CN104640620A - Nfc稳定化泡沫 - Google Patents
Nfc稳定化泡沫 Download PDFInfo
- Publication number
- CN104640620A CN104640620A CN201380037253.XA CN201380037253A CN104640620A CN 104640620 A CN104640620 A CN 104640620A CN 201380037253 A CN201380037253 A CN 201380037253A CN 104640620 A CN104640620 A CN 104640620A
- Authority
- CN
- China
- Prior art keywords
- foam
- nfc
- fibril
- hydrophobization
- fibrillating fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000006260 foam Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 6
- BDKGLFDNNWAJLF-UHFFFAOYSA-M [Br-].[NH4+].C(CCCCCCC)[N+](C)(C)C.[Br-] Chemical group [Br-].[NH4+].C(CCCCCCC)[N+](C)(C)C.[Br-] BDKGLFDNNWAJLF-UHFFFAOYSA-M 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
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- 238000007906 compression Methods 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000005501 phase interface Effects 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 abstract description 35
- 229920002678 cellulose Polymers 0.000 abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 14
- 230000006641 stabilisation Effects 0.000 description 12
- 230000031709 bromination Effects 0.000 description 10
- 238000005893 bromination reaction Methods 0.000 description 10
- 238000005660 chlorination reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000006265 aqueous foam Substances 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004581 coalescence Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 dodecyl amines Chemical class 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000875 Dissolving pulp Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 239000007850 fluorescent dye Substances 0.000 description 3
- 238000001215 fluorescent labelling Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000218657 Picea Species 0.000 description 2
- 235000008124 Picea excelsa Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
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- 238000002477 conductometry Methods 0.000 description 2
