CN117186377A - Polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets and preparation method thereof - Google Patents
Polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets and preparation method thereof Download PDFInfo
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- CN117186377A CN117186377A CN202210607984.4A CN202210607984A CN117186377A CN 117186377 A CN117186377 A CN 117186377A CN 202210607984 A CN202210607984 A CN 202210607984A CN 117186377 A CN117186377 A CN 117186377A
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- Prior art keywords
- polyoxymethylene
- nanoplatelets
- copolymer
- surfactant
- nano
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 182
- -1 Polyoxymethylene Polymers 0.000 title claims abstract description 158
- 229930040373 Paraformaldehyde Natural products 0.000 title claims abstract description 156
- 239000002135 nanosheet Substances 0.000 title claims abstract description 133
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 87
- 239000000178 monomer Substances 0.000 claims abstract description 57
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000004888 barrier function Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002064 nanoplatelet Substances 0.000 claims description 101
- 229920001223 polyethylene glycol Polymers 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 60
- 239000000463 material Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000013078 crystal Substances 0.000 claims description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 23
- 239000002356 single layer Substances 0.000 claims description 21
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 229920001400 block copolymer Polymers 0.000 claims description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 125000001165 hydrophobic group Chemical group 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 150000001720 carbohydrates Chemical class 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011232 storage material Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920000881 Modified starch Polymers 0.000 claims description 3
- 239000004368 Modified starch Substances 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 239000011951 cationic catalyst Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 150000004676 glycans Chemical class 0.000 claims description 3
- 229920000591 gum Polymers 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 235000019426 modified starch Nutrition 0.000 claims description 3
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 229950008882 polysorbate Drugs 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 230000035939 shock Effects 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 29
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 239000012071 phase Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 19
- 238000010538 cationic polymerization reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000005191 phase separation Methods 0.000 description 13
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 241001506047 Tremella Species 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000003384 imaging method Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 1
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011359 shock absorbing material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/50—Surfactants; Emulsifiers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
-
- 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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/08—Polymerisation of formaldehyde
-
- 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
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
-
- 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
- C08G65/04—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 only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals
- C09J159/04—Copolyoxymethylenes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
Abstract
The invention discloses a polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet and a preparation method thereof, wherein the preparation method comprises the following steps: (1) mixing a surfactant with a monomer to obtain a mixed solution; wherein the monomer is trioxymethylene or comprises trioxymethylene and comonomer; (2) And (3) adding a catalyst into the mixed solution obtained in the step (1) to react to form a system containing the polyoxymethylene nano-sheets or the polyoxymethylene copolymer nano-sheets. The polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets of the invention can be applied to various fields of catalysis, hydrogen storage, barrier, composite material reinforced wear resistance and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a polyoxymethylene nano-sheet or a polyoxymethylene copolymer nano-sheet and a preparation method thereof.
Background
Since 2004 single-layer graphene was successfully isolated (Novoselov K S, et al electric Field Effect in Atomically Thin Carbon Films [ J ]. Science, 306), two-dimensional materials have been under vigorous development (Chowalla M, et al the Chemistry of two-dimensional layered transition metal dichalcogenide nanosheets [ J ]. Nature Chemistry,2013,5 (4): 263-275;Tan C,et al.Recent Advances in Ultrathin Two-Dimensional Nanomaterials [ J ]. Chemical Reviews,2017:6225;Bhimanapati G R,et al.Recent Advances in Two-Dimensional Materials Beyond Graphene [ J ]. ACS Nano,2015,9 (12): 11509-11539). In addition to graphene, graphene-like inorganic materials such as boron nitride, graphitized carbon nitride, layered metal oxides, and the like have also been widely studied (Weng Q, et al functionalized Hexagonal Boron Nitride Nanomaterials: emerging Properties and Applications [ J ] Chemical Society Reviews,2016,45 (14); ma R, sasaki T.two-dimensional oxide and hydroxide nanosheets: controllable high-quality exfoliation, molecular assembly, and exploration of functionality [ J ] Accounts of Chemical Research,2015,48 (1): 136-43), but research into organic two-dimensional materials has been in the initiation stage (Boott C E, et al synthetic equivalent and Non-equivalent 2D materials [ J ] Angewandte Chemie International Edition,2015,54 (47)).
The preparation method of the two-dimensional material can be divided into two major categories (Sun Sai and the like) of top-down and bottom-up, the design and preparation of novel two-dimensional functional materials and derivatives [ J ]. Functional polymer journal, 2018, v.31 (04): 89-89). The synthesis method from top to bottom is to strip the material with the layered structure by using mechanical stripping, intercalation and other methods to obtain the corresponding two-dimensional material, and usually some inorganic materials with the layered structure can be stripped by using the method, such as graphite, molybdenum disulfide, hexagonal boron nitride and the like (Y Hernandez, et al high yield production of graphene by liquid phase exfoliation of graphite [ J ]. 2008). The method has the advantages that the required conditions are severe, the sources of raw materials are wide, the method is a main stream means for preparing the two-dimensional material at present, and the high polymer generally has no regular lamellar structure, so that the organic two-dimensional material cannot be prepared by the method. In contrast, the "bottom-up" method mainly uses molecules (atoms) or nanostructures as precursors, and the two-dimensional materials are prepared through a series of synthesis steps, and the method has the advantages of mild conditions, controllable structure and the like, and the reported organic two-dimensional materials are also prepared by adopting the method (Boott C E, et al, synthetic content and Non-content 2D materials [ J ]. Angewandte Chemie International Edition,2015,54 (47); Y Zhong, et al, wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices [ J ]. Science,2019,366 (6471):1379-1384). However, such methods also present challenges such as: how to control the structure to be a two-dimensional structure, how to reduce defects, and the molecular design for the organic material itself is complex.
