preferred. The amount of the catalyst to be used is usually 0.01 to 1.0wt%, preferably 0.05 to 0.3wt%, based on the total weight of the initiator, ethylene oxide and/or propylene oxide to be fed into 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, preferably the control pressure is not higher than 0.3MPa. With regard to the block sequence pattern of the block polyether, the design is carried out by changing the order of EO and/or PO introduction reactions. 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 both 0; preferably, m is an integer from 0 to 150, n is an integer from 20 to 80 or m is an integer from 20 to 150, n is an integer from 0 to 80 or m is an integer from 20 to 150, n is an integer from 20 to 80.
The specific method for preparing the multifunctional composite material comprises the following key parts:
the synthesis of the light response type molecule is an azobenzene type molecule, wherein para position of the molecule is respectively amino and hydroxyl substituent groups, and four ortho position substituent groups are F, cl, br, CH 3 、OCH 3 、CF 3 and OCF3 One of them. The diazotization coupling reaction is adopted in the reaction, the water/acetone mixed solution with the volume ratio of 5:1 is adopted as the reaction solution, 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 invention is exemplified by water/acetone, but is not limited to water/acetoneSolvents such as NMP, DMF, tetrahydrofuran, etc. may also be selected according to the nature of the reactants.
In the embodiment, the synthesis of the multifunctional composite material adopts diazonium salt free radical reaction, the reaction temperature of the reaction is room temperature, and the reaction is milder. Meanwhile, the diazotization free radical reaction is to react with carbon-carbon double bonds on the surface of the graphite sheet material by utilizing free radicals generated by amino diazotization of azobenzene, so that the azobenzene is covalently grafted on the surface of the graphite sheet material instead of the edge. The grafting ratio can be improved by repeating the reaction.
In this embodiment, the polyether of the multifunctional composite material is synthesized by using DMF as a dispersing initiator of a dispersing agent, using a dispersion liquid as the initiator for polyether synthesis, and removing DMF solvent at a high temperature (120-140 ℃) after the reaction by vacuumizing. The solvent used in the present invention is DMF, but not limited to DMF, NMP, DMAC, etc. which can disperse the multifunctional composite material and which does 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 the reaction temperature, a catalyst and other conditions, and the catalyst is preferably a phosphazene catalyst.
The invention further provides application of the multifunctional composite material in polyether synthesis, polymer modification, heat insulation materials, paint additives, photoelectric fields, photovoltaic fields and the like.
The invention further provides application of the polyether in fields of washing, pharmacy, textile, 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 a temporary tetrasubstituted para-push-pull electronic structure, the molecules can realize visible light response, the damage of ultraviolet light to the environment is avoided, and the light response composite material synthesized by the invention is a novel nano composite with a molecular structure and is not reported at present.
2. According to the multifunctional composite material, azobenzene molecules are uniformly grafted on the surface of the graphite sheet instead of being grafted on the edge, so that polyether is polymerized on the surface of the graphite sheet, and uniform molecular-level compounding of the polyether and the graphite sheet is realized. The grafting rate of azobenzene molecules on the surface of the graphite flake and the polymerization degree of polyether are regulated, so that composite materials with different graphite flake/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 sheet material can enhance the near infrared light absorption characteristic of polyether, and is used for heat insulation materials; and meanwhile, the high strength and flexibility of the graphite sheet material can improve the mechanical strength of the downstream polyether product. The presence of azobenzene molecules can achieve photoresponsive properties, which would be advantageous for achieving remote control of polyether properties.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
1.2,2', synthesis of 6,6' -tetrafluoro-4-amino-4 ' -hydroxyazobenzene (AZO-1) 10mol of 3, 5-difluoro-4-aminophenol (1450 g) was weighed out and dissolved in 25mol of HCl solution (38% strength) and designated A1. Weighing 10mol of NaNO 2 (690g) Dissolving in 5000mL deionized water, stirring with ice bath to obtain NaNO 2 Slowly drop-wise into A1. Keeping the temperature at 0-5 ℃, stirring and reacting for 30min to obtain diazonium salt solution B1, weighing 10mol of 3, 5-difluoroaniline (1290 g) and dissolving in 5000mL of water/acetone mixed solution with the volume ratio of 0-5 ℃ being 5:1, slowly dropwise adding the solution B1 into the solution, and using saturated NaHCO 3 The aqueous solution was adjusted to a pH of about 6 and the reaction time was 6 hours. And (3) recrystallizing by using ethanol/water (volume ratio is 1:1) after the reaction to obtain the AZO-1 product. 19 F 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 (285 g) and 1.1mol NaNO were weighed out 2 (69g) Into a flask containing 5000mL of deionized water, 3mol of hydrochloric acid (38% aqueous hydrochloric acid) was then added, and the mixture was placed in an ice bath to react for 1 hour to obtain diazonium salt solution C1. Then, C1 was slowly dropped into 500mL of an aqueous solution of graphite flake material (5 mg/m L), and reacted at 0-5℃for 4 hours and at room temperature for 12 hours. The product is treated by deionized water, acetone andDMF is 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 grafting density. And vacuum drying to obtain the final product. (UV-Vis: 450nm tan-to-cis; 290nm pi-pi conjugation).