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- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000892 gravimetry Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- XFQLOSBBYVMBGT-UHFFFAOYSA-N n,n-dimethyl-7-piperazin-1-yl-2,1,3-benzoxadiazole-4-sulfonamide Chemical compound C12=NON=C2C(S(=O)(=O)N(C)C)=CC=C1N1CCNCC1 XFQLOSBBYVMBGT-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003325 tomography Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 241000218642 Abies Species 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000005456 Pinus sylvestris var mongolica Nutrition 0.000 description 1
- 241000114025 Pinus sylvestris var. mongolica Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VJTAZCKMHINUKO-UHFFFAOYSA-M chloro(2-methoxyethyl)mercury Chemical compound [Cl-].COCC[Hg+] VJTAZCKMHINUKO-UHFFFAOYSA-M 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000001218 confocal laser scanning microscopy Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000008258 liquid foam Substances 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000010603 microCT Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
- C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0028—Use of organic additives containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/288—Alkyl ethers substituted with nitrogen-containing radicals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
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Abstract
一种包括带电疏水胺的疏水化纳米原纤化纤维素泡沫及用于提供这种泡沫的方法和它的用途。
Description
技术领域
本发明属于由改性纤维素纳米原纤(nanofibril)稳定的干性多孔材料和湿性多孔材料，如干性泡沫和湿性泡沫的领域。
背景技术
在我们的日常生活中，主要由石油基聚合物制成的大孔及微孔材料用于各类形式和组合物中。这些的实例是建筑物和飞机的绝缘材料以及包装用的聚合物泡沫。用于此类用途的泡沫必须是稳定的、轻质的容易制造的。
随着人们对使用可再生材料需求意识的增强，人们试图使用源自可再生资源的聚合物来代替石油基聚合物。纤维素作为地球上最丰富的可再生天然聚合物，具有晶体结构且适合大规模工业化制备方法，因此其拥有独特潜力。植物中的长纳米原纤填充有具有β-(1-4)-D-吡喃葡萄糖重复单元的纤维素链，根据植物来源，横截面尺寸为5-30nm。纤维素链的并行结构通过氢键结合在一起并形成薄片，从而构成杨氏模量约为130GPa的晶体结构。正是由于这些晶畴，天然纤维素I具有较高的模量和强度，因此值得注意的是可考虑将这些纳米原纤用作石油基结构的部分替代材料。源自纤维素的纳米原纤在用作纳米材料工程中的结构单元方面已开辟了一个新领域。