Few reports on organic two-dimensional materials are currently available, and are prepared by a bottom-up method. For example, a polymer film with a given structural design can be deposited on the surface of a metal single crystal by a vacuum evaporation method, such as a tribromo-dimethyl methylene bridged-triphenylamine (DPTA) film (Bieri M, et al surface-supported 2Dheterotriangulene polymers[J ]. Chemical Communications,2011,4) deposited on the surface of Ag (111), a polyimide network (Treier M, et al surface-supported low-dimensional polyimide networks. [ J ]. Journal of the American Chemical Society,2008,130 (43): 14054), polyphenylene (Lipton-Duffin J A, et al Synthesis of polyphenylene molecular wires by surface-confined polymerization [ J ]. Small,2010,5 (5): 592-597) and polythiophene (Lipton-Duffin J A, et al step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction) [ J ]. Proceedings of the National Academy of Sciences of the United States of America,2010,107 (25): 11200-11204) molecular wires, and fullerene self-assembly on Pt (111) (Konstlatin, et al Towards the Isomer-Specific Synthesis of Higher Fullerenes and Buckybowls by the Surface-3996 [ J ]. Angewandte Chemie International Edition,2010,49 (49): 9392-9396), iron-Phthalocyanine flakes generated on NaCl crystals (Abel M, et al Single Layer of Polymeric Fe-phtalocyanine: an Organometallic Sheet on Metal and Thin Insulating Film [ J ]. Journal of the American Chemical Society,2011,133 (5):1203-1205). Recently, two-dimensional porphyrin polymers have been reported to be prepared by the method of oil-water interface synthesis and to be self-assembled layer by layer with metal compounds (Y Zhong, et al wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices [ J ]. Science,2019,366 (6471):1379-1384). The two methods for preparing the two-dimensional organic materials have the advantages that the precise regulation and control of the nano structure can be realized, and the method has great significance for theoretical research, but has the greatest defects that reaction places are positioned on narrow crystal surfaces or phase interfaces, and the large-scale preparation of the two-dimensional organic materials by adopting the method is almost impossible, so that the two-dimensional organic materials can only stay in the theoretical research stage and cannot realize industrial production. In addition, the current organic two-dimensional materials are limited to polymerization with monomer molecules having planar structures (e.g., aniline, thiophene, porphyrin, etc.), and some conventional polymers not having planar molecular structures have not been prepared into two-dimensional materials.
Polyoxymethylene (POM) is an engineering plastic with excellent comprehensive properties, and has high mechanical properties such as strength, modulus, wear resistance, toughness, fatigue resistance and creep resistance, and also has excellent electrical insulation and solvent resistance. The two-dimensional polyoxymethylene nanosheets are expected to be applied to the fields of composite materials, supported catalysis, gas adsorption and the like due to the characteristics of the nanostructural structures of the two-dimensional polyoxymethylene nanosheets, but no method for preparing the polyoxymethylene nanosheets exists at present.
Disclosure of Invention
The invention aims to provide a polyoxymethylene nano-sheet or a polyoxymethylene copolymer nano-sheet and a preparation method thereof. The preparation method of the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet provided by the invention has the advantages of extremely high yield, simple preparation process, environment friendliness, regular structure of the prepared polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet, and can be applied to various fields of catalysis, hydrogen storage, barrier, composite material reinforced wear resistance and the like.
In particular, one aspect of the present invention provides a method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets, the method comprising the steps of:
(1) Mixing a surfactant and a monomer to obtain a mixed solution; wherein the monomer is trioxymethylene, or comprises trioxymethylene and comonomer;
(2) And (3) adding a catalyst into the mixed solution obtained in the step (1) to react to form a system containing the polyoxymethylene nano-sheets or the polyoxymethylene copolymer nano-sheets.
In one or more embodiments, the surfactant is a surfactant that is miscible with the monomer at a temperature not greater than the crystallization temperature of the polyoxymethylene or polyoxymethylene copolymer.
In one or more embodiments, the surfactant contains hydrophobic groups and/or hydrophobic segments, and hydrophilic groups and/or hydrophilic segments.
In one or more embodiments, the surfactant is selected from one or more of polyether polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone, polyester-based polymers, and saccharide surfactants.
In one or more embodiments, the polyether polymer is selected from one or more of polyethylene glycol, polyethylene glycol-polypropylene glycol copolymer, and polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer.
In one or more embodiments, the polyvinyl alcohol-based polymer is polyvinyl alcohol.
In one or more embodiments, the polyester-based polymer is selected from one or both of a di-polyethylene glycol maleate and a polysorbate.
In one or more embodiments, the saccharide surfactant is selected from one or more of starch, gum, polysaccharide, modified starch, cellulose, protein, and chitosan.
In one or more embodiments, the surfactant is a water-soluble surfactant, such as one or more selected from the group consisting of polyether polymers, polyvinyl alcohol polymers, and polyvinylpyrrolidone.
In one or more embodiments, the surfactant has a number average molecular weight of 400 to 50000g/mol, preferably 2000 to 50000g/mol, for example 10000 to 20000g/mol.
In one or more embodiments, the comonomer is selected from one or more of dioxolanes and alkylene oxide-based comonomers, for example selected from one or more of ethylene oxide, 1, 2-propylene oxide, and 1, 3-propylene oxide.
In one or more embodiments, the mass ratio of the surfactant to the monomer is ≡1:10, for example 1:9 to 5:1, preferably 1:5 to 2:1, for example 3:7 to 1:1.
In one or more embodiments, when the monomer includes a comonomer, the comonomer comprises no more than 30%, such as no more than 20%, no more than 15% of the mass fraction of the monomer.
In one or more embodiments, when the monomer includes a comonomer, the comonomer comprises not less than 1%, such as not less than 2%, not less than 5% of the mass fraction of the monomer.
In one or more embodiments, the catalyst is a cationic catalyst, such as a lewis acid, for example, selected from one or more of aluminum trichloride, aluminum tribromide, aluminum alkyls, titanium tetrachloride, tin tetrachloride, zinc dichloride, lead chloride, and boron fluoride.
In one or more embodiments, the molar ratio of the catalyst to the monomer is from 1:10000 to 1:100, for example from 1:1000 to 1:100.
In one or more embodiments, in step (1), the surfactant and the monomer are mixed at a temperature not lower than the melting point of the monomer and the melting point of the surfactant.
In one or more embodiments, in step (2), the reaction temperature is not lower than the melting point of the monomer and the melting point of the surfactant, and not higher than the crystallization temperature of the polyoxymethylene or polyoxymethylene copolymer, preferably not higher than 120 ℃.
In one or more embodiments, the method further comprises extracting polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets from the system comprising polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets, and optionally crushing, washing and/or drying the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets.
Another aspect of the present invention provides polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets prepared by the method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets described in any of the embodiments herein.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets have a regular folded chain platelet structure, preferably in the form of hexagonal crystals, preferably in the form of 30% to 80%, more preferably 40% to 70%.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets have a single-layer structure or have a multi-layer structure of two or more layers, and the single-layer thickness of the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets is preferably 5nm to 50nm, more preferably 10nm to 30nm, for example 20±5nm.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets have oxygen atoms uniformly distributed on the surface.
Another aspect of the present invention provides a polyoxymethylene nano-sheet or a polyoxymethylene copolymer nano-sheet having a single-layer structure or a multi-layer structure having two or more layers.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets have a monolayer thickness of 5nm to 50nm, preferably 10nm to 30nm, for example 20±5nm.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets have a regular folded chain platelet structure, preferably in the form of hexagonal crystals, preferably having a platelet crystallinity of 30% to 80%, for example 40% to 70%.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets have oxygen atoms uniformly distributed on the surface.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets are formed from monomers comprising polyoxymethylene and optionally comonomers in the presence of a surfactant, preferably as described in any of the embodiments herein.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets are prepared using the method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets described in any of the embodiments herein.