3. Synthesis of polyether: first, using 150mL DMF to carry out ultrasonic dispersion on 2g of the multifunctional composite material, adding the dispersion into a 0.5L reaction kettle with stirring, a heating jacket and an internal water-cooling coil, adding 0.05wt% phosphazene catalyst, and sealing the reaction kettle. Nitrogen was replaced three times, stirring was started, the temperature was raised to 90 ℃ and dehydration was performed at-0.1 MPa, then the temperature was raised to 130 ℃. Then slowly introducing ethylene oxide, keeping the reaction pressure less than 0.3MPa by controlling the feeding speed, stopping feeding after 20g of ethylene oxide is introduced, carrying out aging reaction for 3 hours at 130 ℃, and carrying out de-singulation at-0.1 MPa; cooling to room temperature to obtain polyether. GPC test: mw 5000g/mol, PDI 1.32.
Example 2
1.2,2', synthesis of 6,6' -tetrabromo-4-amino-4 ' -hydroxyazobenzene (AZO-2) 10mol of 3, 5-dibromo-4-aminophenol (2670 g) was weighed and dissolved in 30mol of HCl solution (38% strength) and designated A2. Weighing 11mol NaNO 2 (759g) Dissolving in deionized water, stirring with ice bath to obtain NaNO 2 Slowly drop-wise into A2. Keeping the temperature at 0-5 ℃, and stirring and reacting for 45min to obtain diazonium salt solution B2. 10mol of 3, 5-dibromoaniline (2510 g) was weighed and dissolved in a 5:1 volume ratio water/acetone mixed solution at 0-5 ℃, solution B2 was slowly added dropwise to the solution, saturated NaHCO was used 3 The aqueous solution was adjusted to a pH of about 6.5 and the reaction time was 7 hours. And (3) recrystallizing by using ethanol/water (volume ratio is 1:1) after the reaction to obtain the AZO-2 product. HRMS-ESI: M/z 528.7279 (calcd.for [ M+H)] + ,528.7282)。
2. Multifunctional composite material: weighing 1mol of AZO-2 and 1.1mol of NaNO 2 Into a flask containing 500mL of deionized water, 3.5mol of hydrochloric acid (38% strength) was then added, and the mixture was allowed to react in an ice bath for 1 hour to obtain diazonium salt solution C2. Then C2 is slowly dropped into 500mL of aqueous solution of graphite lamellar material (5 mg/m L) to react for 4 hours at 0-5 ℃ and 16 at room temperatureh. The product is repeatedly washed by deionized water, acetone and DMF, filtered (PTFE film) to remove unreacted AZO-2 and diazonium salt, and then the product is repeatedly reacted with diazonium salt solution twice by the functionalization method to improve grafting density. And vacuum drying to obtain the final product. (UV-Vis: 440nm tan-to-cis; 290nm pi-pi conjugation).
3. Synthesis of polyether: firstly, using 150mL of DMF to carry out ultrasonic dispersion on 2g of the multifunctional composite material, adding the dispersion liquid into a 0.5L reaction kettle with stirring, a heating sleeve and an internal water-cooling coil, adding 0.1% sodium methoxide catalyst, and sealing the reaction kettle. Nitrogen was replaced three times, stirring was started, dehydration was performed at-0.1 MPa after heating to 90 ℃, and then heating to 120 ℃. Slowly introducing propylene oxide, keeping the reaction pressure less than 0.3MPa by controlling the feeding speed, stopping feeding after 40g of propylene oxide is introduced, carrying out aging reaction for 3 hours at 120 ℃, and carrying out de-singulation at-0.1 MPa; cooling to room temperature to obtain polyether. GPC test: mw 14023g/mol, PDI 1.34.