采用胶体粒子来稳定所谓皮克林乳液(Pickering emulsion)中的高能界面已有一个多世纪之久的历史。但这一概念直到最近才应用于制备超稳定湿泡沫和在干燥状态下保存这些结构以保持多孔材料。粒子在部分疏液或疏水时会粘附到气液界面。这是由于它非常有利于粒子粘附到气液界面并通过低能固-气区替代部分高能固-液区。优选地，所述粒子以约90°的接触角粘附到界面。这最终是由气-液、气-固和固-液界面张力之间的平衡所决定。由于粒子具有高吸附能，因此它们在界面的吸附倾向比表面活性剂更强。因此，与表面活性剂基体系相比，粒子稳定化泡沫(particle-stabilized foam)表现出优异的稳定性。聚并作用(coalescence)受到吸附的粒子的空间斥力的阻碍，而且界面上形成一层粒子有效阻止气泡收缩和扩张，从而将奥斯瓦尔德熟化降到最低程度并形成持久稳定的泡沫。Studart、Gonzenbach、Tervoort和Gauckler等在《美国陶瓷协会杂志》(2006，89,1771-1789)中对此有进一步论述。
专利US331115公开了一种由干性多孔纤维素制成的香烟过滤嘴，其密度为约0.0008g/cm3左右(相当于美国单位约0.05磅/立方英尺)。专利EP1960097B1公开了如何由粒子制成稳定化泡沫的方法，但未教导如何由纤维素纳米原纤来制备泡沫。
在这方面，采用改性纤维素纳米原纤制备高孔隙率可再生材料是很有意义的。然而，当通过冷冻干燥对湿性泡沫进行干燥时通常会在材料中产生裂缝。因此，需要改进的方法对湿性泡沫进行干燥，从而使多孔材料保持在干燥状态。
同时，对基于可再生材料如纤维素制成的泡沫也有需求。
发明内容
本发明的目的在于提供由可再生材料制成的稳定化干性泡沫和湿性泡沫。
本发明的另一个目的在于提供一种具有高孔隙率和良好孔径分布的稳定化可再生材料，这是实现良好绝缘性能的先决条件。
本发明的一方面是一种包括带电疏水胺的疏水化纳米原纤化纤维素(NFC)泡沫。
本发明的另一方面是一种用于制备疏水化纳米原纤化纤维素泡沫的方法，包括：
a)提供NFC纳米原纤的水分散体，
b)计算所述纳米原纤的电荷密度，
c)使所述NFC原纤与疏水胺反应，
d)通过向所述水分散体中引入气体进行发泡，
e)对来自步骤d)的泡沫进行干燥，但不进行冷冻干燥。
本发明的另一方面是包括带电疏水胺的疏水化纳米原纤化纤维素泡沫用于绝缘和或包装材料的用途。
附图说明
图1示出用于制备NFC稳定泡沫的各不同步骤的示意图；
图2示出具有NFC和辛胺的不同水性泡沫(液体泡沫，aqueous foam)的泡沫稳定性试验；
图3示出在室温条件下干燥时的NFC和辛胺稳定化泡沫的图像；
图4示出共聚焦显微扫描图，显示了用已经由辛胺改性的荧光标记纤维素原纤覆盖的在水中的气泡；
图5示出了来自高速摄像实验的图像，显示了(a)由纤维素纳米原纤覆盖的与(b)无纤维素纳米原纤的两个气泡之间的相互作用；
图6示出了(a)示出球状孔的干纤维素疏水化纳米原纤化泡沫的横截面的低放大倍率(x30)FE-SEM图像，以及(b)泡沫的X射线断层扫描图；
图7示出了干性疏水化纳米原纤化纤维素泡沫的孔隙大小(孔尺寸，pore size)分布曲线图(前进与后退)；
图8示出了疏水化纳米原纤化纤维素泡沫的压缩应力-应变曲线图。
具体实施方式
根据本发明的包括疏水胺的疏水化纳米原纤化纤维素泡沫，其特征可在于具有：
i)低于0.10g/cm3的密度；
ii)至少95％的孔隙率；以及
iii)至少400kPa的压缩杨氏模量。
根据本发明的包括疏水胺的疏水化纳米原纤化纤维素泡沫，其密度低于0.10g/cm3，如低于0.08g/cm3、或低于0.06g/cm3、或低于0.05g/cm3、或低于0.04g/cm3或低于0.03g/cm3。
根据本发明的疏水化纳米原纤化纤维素泡沫，可具有为最低95％至最高99％范围内的孔隙度。
根据本发明的疏水化纳米原纤化纤维素泡沫，其压缩杨氏模量范围可为最低400kPa上达至并包括最高500kPa。
根据本发明的疏水化纳米原纤化纤维素泡沫，其特征还可在于具有气体或液体的受限通路(有限的通道，limited passage)。更具体地，根据本发明的疏水化纳米原纤化纤维素泡沫可用过气体或液体的阻隔物(barrier)。
根据本发明的疏水化纳米原纤化纤维素泡沫的孔隙的至少50％在300μm至500μm的范围内。优选地，至少70％的孔隙在300μm至500μm的范围内。
根据本发明的疏水化纳米原纤化纤维素泡沫不包含二氧化硅。
根据本发明的疏水化纳米原纤化纤维素泡沫的上述技术特征可以以任何适宜的方式进行应用和组合。