The present invention also provides a composite, gas adsorbing material or supported catalytic material comprising polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets as described in any of the embodiments herein.
The invention also provides the use of polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets as described in any of the embodiments herein in the preparation of a composite, a gas adsorbing material or a supported catalytic material.
In one or more embodiments, the composite is a reinforced composite, a wear resistant composite, a gas barrier composite, an oil resistant composite, or a shock absorbing composite.
In one or more embodiments, the gas adsorbing material is a hydrogen storage material.
The present invention also provides the use of a surfactant, preferably as described in any of the embodiments herein, in the preparation of polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets.
In one or more embodiments, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets are as described in any of the embodiments herein.
In one or more embodiments, the use comprises preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets using the method described in any of the embodiments herein.
The present invention also provides a method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets having one or more or all of the following properties:
The thickness of the single-layer structure is 5nm-50nm;
the appearance is tremella, bud, single piece or a few pieces (such as 2 pieces, 3 pieces, 4 pieces, 5 pieces, 6 pieces, 7 pieces, 8 pieces, 9 pieces and 10 pieces) of single piece adhesion, especially single piece or a few pieces of single piece adhesion;
the thickness of the single sheet is 5nm-500nm;
with a regular folded chain platelet structure, the platelet form is preferably hexagonal, the platelet crystallinity is preferably 30% -80%, such as 40%, 50%, 60%, 70%;
oxygen atoms are uniformly distributed on the surface; and
has an increased specific surface area;
wherein the method comprises using the surfactant of any of the embodiments herein as a solvent or continuous phase of a reaction system for synthesizing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets.
Drawings
FIG. 1 is a scanning electron micrograph of a polyoxymethylene aggregate prepared in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a polyoxymethylene aggregate prepared in example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 3 of the present invention.
FIG. 4 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 4 of the present invention.
FIG. 5 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 5 of the present invention.
FIG. 6 is a scanning electron micrograph of formaldehyde-dioxolane copolymer nanoplatelets prepared according to example 6 of the present invention.
FIG. 7 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared according to example 7 of the present invention.
FIG. 8 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 8 of the present invention.
FIG. 9 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 9 of the present invention.
FIG. 10 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 10 of the present invention.
FIG. 11 is a scanning electron micrograph of a polyoxymethylene nanoplatelet prepared in example 11 of the present invention.
Fig. 12 is a scanning electron microscope picture (a, b) and an atomic force microscope scanning picture (c) of the platelet structure of polyoxymethylene nanoplatelets prepared in example 4 of the present invention.
FIG. 13 is a transmission electron micrograph and an XRD diffraction pattern of polyoxymethylene nanoplatelets prepared in example 3 of the present invention.
Fig. 14 is a transmission electron micrograph (a), a carbon element imaging picture (b) and an oxygen element imaging picture (c) of a polyoxymethylene nano-sheet prepared in example 3 of the present invention.
FIG. 15 is a DSC thermogram of polyoxymethylene nanoplates prepared in example 3 of the present invention and polyoxymethylene copolymer nanoplates prepared in example 6 (a is example 3 and b is example 6).
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
Herein, "comprising," "including," "containing," and similar terms are intended to cover the meaning of "consisting essentially of … …" and "consisting of … …," e.g., "a consisting essentially of B and C" and "a consisting of B and C" should be considered to have been disclosed herein when "a comprises B and C" is disclosed herein.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise specified, percentages refer to mass percentages, and proportions refer to mass ratios.
Herein, when embodiments or examples are described, it should be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention provides a method for preparing a polyoxymethylene nano-sheet or a polyoxymethylene copolymer nano-sheet. Different from the 'bottom-up' method, the preparation method does not need a precursor structure to guide and generate a two-dimensional structure, and does not need special structural design on a material monomer. The invention adopts the surfactant as the solvent/surfactant of the polymerization reaction, and carries out the cationic polymerization of the polyformaldehyde or the polyformaldehyde copolymer in the solvent/surfactant, the polyformaldehyde or the polyformaldehyde copolymer molecule can grow in a system in the form of a platelet, when the reaction is carried out to a certain extent, the system is solidified due to the rapid increase of the viscosity of the system, thereby freezing the microstructure of the polyformaldehyde or the polyformaldehyde copolymer platelet, realizing the precise control of the two-dimensional structure and interrupting the curing process of the polyformaldehyde or the polyformaldehyde copolymer platelet to the three-dimensional structure. The solid content of the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet prepared by the method can reach more than 80wt% in a system, and if a water-soluble surfactant is adopted, the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet can be obtained by direct water washing. The preparation method disclosed by the invention is simple and convenient in process, can be used for large-scale industrial production, is environment-friendly in process, and is a green and efficient method for preparing the polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets. The polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets prepared by the method have regular folded chain sheet crystal structures, and the crystallinity can be 30% -80%, such as 40% -70%, according to different copolymer contents. The polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets prepared by the method have regular structures, the single-layer thickness can be about 5-50nm, for example about 20nm, and the polyoxymethylene nanosheets have higher specific surface area and are expected to be widely applied to the field of composite materials, such as reinforced, wear-resistant, gas-barrier, oil-resistant and shock-absorbing composite materials; in addition, the surface of the catalyst has a regular folded chain plate crystal structure, an extremely high specific surface area and rich oxygen atom distribution, so that the catalyst has potential application in the fields of supported catalysis and hydrogen storage.
Herein, two-dimensional materials have the meaning conventional in the art, meaning materials with dimensions in one dimension up to nano-scale (e.g., 1-500nm, 1-200 nm). The sheet diameter of the two-dimensional material is not particularly limited, and may be several micrometers to several hundreds of micrometers, for example. The organic two-dimensional material refers to a two-dimensional material formed by reacting, depositing or self-assembling organic matters. The polyoxymethylene nanosheets refer to two-dimensional materials with components of polyoxymethylene. The polyoxymethylene copolymer nanosheets refer to two-dimensional materials with components of polyoxymethylene copolymer. Polyoxymethylene copolymer refers to a polymer formed by copolymerizing trioxymethylene and a comonomer.
In the present invention, the polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets include nanosheets in the form of a single sheet, and also include nanosheet aggregates and clusters adhered together, and the shape of the aggregates and clusters is not particularly limited, and may be, for example, tremella, bud, etc. In a preferred embodiment, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets exist in the form of free monoliths or in the form of a minority of monoliths (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10) that are monolithically adhered together.