Example 3
1.2,2', 6' -tetramethoxy-4-amino-4 ' -hydroxyazobenzene (AZO-3) Synthesis 10mol of 3, 5-dimethoxy-4-aminophenol (1690 g) were weighed out and dissolved in 40mol of HCl (38% strength) solution, designated A3. 21mol NaNO was weighed 2 (1449g) Dissolving in deionized water, stirring with ice bath to obtain NaNO 2 Slowly drop-wise into A3. Keeping the temperature at 0-5 ℃, and stirring and reacting for 60min to obtain diazonium salt solution B3. 18mol of 3, 5-dimethoxyaniline (2754 g) was weighed and dissolved in a 5:1 volume ratio water/acetone mixed solution at 0-5℃to slowly drop solution B3 into the solution, using saturated NaHCO 3 The pH of the aqueous solution is regulated to 5-7, and the reaction time is 8h. And (3) recrystallizing by using ethanol/water (volume ratio is 1:1) after the reaction to obtain the AZO-3 product. HRMS-ESI: M/z 333.1324 (calcd.for [ M+H)]+,333.1325)。
2. Multifunctional composite material: weighing 1mol of AZO-3 and 1.18mol of NaNO 2 Into a flask containing 500mL of deionized water, 4mol of hydrochloric acid was then added, and the mixture was placed in an ice bath to react for 1 hour to obtain diazonium salt solution C3. C3 was then slowly added dropwise to 500mL of an aqueous solution of graphite platelet material (2 mg/m L),reacting for 4h at 0-5 ℃ and reacting for 20h at room temperature. The product is repeatedly washed by deionized water, acetone and DMF, filtered (PTFE film) to remove unreacted AZO-3 and diazonium salt, and the product is repeatedly reacted twice by the functionalization method to improve the grafting density. And vacuum drying to obtain the final product. (UV-Vis: 430nm tan-to-cis; 285nm pi-pi conjugation.)
3. Synthesis of polyether: firstly, using 150mL of DMF to carry out ultrasonic dispersion on 2g of the multifunctional composite material, adding the dispersion liquid into a 0.5L reaction kettle with stirring, a heating sleeve and an internal water-cooling coil, adding 0.1% of potassium hydroxide catalyst, and sealing the reaction kettle. Nitrogen was replaced three times, stirring was started, dehydration was performed at-0.1 MPa by heating to 90 ℃, 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 after 50g of the epoxidized alkane is introduced, carrying out aging reaction for 3 hours at 125 ℃, and carrying out dealkylation under-0.1 MPa; cooling to room temperature to obtain polyether. GPC test: mw13654g/mol, PDI 1.36.
Application example 1
Polymer modification applications: a multifunctional composite was prepared as in example 1. According to the addition amount of 0.5 percent, the multifunctional material is added into DMF solution of the polyurethane elastomer, and the solution is placed in a vacuum oven for vacuum drying at 140 ℃ for 48 hours, so as to obtain the multifunctional material modified polyurethane elastomer. The modified polymer was irradiated with near infrared light, and the polymer was subjected to a temperature increase of 10 ℃. The comparative test is a polymer without added multifunctional material, with a temperature rise of only 1 ℃. Thus, the modified polymer can be used as a thermal insulation coating.
Application example 2
Polyether application: polyether was prepared as in example 1. The polyether was added to a commercial laundry detergent at an addition level of 0.3% to prepare a novel detergent. 5g of the compounded detergent is taken and dissolved in a closed glass container filled with 500ml of water, and the mixture is shaken vigorously for 3min, so that a large amount of foam is generated. Commercial laundry detergent without the polyether was used as a comparative experiment under the same conditions. The comparison shows that after 0.3% polyether is added, the foam height is 5-6cm lower than that of the non-added polyether, and meanwhile, after the visible light irradiation is used, the foam height of the liquid laundry detergent added with polyether is further reduced by 3-5cm. It can be seen that the novel washing liquid after polyether addition has the advantages of low foam and light response defoaming.
Claims (19)
1. A polyether having the structural formula:
wherein ,
m is an integer of 0 to 200, n is an integer of 0 to 100, and m and n are not simultaneously 0;
all R 2 Selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 One of the following;
R 3 each independently selected from the group consisting of single bond (-), -CH 2 -、-CH 2 CH 2 -。
2. The polyether of claim 1, wherein m is an integer from 0 to 150 and n is an integer from 20 to 80.
3. The polyether of claim 1, wherein m is an integer from 20 to 150 and n is an integer from 0 to 80.
4. The polyether of claim 1, wherein m is an integer from 20 to 150 and n is an integer from 20 to 80.
5. The polyether of any one of claims 1-4 wherein R 3 Is a single bond (-), all R 2 F, cl, br, CH of a shape of F, cl, br, CH 3 、OCH 3 、CF 3 and OCF3 One of them.