在本发明的方法中，步骤a)中使用的NFC纳米原纤可由羧甲基化的纤维素纤维制备，或由经过其他类型预处理的纤维，如酶处理纤维(Henriksson M.、Henriksson G.、Berglund L.A.和T.，《欧洲聚合物期刊》43(2007)3434-3441)或TEMPO氧化纤维(Saito T、NishiyamaT、Putaux JL、Vignon M和Isogai A，《生物大分子》7(2006)1687-1691)制备。
方法的步骤a)的水分散体中的NFC纳米原纤可均质化。均质化可用高压均质技术实现。进一步地，步骤a)中使用的NFC原纤的数值平均长度可小于10μm，宽度为至少5nm上达至最大20nm。
根据本发明的方法中使用的NFC纳米原纤可带负电。步骤b)中计算出的电荷密度可由电导滴定法计算。
方法的步骤c)中所使用的疏水胺带正电。疏水胺所带的电荷与NFC纳米原纤所带的电荷相反。
根据本发明的方法的步骤c)中使用的疏水胺可以是伯胺、仲胺、叔胺或季胺，其通式为R1NH2、R1R2NH、R1R2R3N或R1R2R3R4N+，其中R1、R2、R3和R4代表烷基和芳基。烷基可选自具有1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29和30个碳原子的烷基。烷基可以是直链的、支链的或环状的，并且它们可以是饱和或不饱和的，如，例如具有上述数目的碳原子的烯烃和炔烃。
伯胺的实例是甲胺、乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、癸胺、十二烷胺等具有较长的烷基链。
仲胺的实例是二甲胺、二乙胺、二丙胺、二丁胺、二戊胺、二己胺、二庚胺、二辛胺、二癸胺、双十二烷胺等具有较长的烷基链。对于所有这些实例而言，R1＝R2，但当然也可采用其中R1≠R2的仲胺，如N-甲基-N-辛胺。
叔胺的实例是三甲胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺、十三烷胺、三月桂胺等具有较长的烷基链。同样地，也可采用其中R1、R2和R3其中之一不同于另外两者或其中R1、R2和R3三者彼此各不相等的叔胺，如N,N-二甲基辛胺。
季胺的实例是四甲基氯化/溴化/氟化铵、四乙基氯化/溴化/氟化铵、四丙基氯化/溴化/氟化铵、四丁基氯化/溴化/氟化铵、四戊基氯化/溴化/氟化铵、四己基氯化/溴化/氟化铵、四庚基氯化/溴化/氟化铵、四辛基氯化/溴化/氟化铵、十四烷基氯化/溴化/氟化铵、四月桂基氯化/溴化/氟化铵等，具有较长的烷基链。对于所有这些实例而言，R1＝R2＝R3＝R4，但当然也可采用其中R1、R2、R3和R4其中之一不同于另外三者，或R1、R2、R3和R4其中两者不等于另外两者，或R1、R2、R3和R4彼此各不相等的季胺，如正辛基三甲基溴化铵或十六烷基三乙基溴化铵。
更具体地，根据本发明供的方法，步骤c)中使用的疏水胺可选自由正辛基三甲基溴化铵和辛胺组成的组中。甚至更具体地，疏水胺为辛胺。
NFC纳米原纤与带电疏水胺的电荷密度比可在1:1至10:1的范围内。更具体地，电荷比可为2:1、3:1、4:1、5:1、6:1、7:1、8:1或9:1。
方法的步骤d)中的发泡可通过向分散体中引入空气或惰性气体实现。气体可通过拍打(beating)、搅动(agitation)、搅打(whipping)、起泡(bubbling)或其他适合泡沫形成的方式引入所述分散体。
水在疏水性NFC原纤上的接触角大于其在未处理的NFC原纤上的接触角。疏水性NFC原纤的水接触角可为至少35°或至少40°。
根据本发明的用于制备疏水化纳米原纤化纤维素泡沫的方法的上述技术特征可以以任何适宜的方式进行应用和组合。
为了使NFC能粘附到气相-水相界面(air-water phase boundary)，不得不降低NFC的表面能。通过辛胺的物理吸附作用降低表能，并将接触角从大约20°增大到40°。Studart等人在《美国陶瓷协会杂志》(2006，89，1771-1789)中指出，对于100nm的粒子而言，接触角低至20°时能提供103kT(k为波尔兹曼常数，T为温度)数量级的粘附能。当接触角从20°增大到40°时，表面能降低，这足以使NFC能够与气相-水相界面粘附。
根据本发明的方法的一个优点在于，可通过NFC和疏水胺，如辛胺稳定气泡以形成干性多孔泡沫。疏水性NFC积聚在气泡周围。泡沫在已经干燥时仍能保持多孔结构。
当去除水分时，疏水性原纤覆盖的气泡提供了高度多孔材料。这些孔是球形孔。通过使用方程(1)计算得出泡沫的孔隙度，其中ρ是根据本发明的疏水化纳米原纤化纤维素泡沫的密度，ρ纤维素是NFC的密度：
根据本发明的由辛胺和NFC制成的具有NFC纳米原纤与带电疏水胺的电荷密度比为3:1的泡沫的泡沫稳定性比具有等摩尔电荷比的泡沫更好。
以下实施例将进一步论述本发明的泡沫的技术特征。
实施例
材料