In the present invention, the polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets may have a single layer structure alone or a multilayer structure formed by stacking two or more layers (for example, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers, 10 layers) of single layer structures. The layered structure of the polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets can be observed by means of scanning electron microscopy, transmission electron microscopy, atomic force microscopy, and the like. The thickness of the monolayer structure may be 5nm to 50nm, preferably 10nm to 30nm. In some embodiments, the monolayer thickness is 20±5nm. Thus, the monolithic thickness of the polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets of the present invention may be 5nm to 500nm, for example, 10nm to 300nm, 15nm to 250nm, 20nm, 50nm, 100nm, 200nm, depending on the number of layers and the thickness of the monolayer contained in the monolithic.
The polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets of the present invention have a regular folded chain platelet structure, the platelet crystal form is preferably hexagonal, and the platelet crystallinity may be 30% -80%, for example 40%, 50%, 60%, 70%. The platelet crystallinity can be adjusted by adjusting the amount of comonomer added, the crystallinity decreasing with increasing comonomer addition.
The surface of the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet is uniformly distributed with oxygen atoms. The oxygen atom distribution condition of the surface of the nano-sheet can be confirmed by a scanning electron microscope or a transmission electron microscope oxygen element imaging mode.
The preparation method of the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet comprises the following steps:
(1) Mixing a surfactant and a monomer to obtain a mixed solution; wherein the monomers comprise trioxymethylene and optionally a comonomer;
(2) And (3) adding a catalyst into the solution obtained in the step (1) to react to form a system containing the polyoxymethylene nano-sheets or the polyoxymethylene copolymer nano-sheets.
Surfactants suitable for use in the present invention are miscible with polyoxymethylene and optionally comonomers at temperatures no greater than the crystallization temperature of polyoxymethylene or polyoxymethylene copolymers. The crystallization temperature of polyoxymethylene or the crystallization temperature of polyoxymethylene copolymer can be measured by a differential scanning calorimeter or the like. The crystallization temperature of polyoxymethylene or polyoxymethylene copolymers is generally between 130℃and 150℃e.g.around 140 ℃. In some embodiments, the present invention uses surfactants that are miscible with polyoxymethylene and optionally comonomers at temperatures no greater than 140 ℃, e.g., no greater than 120 ℃, no greater than 100 ℃, no greater than 80 ℃.
The surfactant suitable for the present invention may be one or more selected from polyether polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone, polyester-based polymers and saccharide surfactants. In some embodiments, the present invention uses nonionic surfactants. Examples of polyester-based polymers include di-polyethylene glycol maleate, polysorbate, and the like. Examples of the saccharide surfactant include starch, gum, polysaccharide, modified starch, cellulose, protein, chitosan, and the like. Examples of polyether polymers include polyethylene glycol, polyethylene glycol-polypropylene glycol copolymers, polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymers, and the like. Examples of polyvinyl alcohol polymers include polyvinyl alcohol. In embodiments where the surfactant is a polyethylene glycol-polypropylene glycol copolymer or a polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, the mass ratio of polyethylene glycol blocks to polypropylene glycol blocks may be from 10:1 to 1:1, such as 8:1, 6:1, 5:1, 4:1, 3:1, 2:1. In some embodiments, the surfactant is selected from the group consisting of polyethylene glycol, polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymers, polyvinyl alcohol, and polyvinylpyrrolidone.
The surfactants suitable for the invention, such as polyether polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone, polyester polymers, saccharide surfactants and the like, have hydrophilic segments/hydrophilic groups and hydrophobic segments/hydrophobic groups, the hydrophilic segments/hydrophilic groups are self-assembled on the inner layer due to the formation of hydrogen bonds with polyoxymethylene or polyoxymethylene copolymers, the hydrophobic segments/hydrophobic groups are assembled on the outer layer, and the hydrophobic segments/hydrophilic groups and the hydrophobic groups form a protective layer, so that the polyoxymethylene or polyoxymethylene copolymer molecular chains can grow according to the platelet of a kinetic model of the polyoxymethylene or polyoxymethylene copolymer molecular chains, active centers are prevented from mutually colliding and combining to form larger particles, and curing of the particles is blocked, so that the polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets with two-dimensional structures can be finally synthesized. In the present invention, the hydrophilic group includes, but is not limited to, a hydroxyl group, an ester group, an ether bond, a carbonyl group, and the like, which are capable of forming hydrogen bonds with polyoxymethylene or polyoxymethylene copolymer. Hydrophilic segments refer to segments containing hydrophilic groups. Examples of hydrophobic groups include hydrocarbon groups. The hydrophobic segment refers to a segment that does not contain hydrophilic groups.
In a preferred embodiment, the present invention uses water-soluble surfactants such as polyether polymers, polyvinyl alcohol polymers, polyvinylpyrrolidone, and the like. The water-soluble surfactant is adopted, so that the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet can be obtained by direct water washing, and the process is environment-friendly.
In the present invention, the number average molecular weight of the surfactant may be 400 to 50000g/mol, for example 500g/mol, 1000g/mol, 2000g/mol, 5000g/mol, 8000g/mol, 10000g/mol, 12000g/mol, 13000g/mol, 14000g/mol, 15000g/mol, 16000g/mol, 17000g/mol, 18000g/mol, 20000g/mol. Preferably, the surfactant has a number average molecular weight of 2000-50000g/mol, e.g. 10000-20000g/mol, which is advantageous in providing a suitable viscosity to the reaction system, in facilitating control of the two-dimensional structure of the product, avoiding maturation growth of polyoxymethylene or polyoxymethylene copolymer, such that the microstructure of polyoxymethylene or polyoxymethylene copolymer platelets "freezes" in a two-dimensional state. If a small molecular compound is used as a solvent, polyoxymethylene or polyoxymethylene copolymer can be cured and grown into an amorphous structure in the solvent, and two-dimensional polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets cannot be obtained. In the present invention, it is preferable that the mixed solution in step (1) does not contain a small molecular compound solvent, for example, a solvent having a molecular weight of < 400 g/mol. Therefore, preferably, the mixed liquid in step (1) is composed of a surfactant and a monomer.
The invention comprises the application of the surfactant in preparing polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets and the application of the surfactant in preparing polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets with one or more or all of the following properties:
The thickness of the single-layer structure is 5nm-50nm;
the appearance is tremella, bud, single piece or a few pieces (such as 2 pieces, 3 pieces, 4 pieces, 5 pieces, 6 pieces, 7 pieces, 8 pieces, 9 pieces and 10 pieces) of single piece adhesion, especially single piece or a few pieces of single piece adhesion;
the thickness of the single sheet is 5nm-500nm;
with a regular folded chain platelet structure, the platelet form is preferably hexagonal, the platelet crystallinity is preferably 30% -80%, such as 40%, 50%, 60%, 70%;
oxygen atoms are uniformly distributed on the surface; and
has an increased specific surface area.