6. The method for preparing polyether as claimed in claim 1, comprising the steps of:
(A) Make the following steps3, 5-disubstituted-4-amino phenylalkyl alcohols of the formula (I) in HCl solution with NaNO 2 Reacting to generate diazonium salt solution, and then reacting with 3, 5-disubstituted aniline shown in a formula (II) to obtain a product AZO-1 shown in a formula (III);
(B) Preparing a product AZO-1 of the formula (III) into diazonium salt solution, and then reacting with a graphite sheet material of the formula (IV) to obtain a multifunctional composite material of the formula (V);
(C) Introducing ethylene oxide and/or propylene oxide in the presence of a multifunctional composite of formula (V) to react to obtain a polyether of formula (VI):
in the above-mentioned formulae, the first and second light-emitting elements,
m is an integer of 0 to 200, n is an integer of 0 to 100, and m and n are not simultaneously 0;
all R 2 Selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 One of the following;
R 3 each independently selected from the group consisting of single bond (-), -CH 2 -、-CH 2 CH 2 -。
7. The process according to claim 6, wherein in the step (A), the 3, 5-disubstituted-4 aminophenylalkyl alcohol is selected from the group consisting of 3, 5-disubstituted-4 aminophenol, 3, 5-disubstituted-4 aminophenol methanol, 3, 5-disubstituted-4 aminophenol alcohol; and/or the number of the groups of groups,
the HCl solution is 10-38% HCl solution.
8. The process according to claim 6 or 7, wherein in step (A), 3, 5-disubstituted-4-aminophenylalkyl alcohol, HCl solution, naNO 2 The molar ratio of the catalyst to the 3, 5-disubstituted aniline is 1:2.0-8:1-2.5:1-2.0; and/or
The two substituents at the 3,5 position in the 3, 5-disubstituted-4 amino phenylalkyl alcohol are selected from F, cl, br, CH 3 、OCH 3 、CF 3 、OCF 3 One of them.
9. The preparation method of claim 8, wherein 3, 5-disubstituted-4-amino phenylalkyl alcohol, HCl solution, naNO 2 The molar ratio of the catalyst to the 3, 5-disubstituted aniline is 1:2.5-4:1.05-1.15:1-1.1.
10. The process according to claim 6 or 7, wherein in step (A), 3, 5-disubstituted-4-amino phenylalkyl alcohols of the formula (I) are reacted with NaNO in HCl solution 2 Stirring and reacting for 30-60min at 0-5 ℃; the diazonium salt solution reacts with 3, 5-disubstituted aniline of formula (II) at 0-5 ℃ and pH 5-7 for 6-8h.
11. The preparation method according to claim 10, wherein the preparation is performed in a water/acetone mixed solution having a solvent volume ratio of 5:1.
12. The production process according to claim 6 or 7, wherein, in the production diazonium salt solution of step (B), AZO-1 and NaNO 2 Reacting AZO-1 and NaNO in HCl solution 2 The molar ratio of the diazonium salt solution to the hydrochloric acid is 1:1.05-2:2-6, and the prepared diazonium salt solution and graphite sheet material are 2-24h at 0-50 ℃; and/or the number of the groups of groups,
the mass ratio of the diazonium salt to the graphite flake material is 20-1000:1; and/or
The graphite sheet material is one or more selected from crystalline flake graphite, expanded graphite, graphene oxide and reduced graphene oxide.
13. The preparation method according to claim 12, wherein the HCl solution is a HCl solution having a concentration of 10-38%; and/or the number of the groups of groups,
the mass ratio of the diazonium salt to the graphite flake material is 100-400:1; and/or
The graphite sheet material is selected from reduced graphene oxide.
14. The production method according to claim 6, wherein m is an integer of 0 to 150, and n is an integer of 20 to 80.
15. The production method according to claim 6, wherein m is an integer of 20 to 150, and n is an integer of 0 to 80.
16. The production method according to claim 6, wherein m is an integer of 20 to 150, and n is an integer of 20 to 80.
17. The process of claim 6, wherein the reaction of step (C) is carried out in the presence of a catalyst comprising one or more of NaOH, KOH, na, naH, sodium methoxide, bimetallic catalyst, alkaline earth metal catalyst, phosphazene catalyst, lewis acid catalyst; and/or
The mass ratio of the multifunctional composite material to the ethylene oxide and/or the propylene oxide is 1:10-100.
18. The production method according to claim 17, wherein the catalyst is selected from the group consisting of an alkali metal catalyst and a phosphazene catalyst; and/or
The mass ratio of the multifunctional composite material to the ethylene oxide and/or the propylene oxide is 1:20-40.
19. Use of the polyether of claim 1 in the washing, pharmaceutical, or textile fields.
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| CN104844781A (en) * | 2015-05-29 | 2015-08-19 | 杨秀莲 | Graphene chemically-modified hard polyurethane foam |
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