采用由60％的挪威云杉(冷杉属(Picea abies))和40％的欧洲赤松(樟子松)制成的商业亚硫酸盐软木溶解浆(瑞典，FabrikerAB公司，溶解浆)(其中溶解浆的半纤维素含量为4.5％、木质素含量为0.6％)来制造主要由横截面为5-20nm且长度为微米级的纤维素I组成的纳米原纤化纤维素(NFC)。采用由MEMC电子材料SpA(意大利诺瓦拉)制成的抛光硅片作为基材制备纤维素模型表面。采用聚乙烯亚胺(PEI)(Mw＝60kDa，50％水溶液，美国Acros Organics公司)将NCF锚定至硅片，并采用从Sigma Aldrich公司采购的辛胺(99％)对NFC的表面能进行改性。假设辛胺完全质子化，计算得出辛胺的电荷密度在pH＝9的条件下为7.7meq/g。
NFC的制备
瑞典斯德哥尔摩Innventia AB公司通过高压均质技术的辅助，对纤维进行羧甲基化预处理以制备NFC。首先，采用普通实验室再冲洗机将从未干燥的纤维以10000转的速度分散在去离子水中。然后，用乙醇将所述纤维清洗四次并进行中间过滤从而使纤维的溶剂变为乙醇，采用在500mL异丙醇中的10g一氯乙酸的溶液将纤维浸渍30分钟。将这些纤维按比例加入刚加热到沸点以下的NaOH、甲醇和异丙醇的溶液中，允许羧甲基化反应持续一小时。羧甲基化步骤完成后，通过三个步骤依次对纤维进行过滤和清洗：首先采用去离子水，然后采用醋酸(0.1M)，最后再次采用去离子水。然后，使用NaHCO3溶液(4wt％溶液)将纤维浸渍60分钟，从而将羧基转化为其钠的形式。最后，用去离子水清洗所述纤维，并采用布氏漏斗进行排水。上述处理完成后，使上述纤维通过高压均质机(微流化器M-110EH，Microfluidics公司)。该均质机具有两个大小不同的串联腔室(200μm和100μm)。实现均质化，水溶液中单次送料的纤维稠度(fiberconsistency)为2wt％，电导滴定法确定的纤维电荷密度为647μeq/g。
纤维素模型表面
采用抛光硅晶片作为基材制备纤维素表面。通过依次用水、乙醇和水冲洗来清洗晶片。使用等离子炉(PDC-200，美国Harrick Scientific公司)在30W、减压条件下处理3分钟去除任何污染物。
采用PEI作为锚定聚合物将纤维素粘结至硅晶片。将基材在pH为7.5的0.1wt％的PEI溶液中浸渍10分钟，然后采用MilliQ水冲洗并在氮气中进行干燥。然后将相同的基材在pH为9的0.1wt％的NFC溶液中浸渍10分钟，随后用MilliQ水冲洗并在氮气中进行干燥。上述两个步骤完成后，将所述基材在浓度为0.1wt％且pH为9的辛胺水溶液(辛胺的CMC为22.8g/l)中浸渍10分钟，然后用MilliQ水冲洗并在氮气中进行干燥。
接触角测量
采用CAM 200(芬兰赫尔辛基KSV仪器有限公司)接触角测量仪测量静态接触角。采用软件根据完整的Young-Laplace方程的数值解计算出接触角。测量通过MilliQ水在温度为23℃、相对湿度为50％的条件下进行。根据各样品上的三个不同位置确定接触角。当接触角达到稳定值后取所报道的值，在通常液滴沉积后小于10秒，整个测量需要5μl液滴。
发泡
由羧甲基化NFC和不同添加量的辛胺制备两种不同类型的泡沫。其中一种采用相当于原纤三分之一阴离子电荷的辛胺制备；另一种具有等摩尔量的阴离子和阳离子电荷。将30ml浓度为0.8g/l或2.4g/l且pH为9的辛胺倾倒至46g NFC凝胶(2wt％，pH＝7)中，在Ultra Turrax混合器中以8000rpm的速度混合10分钟然后以13500rpm的速度混合10分钟。使用不锈钢牛奶搅拌器将混合物发泡10分钟，为了排出多余水分并实现在室温下对所述泡沫进行干燥，将所得水性泡沫倒入具滤纸(Munktell 3号)的布氏漏斗，见图1。NFC和辛胺在pH＝7和pH＝9的条件下的电荷密度分别为647μeq/g和7.7meq/g。
图1示出用于制备NFC稳定化泡沫的各不同步骤的示意图。a)NFC凝胶(水溶液中，2wt％)。b)将辛胺加入NFC凝胶并采用Ultra Turrax混合器混合。c)辛胺由于静电吸附作用而与原纤粘结。d)采用搅拌器产生气泡，且气泡被改性原纤覆盖。e)水性泡沫被纤维素原纤稳定化。f)将湿性泡沫倒入布氏漏斗以排出大部分水，以允许泡沫在室温下进行干燥，见图x。
同时，采用由TEMPO氧化纤维和辛胺制备的NFC制备泡沫。将1.5ml浓度为20g/L的辛胺加入到30g NFC凝胶(0.4wt％)中，采用实验室机械搅拌器以2000rpm的速度混合发泡5分钟。将所形成的水性泡沫倒在滤纸上，并在50℃的炉子中进行干燥。
同时，采用由TEMPO氧化纤维和正辛基三甲基溴化铵制备的NFC制备泡沫。将1.5ml浓度为20g/L的正辛基三甲基溴化铵加入到30g NFC凝胶(0.4wt％)中，采用实验室机械搅拌器以2000rpm的速度混合发泡5分钟。将所形成的水性泡沫倒在滤纸上，并在50℃的炉子中进行干燥。