The aforementioned uses of the surfactant preferably include using the surfactant of the present invention as a solvent or continuous phase of a reaction system for preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets. Preferably, the use comprises preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets using the method described in any of the embodiments herein.
The melting point of the surfactant may be above room temperature, for example 40-120 ℃. Therefore, the surfactant and the monomer may be heated to be in a molten state when they are mixed, and for example, the surfactant may be heated to 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃. The melting point of the surfactant is not higher than the crystallization temperature of polyoxymethylene or the crystallization temperature of polyoxymethylene copolymer, so that the product polyoxymethylene or polyoxymethylene copolymer can be crystallized in the surfactant in a molten state.
In the present invention, a comonomer is optionally used. Comonomers suitable for use in the present invention include, but are not limited to, one or more selected from dioxolane and alkylene oxide-based comonomers. Alkylene oxide comonomers refer to alkanes having an epoxide substituent and may contain 2 to 5 carbon atoms. Examples of alkylene oxide comonomers include ethylene oxide, 1, 2-propylene oxide, 1, 3-propylene oxide, and the like. When the monomer includes a comonomer, the mass fraction of the comonomer is preferably not higher than 30%, for example not higher than 20%, not higher than 15% in order to maintain the platelet structure of the nanoplatelets. In some embodiments, the mass fraction of comonomer is not less than 1%, for example not less than 2%, not less than 5%. For example, the mass fraction of comonomer may be 15%, 12%, 10%, 8%, 5%, 2%, 1%.
In the invention, the feeding mass ratio of the surfactant to the monomer is more than or equal to 1:10, for example, 1:9 to 5:1, which is beneficial to avoiding the structure development of the polyoxymethylene or the polyoxymethylene copolymer from two dimensions to three dimensions. Preferably, the feeding mass ratio of the surfactant to the monomer is 1:5 to 2:1, for example, 1:4, 3:7, 2:3 and 1:1, and the control of the feeding mass ratio in the range is beneficial to the control of the two-dimensional structure of the product, so that tremella-shaped, bud-shaped, few adhered (for example, 1-10 sheets) or single-sheet nano sheets are obtained. In a preferred embodiment, the surfactant to monomer feed mass ratio is from 3:7 to 1:1, which is advantageous in obtaining nanoplatelets in monolithic form or nanoplatelets with only a few (10 sheets or less, preferably 5 sheets or less, for example 2, 3, 4, 5 sheets) of adhesion.
Preferably, anhydrous surfactants are used in combination with the monomers, which facilitates the polymerization reaction.
In step (1), the surfactant and the monomer are mixed at a temperature not lower than the melting point of the monomer and the melting point of the surfactant, so that the surfactant and the monomer can form a uniform mixed solution, typically a solution. The solution may be transparent. Mixing can be performed by stirring for 5min-1h, such as 10min, 20min, and 30min.
Catalysts suitable for use in the present invention may be cationic catalysts, such as lewis acids. Suitable lewis acids include, but are not limited to, one or more of aluminum trichloride, aluminum tribromide, aluminum alkyls, titanium tetrachloride, tin tetrachloride, zinc dichloride, lead chloride, and boron fluoride. The aluminum alkyls suitable for use in the present invention include trimethylaluminum, triethylaluminum, triisobutylaluminum, and the like. In some embodiments, a catalyst (e.g., boron fluoride) is dissolved in a suitable solvent (e.g., dichloroethane) to prepare a catalyst solution, which is then added to the reaction system to promote uniform dispersion of the catalyst. The concentration of the catalyst solution may be 0.1-10mmol/ml, for example 0.2mmol/ml, 0.5mmol/ml, 1mmol/ml, 2mmol/ml, 5mmol/ml, in the present invention the molar ratio of catalyst to monomer may be 1:10000 to 1:100, for example 1:5000, 1:2000, 1:1000, 1:500, 1:200. After adding the catalyst to the solution, the catalyst may be stirred to disperse the catalyst uniformly for a period of time ranging from 1 to 30 minutes, for example, 5 minutes, 10 minutes, 20 minutes.
In the step (2), a catalyst is added into the mixed solution obtained in the step (1), and the mixed solution can be uniformly mixed for reaction. The reaction may be carried out under heating. The reaction temperature is not lower than the melting point of the monomer and the melting point of the surfactant, and is not higher than the crystallization temperature of polyoxymethylene or the crystallization temperature of polyoxymethylene copolymer, for example not higher than 140 ℃, preferably not higher than 120 ℃, for example not higher than 100 ℃, not higher than 90 ℃, not higher than 80 ℃. The use of lower temperatures facilitates control of the rate of polymerization, depending on the cationic reaction mechanism.
In the invention, the monomer dissolved in the surfactant is subject to cationic polymerization under the action of the catalyst, and the product obtained by polymerization is insoluble in the surfactant so as to generate phase separation, and the system is changed into a heterogeneous system. The system may become milky white. Therefore, the mixed solution of the monomer and the surfactant before the reaction is a uniform phase system, and the generated polyoxymethylene or polyoxymethylene copolymer is insoluble in the surfactant after the reaction, so that phase separation is generated, and a multiphase alloy system is formed. When the reaction proceeds to some extent, the system is fully cured and the product structure "freezes". The reaction time is dependent on the type and proportion of surfactant, monomer, catalyst and reaction temperature, and may be 2min-2h, for example 5min, 10min, 15min, 20min, 25min, 30min, 40min, 50min, 60min. The reaction may be carried out in a sealed vessel. An oven may be used to control the reaction temperature.
In the present invention, it is preferred that the reaction system in step (2) is free or substantially free of small molecule compound solvents, such as solvents having a molecular weight of < 400 g/mol. It is understood that in the present invention, the reaction system in step (2) being substantially free of the small molecule compound solvent means that the small molecule solvent introduced for dissolving the monomer is not present in the reaction system, but it is not excluded that in the case where the catalyst is added to the reaction system in the form of a catalyst solution, a small amount of the solvent introduced with the catalyst solution is present in the reaction system. Thus, preferably, the reaction system in step (2) consists of surfactant, monomer, catalyst and optionally solvent from the catalyst solution.
After the reaction is completed, the product may be subjected to post-treatment. Post-treatment may include crushing, washing and/or drying. For example, the post-processing may be: taking out the product from the system, crushing the product, washing with water to remove the surfactant, filtering, repeatedly washing for a plurality of times, and drying to obtain the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet.
In some embodiments, the method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets of the present invention comprises:
(1) Mixing a surfactant and a monomer to obtain a mixed solution; wherein the monomers comprise trioxymethylene and optionally a comonomer; wherein the surfactant is selected from polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, polyethylene glycol, polyvinylpyrrolidone and polyvinyl alcohol, the molecular weight of the surfactant is 10000-20000g/mol, the monomer is trioxymethylene and optional comonomer (such as dioxolane), and the feeding mass ratio of the surfactant to the monomer is 1:5-2:1, such as 3:7-1:1;
(2) Adding a catalyst into the solution obtained in the step (1), and reacting to form a system containing polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets; among them, the catalyst is preferably a Lewis acid (e.g., BF 3 Aluminum alkyl), the molar ratio of catalyst to monomer is preferably 1:1000 to 1:100, the reaction temperature is preferably not higher than 90 ℃, for example not higher than 80 ℃, the reaction time can be 10-60min, for example 15-40min; the reaction gives polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets in the form of a single sheet or in the form of adhesion of only a few sheets (10 sheets or less, preferably 5 sheets or less, for example 2 sheets, 3 sheets, 4 sheets, 5 sheets).
The invention includes polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets prepared by the method described in any of the embodiments herein. The polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets of the invention have regular folded chain sheet crystal structures. The platelet crystal form is hexagonal crystal form. Depending on the copolymer content, the crystallinity may be up to 30% to 80%, for example 40% to 70%. The thickness of the single layer of the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet can reach 5-50nm, such as 10-30nm and 20+/-5 nm, and the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet has higher specific surface area. The surface of the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet is densely and uniformly distributed with oxygen atoms. Accordingly, the present invention includes a method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets having one or more or all of the following properties:
The thickness of the single-layer structure is 5nm-50nm;
the appearance is tremella, bud, single piece or a few pieces (such as 2 pieces, 3 pieces, 4 pieces, 5 pieces, 6 pieces, 7 pieces, 8 pieces, 9 pieces and 10 pieces) of single piece adhesion, especially single piece or a few pieces of single piece adhesion;
the thickness of the single sheet is 5nm-500nm;
with a regular folded chain platelet structure, the platelet form is preferably hexagonal, the platelet crystallinity is preferably 30% -80%, such as 40%, 50%, 60%, 70%;
oxygen atoms are uniformly distributed on the surface; and
has an increased specific surface area;
the method comprises preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets using the method described in any of the embodiments described herein above.
The polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets of the invention have high mechanical properties such as strength, modulus, wear resistance, toughness, fatigue resistance and creep resistance, and also have excellent electrical insulation, solvent resistance, extremely high specific surface area, and uniformly distributed oxygen atoms on the surface, and are particularly suitable for preparing composite materials, supported catalytic materials and gas adsorption materials. The composite material can be a reinforced composite material, a wear-resistant composite material, a gas barrier composite material, an oil-resistant composite material, a damping composite material and the like. The composite material can be prepared from the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet and the functional material through a composite process. The functional material can be a reinforcing material, a wear-resistant material, a gas barrier material, an oil-resistant material, a shock-absorbing material, and the like. The composite material may be prepared by a composite process such as blending, extrusion, lamination, molding, injection molding, and the like. The supported catalytic material refers to a material comprising a support and a catalytically active substance supported on the support. The polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets of the present invention can be used as a support or a portion of a support to support a catalytic material. The catalytically active material may be supported on the carrier by a wet or dry process. The catalytically active material may be various types of chemical and/or biological reaction catalysts. The gas adsorbing material refers to a material for adsorbing a gas, such as a hydrogen storage material. The gas adsorbing material may include a porous framework material and an adsorbent present with the surface of the porous framework material. The polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets of the present invention may be used as a porous scaffold material or a part of a porous scaffold material of a gas adsorbing material.
The invention has the following beneficial effects:
(1) The method for preparing the polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets, namely the macromolecular surfactant method, is different from the existing synthesis method from bottom to top, and is different from the traditional wet chemical synthesis because a small molecular organic solvent is not used as a carrier of a system. The reaction synthesis sites are not limited to narrow crystal surfaces or phase interfaces as in the prior reported two-dimensional material 'bottom-up' method, so the synthesis efficiency is high. The preparation method provided by the invention realizes the first successful preparation of the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet, and can truly realize industrialization and large-scale application of the polyoxymethylene nano-sheet or the polyoxymethylene copolymer nano-sheet, and the preparation method is not only remained in theoretical research.
(2) The key point of the invention is that a surfactant is used as a solvent for cationic polymerization of polyoxymethylene or polyoxymethylene copolymer, and the surfactant has the following two functions:
firstly, the solvent used as a reaction system can well disperse monomers and catalysts. The cationic polymerization is usually high in polymerization speed and more in side reaction, and is difficult to regulate and control, and the macromolecular solvent can slow down the reaction speed to a certain extent, so that the explosion polymerization is not caused under the condition of high monomer concentration, and the polyoxymethylene or polyoxymethylene copolymer can grow in the form of a single crystal wafer from an active center;
Secondly, as a surfactant, after cationic polymerization is initiated, a protective layer consisting of an inner layer and an outer layer can be formed by self-assembly around an active center, the hydrophilic segment/hydrophilic group is self-assembled on the inner layer due to the formation of hydrogen bonds with polyoxymethylene or polyoxymethylene copolymer, and the hydrophobic segment/hydrophobic group is assembled on the outer layer. The protective layer can ensure that polyformaldehyde or polyformaldehyde copolymer molecular chains can grow according to the platelet of the dynamic model, prevent active centers from mutually colliding and combining to form larger particles, and block the curing of the particles, so that the polyformaldehyde nano-sheet or polyformaldehyde copolymer nano-sheet with a two-dimensional structure can be finally synthesized.
(3) The mass fraction of the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet prepared by the method can reach more than 70% or even more than 80% of the system, and the yield is extremely high, so that the method is an extremely efficient preparation method.
(4) The particle size of the prepared polyoxymethylene nanosheets or polyoxymethylene copolymer nanosheets is controllable, and the particle size and morphology of the product can be controlled by adjusting the ratio of the monomer to the surfactant, the molecular structure of the surfactant, the ratio of the monomer to the comonomer, the dosage of the catalyst, the reaction temperature and the like.
(5) The preparation method adopted by the invention has the advantages of simple process, easy control of the process, no need of organic solvent in the preparation process, reduced cost, reduced pollution, environmental protection and large-scale industrial production.
(6) The polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets prepared by the invention are polyoxymethylene or polyoxymethylene copolymer platelet crystals, have regular folded chain platelet structures (figure 12), and the polyoxymethylene or polyoxymethylene copolymer crystals are hexagonal crystal forms (figure 13).