确定气泡聚并
制备两种溶液，其中一种采用以上早些描述的改性原纤(原纤+辛胺)(发泡)制备，另一种只采用辛胺制备，两种溶液的浓度均为0.1g/l。将一种或另一种溶液装入小容器(1.8ml)，并采用玻璃吸管通入气泡；然后将容器放入购自Labinco公司的试管旋转器，旋转10分钟，从而使气泡吸收各自的稳定剂。将具有相同稳定剂的两种气泡相继转入具有Milli-Q水的试管，并在与试管顶端接触时采用高速相机进行记录(请参阅支持资料)。高速相机为IDT N4S3型号，传感器：CMOS PolarisⅡ；物镜：PentaxCosmicar 50mm/F1.4；快门速度：41μs；帧率：3000fps(帧/秒)；照度：IDT 7LED 40mm中环。
共聚焦显微镜分析
为了使原纤在气-水界面的位置可视化，进行了一系列实验，采用了荧光标记原纤和进行了共聚焦显微镜分析。为了标记原纤，使100ml浓度为1.2g/l和pH为4-5的水相NFC与4.8mg水溶性缩合剂1-乙基-3-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC)发生反应，同时将pH调至4-5。加入2mg 4-(N,N-二甲氨基磺酰基)-7-哌嗪-2,1,3-苯并噁二唑(DBD-PZ)，颜色变为橙色。静置过夜然后进行透析。然后使用原纤制备原纤稳定化泡沫，并采用共聚焦显微镜进行分析。
采用具有LSM 5励磁扫描仪的倒置式Zeiss Axiovert Observer.Z1显微镜进行CLSM成像。采用二极管405-25nm激光和长通型420nm过滤器一起对由(DBD-PZ)标记的纤维素稳定的气泡进行成像。所有成像均采用高度消色透镜10x/0.45NA物镜，针孔完全打开，简档被储存为8字节或12字节的行扫描图，其具有的分辨率512像素×512像素表示146.2μm×146.2μm的区域。
压缩试验
采用低密度泡沫用的锐刀片将制备的纤维素泡沫切成大小为1cm的立体几何状。采用直径为50mm的Instron压缩板(T1223-1021)进行压缩试验。试验通过Instron 5566万能试验机在温度为23℃、相对湿度为50％的空调房内进行。采用500N的测压元件，压缩速率为10％原样品厚度/分钟。最终应变为80％原样品高度，使得能够评估出材料在经过大变形间隔后的特性。各试验样品在按照ISO 844:2007(E)进行试验前均在23℃且相对湿度为50％的条件下保持24小时。将泡沫吸收的能量看作所有样品的0％应变与80％应变之间的应力-应变曲线以下的区域。
自动孔隙容积分布(APVD)测量
使用十六烷作为液体采用2008-12版TRI/自动孔隙率测定计(TRI/Princeton，美国普林斯顿)测量泡沫的累计孔隙度分布。膜截断半径为1.2μm，这将最小可测孔隙半径有效限制在5μm左右。采用与500-5μm孔隙半径范围相对应的13个压力点记录累计孔隙度分布。通过以下公式计算与一定室气压相对应的孔隙半径：
其中γ为所采用的液体的液-气表面张力，在此情况下为十六烷(27mN/m)，θ为固-液接触角(cosθ＝1，假设充分润湿)，Δp为室气压与大气压之差，r为孔隙半径。采用重量测定法确定500μm以上的孔隙中含有的液体质量。
X射线断层扫描图
采用Xradia MicroXCT-200进行显微断层。扫描条件：X射线源：电压为30kW，功率为6W；投影次数：1800；曝光时间：3秒/投影。检测器到X射线源的距离分别为7mm和30mm，放大倍率为10x，像素分辨率为2.18μm。泡沫图像如图6b所示。
泡沫密度与孔隙度
根据泡沫稳定性结果，决定继续对含有较少辛胺的泡沫进行研究，并探讨是否有可能对泡沫进行干燥以获得干性多孔结构。图3显示，通过采用NFC和辛胺对气泡进行稳定化，可以形成干性多孔泡沫。水性泡沫的体积为85cm3，在室温(23℃，相对湿度为29％)条件下干燥后，其体积变为大约20cm3。如果NFC凝胶不发泡而干燥，则体积为0.42cm3。因此，通过采用上述发泡技术，可以以一定方式布置所述原纤，从而能够在干燥状态下保持多孔结构。泡沫的密度为0.03g/cm3，通过方程(1)可计算出泡沫的孔隙度为98％，其中p为多孔泡沫的密度，ρ纤维素(1.57g/cm3)为NFC的密度。
图3示出了室温下(23℃，相对湿度为29％)干燥时的NFC和辛胺稳定化泡沫，a)湿性泡沫，b)干性泡沫)，c)侧面的干性泡沫。
原纤的表面积聚
为了展示气孔周围的NFC积聚，采用了共聚焦显微镜分析来研究原纤的位置。将荧光原纤染色成绿色，如图4所示，原纤位于气泡周围，这表明辛胺足以能够使原纤在气-水界面积聚。