(7) The thickness of the single layer of the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet prepared by the invention can reach 5-50nm, for example, about 20nm, and oxygen atoms are densely and uniformly distributed on the surface (figure 14), so that the polyoxymethylene nano-sheet or polyoxymethylene copolymer nano-sheet has more advantages in the aspects of gas adsorption, load catalysis and the like compared with the common two-dimensional carbon material.
The invention will be illustrated by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the invention. The methods, reagents and materials used in the examples are those conventional in the art unless otherwise indicated. The starting compounds in the examples are all commercially available.
Example 1
Melting 10g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (number average molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) at 60deg.C, adding 90g of trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG-b-PPG-b-PEG, so that phase separation occurs, and the system becomes milky. When the reaction proceeded to a certain extent, after about 5min, the sample was completely cured, the PEG-b-PPG-b-PEG was removed, the product was washed with water, and an electron micrograph was shown in FIG. 1, and it was observed that the obtained polyoxymethylene had a sheet-like structure, but was adhered to each other, to form a continuous phase.
Example 2
Melting 20g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (data molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) at 60deg.C, adding 80g of trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG-b-PPG-b-PEG, so that phase separation occurs, and the system becomes milky. When the reaction is carried out to a certain extent, the mixture is completely solidified after about 10 minutes, the sample is taken out, the polyoxymethylene is a disperse phase in the polymerization process, PEG-b-PPG-b-PEG is a continuous phase, and the PEG-b-PPG-b-PEG is washed off by water to obtain the polyoxymethylene nano-sheets, the product electron microscope photograph is shown in figure 2, and a plurality of nano-sheets are bonded into a small aggregate to form a tremella shape.
Example 3
Melting 30g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (number average molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) at 60deg.C, adding 70g of trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG-b-PPG-b-PEG, so that phase separation occurs, and the system becomes milky. When the reaction is carried out to a certain extent, the reaction is completely cured after about 15min, a sample is taken out, polyformaldehyde is used as a disperse phase in the polymerization process, PEG-b-PPG-b-PEG is used as a continuous phase, PEG-b-PPG-b-PEG is washed off by water to obtain a polyformaldehyde nano-sheet, a scanning electron microscope photograph of the product is shown in figure 3, a transmission electron microscope photograph and an XRD diffraction picture are shown in figure 13, and a polyformaldehyde crystal can be seen to be in a hexagonal crystal form. The transmission electron microscope photograph, the carbon element imaging (mapping) photograph and the oxygen element imaging photograph of the polyoxymethylene nano-sheet are shown in fig. 14a, 14b and 14c, respectively, and it can be seen that the surface of the polyoxymethylene nano-sheet has oxygen atoms densely and uniformly distributed. The DSC thermogram of the polyoxymethylene nanoplatelets is shown in fig. 15 a.
Example 4
Melting 40g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (number average molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) at 60deg.C, adding 60g of trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. Carrying out cation polymerization on trioxymethylene to obtainIs insoluble in PEG-b-PPG-b-PEG and phase separation occurs, and the system becomes milky white. When the reaction is carried out to a certain extent, the reaction is completely cured after about 40min, a sample is taken out, polyformaldehyde is used as a disperse phase in the polymerization process, PEG-b-PPG-b-PEG is used as a continuous phase, PEG-b-PPG-b-PEG is washed off by water to obtain polyformaldehyde nano-sheets, a product electron microscope photo is shown in figure 4, a scanning electron microscope picture and an atomic force microscope scanning picture of a crystal structure of the polyformaldehyde nano-sheets are shown in figure 12, and the polyformaldehyde nano-sheets are visible to be polyformaldehyde crystal, have a regular folding chain crystal structure and are in a hexagonal crystal form.
Example 5
Melting 50g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (number average molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) at 60deg.C, adding 50g of trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG-b-PPG-b-PEG, so that phase separation occurs, and the system becomes milky. When the reaction is carried out to a certain extent, the reaction is completely cured after about 40min, the sample is taken out, the polyoxymethylene is a disperse phase in the polymerization process, the PEG-b-PPG-b-PEG is a continuous phase, the PEG-b-PPG-b-PEG is washed off by water, and the polyoxymethylene nano-sheet is obtained, and an electron microscope photograph of the product is shown in figure 5.
Example 6
Melting 30g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (number average molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) at 60deg.C, adding 63g of trioxymethylene and 7g of dioxolane, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. Cationic trioxymethylene and dioxolanePolymerization, the formaldehyde-dioxolane copolymer obtained by polymerization is insoluble in PEG-b-PPG-b-PEG, so that phase separation occurs, and the system becomes milky white. And when the reaction is carried out to a certain extent, the reaction is completely cured after about 25 minutes, a sample is taken out, the formaldehyde-dioxolane copolymer is taken as a disperse phase in the polymerization process, the PEG-b-PPG-b-PEG is taken as a continuous phase, the PEG-b-PPG-b-PEG is washed off by water, the formaldehyde-dioxolane copolymer nano-sheet is obtained, an electron microscope photo of the product is shown in figure 6, and a DSC thermal analysis curve of the polyoxymethylene copolymer nano-sheet is shown in figure 15 b.
Example 7
Melting 30g polyethylene glycol PEG (number average molecular weight 400 g/mol) at 60deg.C, adding 70g trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3 Dichloroethane solution (BF 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG so as to generate phase separation, and the system becomes milky white. When the reaction is carried out to a certain extent, the reaction is completely cured after about 15min, the sample is taken out, the polyoxymethylene is a disperse phase, the PEG is a continuous phase in the polymerization process, the PEG is washed off by water to obtain bud-shaped clusters formed by the polyoxymethylene nano-sheets, and an electron microscope photograph of the product is shown in figure 7.
Example 8
Melting 30g polyethylene glycol PEG (number average molecular weight 20000 g/mol) at 60deg.C, adding 70g trioxymethylene, stirring for 10min to form transparent uniform solution, adding BF 3- Dichloroethane solution (BF) 3 Concentration of 0.5 mmol/ml), BF 3 The molar ratio of the formaldehyde to the trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG so as to generate phase separation, and the system becomes milky white. When the reaction is carried out to a certain extent, the reaction is completely cured after about 15min, the sample is taken out, the polyformaldehyde is a disperse phase, the PEG is a continuous phase in the polymerization process, the PEG is washed off by water to obtain the polyformaldehyde nano-sheet, and the electron microscope photograph of the product is shown as figure 8Shown.
Example 9
At 60 ℃, 30g of polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer PEG-b-PPG-b-PEG (number average molecular weight 14700g/mol, mass ratio of PEG section to PPG section 80:20) is melted, 70g of trioxymethylene is added, stirring is carried out for 10min to form transparent uniform solution, triisobutylaluminum is added as a catalyst, and the molar ratio of alkylaluminum to trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG so as to generate phase separation, and the system becomes milky white. When the reaction is carried out to a certain extent, the reaction is completely cured after about 15min, the sample is taken out, the polyoxymethylene is a disperse phase, the PEG is a continuous phase in the polymerization process, the PEG is washed off by water to obtain the polyoxymethylene nano-sheet, and an electron microscope photo of the product is shown in figure 9.