图4示出了共聚焦显微扫描图，显示了由已经用辛胺改性的荧光标记纤维素原纤覆盖的在水中的气泡。
为了进一步量化原纤的稳定作用以阻止气泡的聚并，采用了高速成像技术对两个气泡间的相互作用进行了探讨。在该探讨中，被原纤覆盖的两个气泡一经接触，高速相机便会将其记录。结果如图5所示，原纤覆盖的气泡的耐聚并力能持续10分钟以上，而未被覆盖的气泡一经接触便会立即聚并在一起。仅有辛胺覆盖的气泡的稳定性持续时间小于3秒。
图5示出了高速摄像实验获得的图像，显示了两个气泡间的相互作用：a)MilliQ水中无表面覆盖物的纯气泡立即聚并；b)MilliQ水中有纤维素原纤覆盖的气泡的稳定性持续了10分钟以上。
泡沫中的多孔结构与大小
如图6所示，当去除水时，由原纤覆盖且能形成材料高多孔结构的气泡形成干性泡沫的多孔结构。气泡被原纤覆盖，因此可以合理地假设这能够形成球状孔隙，图6中显示了纤维素泡沫横截面的FE-SEM图也表明确实出现了球状孔隙。
图6a)为干性纤维素泡沫横截面的低放大倍率(x30)FE-SEM图，显示出了球状孔隙。其中比例尺为1mm；图6b)为干性纤维素泡沫的三维X射线断层扫描图(三维动画请参阅支持资料)。
FE-SEM图很明显地表明，孔隙较大，可高达500μm。PVD设备(孔径分布)的实验中也可发现这一特征，这表明孔径分布中大多数孔径在300μm-500μm的范围内，只有很少数孔径小于50μm，参见图7。通过重量测定法确定，约3％的孔隙尺寸大于500μm。从FE-SEM图中可以清楚看出，泡沫中有相当数量的封闭孔隙。也就是说，当在测量PVD时，如果试图向泡沫中充满十六烷，充满所有闭气孔可能会有困难，这也是为什么图7中测得的绝对容积低的原因。然而，仍认为与图6所示的图像相比，孔隙分布是准确的。
图7示出了使用十六烷作为试验液体通过APVD测量以确定泡沫的“干性”结构，确定出的纤维素泡沫的孔径分布曲线(前进与后退)。该曲线表明，多数孔隙的间隔为300μm至500μm。
泡沫的力学性能
纤维素泡沫的压缩应力-应变曲线如图8所示。三条不同曲线表明泡沫内存在一些变化，其中样品1和样品3位于最边缘(见支持资料)，样品2位于样品1与样品3之间。图8中的曲线图分为三个不同阶段：(I)在低应力下的线性弹性变形，(II)由近水平稳定期(plateau)指示的微孔萎塌(cell-collapse)，以及(III)在大应变下的泡沫致密化。通过采用区域(I)中的最大“线性”坡度，可以估计出杨氏模量。456kPa的模量高于冷冻干燥制成的纤维素气凝胶(199kPa)，但低于冷冻干燥制成的纤维素泡沫(718kPa)和聚苯乙烯泡沫(6000kPa)。纤维素泡沫的能量吸收值在80％的应变下较低，大约为56kJ/m3，但对于冷冻干燥制成的纤维素气凝胶(68kJ/m3)和纤维素泡沫(92kJ/m3)而言，其具有相同的量级。
图8示出了原纤稳定化气泡制成的纤维素泡沫的压缩应力-应变曲线。该图分为三个阶段：(Ⅰ)低应力下的主要线性相，(Ⅱ)微孔萎塌，以及(Ⅲ)致密化区域。样品1-3是从泡沫中切取的样品，其中样品1和样品3位于最边缘，样品2位于样品1与样品3之间，详见支持资料。
泡沫稳定性
进行了泡沫稳定性试验，由NFC和不同辛胺浓度的辛胺制成的泡沫的试验结果如图2所示。泡沫1:3表示辛胺的添加量等于NFC电荷的三分之一，而泡沫1:1表示等摩尔电荷平衡。三天后，两种泡沫之间出现明显差异，其中辛胺含量较少的泡沫稳定性最好。即使是过了十天，辛胺含量较少的泡沫仍然是稳定的，而具有等摩尔平衡电荷的泡沫则开始萎塌。
图2示出了具有NFC和辛胺的水性泡沫在不同时间后的稳定性试验结果。泡沫1:3是指辛胺的添加量等于NFC电荷的三分之一，而泡沫1:1表示等摩尔添加量。a)0天、b)3天、c)10天。
Claims (14)
1.一种包括带电疏水胺的疏水化纳米原纤化纤维素泡沫，其特征在于
i.具有低于0.10g/cm3的密度；
ii.具有至少95％的孔隙率；以及
iii.具有至少400kPa的压缩杨氏模量。
2.根据权利要求1所述的疏水化纳米原纤化纤维素泡沫，其特征在于，具有低于0.04g/cm3的密度。
3.根据权利要求1或2所述的疏水化纳米原纤化纤维素泡沫，其特征在于，用作对气体或液体的阻隔物。
4.根据权利要求1至3中任一项所述的疏水化纳米原纤化纤维素泡沫，其特征在于，它不包含二氧化硅。
5.根据权要求1至4中任一项所述的疏水化纳米原纤化纤维素泡沫，其特征在于，至少50％的孔隙在300μm至500μm的范围内。
6.一种用于制备根据权利要求1至5中任一项所述的疏水化纳米原纤化纤维素(NFC)原纤泡沫的方法，包括：
a)提供NFC原纤的水分散体，
b)计算所述原纤的电荷密度，
c)使所述NFC原纤与疏水胺反应，
d)通过拍打所述水分散体进行发泡，以及
e)干燥来自步骤d)的泡沫，但不使用冷冻干燥。