Example 10
At 100 ℃, 30g of polyvinylpyrrolidone (number average molecular weight 10000 g/mol) is melted, 70g of trioxymethylene is added, the mixture is stirred for 10min to form transparent and uniform solution, trimethylaluminum is added as a catalyst, and the molar ratio of alkylaluminum to trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in a 100 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG so as to generate phase separation, and the system becomes milky white. When the reaction is carried out to a certain extent, the reaction is completely cured after about 30min, the sample is taken out, polyformaldehyde is taken as a disperse phase in the polymerization process, polyvinylpyrrolidone is taken as a continuous phase, the polyvinylpyrrolidone is washed with water to obtain the polyformaldehyde nano-sheet, and an electron microscope photo of the product is shown in figure 10.
Example 11
Melting 20g of polyvinyl alcohol (with the number average molecular weight of 16000 g/mol) at 60 ℃, adding 80g of trioxymethylene, stirring for 10min to form transparent and uniform solution, adding triethylaluminum as a catalyst, and the molar ratio of aluminum alkyl to trioxymethylene is 5:1000, stirring for 5min, pouring into a container, and sealing. The vessel was placed in an 80 ℃ oven and reacted. The trioxymethylene is subjected to cationic polymerization, and the polymerized trioxymethylene is insoluble in PEG so as to generate phase separation, and the system becomes milky white. When the reaction is carried out to a certain extent, curing is carried out after about 40 minutes, a sample is taken out, polyformaldehyde is used as a disperse phase in the polymerization process, polyvinyl alcohol is used as a continuous phase, the polyvinyl alcohol is washed off by water, and the polyformaldehyde nano-sheet is obtained, and an electron microscope photo of the product is shown in figure 11.
Claims (10)
1. A method of preparing polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets, the method comprising the steps of:
(1) Mixing a surfactant and a monomer to obtain a mixed solution; wherein the monomer is trioxymethylene, or comprises trioxymethylene and comonomer;
(2) And (3) adding a catalyst into the mixed solution obtained in the step (1) to react to form a system containing the polyoxymethylene nano-sheets or the polyoxymethylene copolymer nano-sheets.
2. The method of claim 1, wherein the method has one or more of the following features:
the surfactant is a surfactant that is miscible with the monomer at a temperature not higher than the crystallization temperature of polyoxymethylene or polyoxymethylene copolymer;
the surfactant contains a hydrophobic group and/or a hydrophobic segment and a hydrophilic group and/or a hydrophilic segment;
the surfactant is selected from one or more of polyether polymers such as polyethylene glycol, polyethylene glycol-polypropylene glycol copolymer and polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, polyvinyl alcohol polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyester polymers such as one or two of polyethylene glycol maleate and polysorbate, and saccharide surfactants such as one or more of starch, gum, polysaccharide, modified starch, cellulose, protein, and chitosan;
The surfactant is a water-soluble surfactant;
the number average molecular weight of the surfactant is 400-50000g/mol, preferably 2000-50000g/mol, for example 10000-20000g/mol.
3. The method of claim 1, wherein the method has one or more of the following features:
the comonomer is selected from one or more of dioxolane and alkylene oxide comonomers, for example selected from one or more of ethylene oxide, 1, 2-propylene oxide and 1, 3-propylene oxide;
the mass ratio of the surfactant to the monomer is ≡1:10, for example 1:9 to 5:1, preferably 1:5 to 2:1, for example 3:7 to 1:1;
when the monomer includes a comonomer, the comonomer comprises not more than 30% of the monomer by mass, for example not more than 20%, not more than 15%; preferably, the comonomer comprises not less than 1% by mass of the monomer, for example not less than 2%, not less than 5%.
4. The method of claim 1, wherein the catalyst is a cationic catalyst, such as a lewis acid, such as one or more selected from the group consisting of aluminum trichloride, aluminum tribromide, aluminum alkyls, titanium tetrachloride, tin tetrachloride, zinc dichloride, lead chloride, and boron fluoride; and/or
The molar ratio of the catalyst to the monomer is from 1:10000 to 1:100, for example from 1:1000 to 1:100.
5. The method of claim 1, wherein,
in step (1), the surfactant and the monomer are mixed at a temperature not lower than the melting point of the monomer and the melting point of the surfactant; and/or
In step (2), the reaction temperature is not lower than the melting point of the monomer and the melting point of the surfactant, and not higher than the crystallization temperature of polyoxymethylene or polyoxymethylene copolymer, preferably not higher than 120 ℃.
6. The method of claim 1, further comprising extracting polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets from the system comprising polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets, and optionally crushing, washing and/or drying the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets.
7. A polyoxymethylene nanosheet or a polyoxymethylene copolymer nanosheet characterized in that the polyoxymethylene nanosheet or the polyoxymethylene copolymer nanosheet has a single-layer structure or a multi-layer structure having two or more layers;
preferably, the monolayer thickness of the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets is from 5nm to 50nm, preferably from 10nm to 30nm, for example 20±5nm;
Preferably, the polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets have a regular folded chain platelet structure, the platelet crystal form is preferably a hexagonal crystal form, and the platelet crystal degree is preferably 30-80%;
preferably, oxygen atoms are uniformly distributed on the surfaces of the polyoxymethylene nano-sheets or polyoxymethylene copolymer nano-sheets;
preferably, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets are formed from monomers comprising polyoxymethylene and optionally comonomers in the presence of a surfactant, preferably as described in claim 2;
preferably, the polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets are prepared by the method of any one of claims 1-6.
8. A composite, gas adsorbing material or supported catalytic material, characterized in that it comprises polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets according to claim 7, for example a reinforced composite, a wear resistant composite, a gas barrier composite, an oil resistant composite or a shock absorbing composite, for example a hydrogen storage material.
9. Use of polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets as defined in claim 7 for the preparation of a composite, such as a reinforced composite, a wear resistant composite, a gas barrier composite, an oil resistant composite or a shock absorbing composite, a gas adsorbing material or a supported catalytic material, such as a hydrogen storage material.
10. Use of a surfactant in the preparation of polyoxymethylene nanoplatelets or polyoxymethylene copolymer nanoplatelets;
preferably, the surfactant is as claimed in claim 2.
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| PCT/CN2023/096927 WO2023231990A1 (en) | 2022-05-31 | 2023-05-29 | Polyoxymethylene nanosheet or polyoxymethylene copolymer nanosheet and preparation method therefor |
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