7.根据权利要求6所述的方法，其中，所述NFC原纤带负电。
8.根据权利要求6至7中任一项所述的方法，其中，所述疏水胺带正电。
9.根据权利要求6至8中任一项所述的方法，其中，所述疏水胺是正辛基三甲基溴化铵或辛胺。
10.根据权利要求6至9中任一项所述的方法，其中，所述NFC原纤与带电疏水胺的电荷密度比为1:1至10:1。
11.根据权利要求6至10中任一项所述的方法，其中，所述方法的步骤d)中的所述发泡是通过将空气或惰性气体引入所述分散体进行的。
12.根据权利要求11所述的方法，其中，通过拍打、搅动、搅打或起泡将所述空气或惰性气体引入所述分散体。
13.根据权利要求6至12中任一项所述的方法，其中，疏水性NFC原纤与气相-水相界面之间的接触角能够为至少35°或至少40°。
14.根据权利要求1所述的疏水化纳米原纤化纤维素泡沫用于绝缘和或包装材料的用途。
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261670046P | 2012-07-10 | 2012-07-10 | |
| US61/670,046 | 2012-07-10 | ||
| SE1250822-2 | 2012-07-12 | ||
| SE1250822 | 2012-07-12 | ||
| PCT/SE2013/050889 WO2014011112A1 (en) | 2012-07-10 | 2013-07-10 | Nfc stabilized foam |
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| Publication Number | Publication Date |
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| CN104640620A true CN104640620A (zh) | 2015-05-20 |
| CN104640620B CN104640620B (zh) | 2016-10-05 |
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| CN201380037253.XA Expired - Fee Related CN104640620B (zh) | 2012-07-10 | 2013-07-10 | Nfc稳定化泡沫 |
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| US (1) | US9556325B2 (zh) |
| EP (1) | EP2872244A4 (zh) |
| JP (1) | JP6297548B2 (zh) |
| CN (1) | CN104640620B (zh) |
| CA (1) | CA2878276A1 (zh) |
| HK (1) | HK1209680A1 (zh) |
| IN (1) | IN2015DN00141A (zh) |
| WO (1) | WO2014011112A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109641061A (zh) * | 2016-07-08 | 2019-04-16 | 切卢特克股份公司 | 包含纤维素纳米纤维(cnf)以及包括闭孔的多孔固体材料药物载体 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101570001B1 (ko) * | 2014-06-25 | 2015-11-18 | 서울대학교산학협력단 | 나노피브릴화 셀룰로오스를 이용한 nfc 폼 제조 방법 및 이를 이용하여 제조된 nfc 폼 |
| JP6786484B2 (ja) * | 2014-10-30 | 2020-11-18 | セルテック アーベー | Ｃｎｆ多孔性固体材料 |
| WO2016068787A1 (en) | 2014-10-30 | 2016-05-06 | Cellutech Ab | Cnf cellular solid material with anionic surfactants |
| EP3023455A1 (en) | 2014-11-21 | 2016-05-25 | Fundacíon Tecnalia Research & Innovation | Porous cellulosic materials and process for their preparation |
| WO2016105598A1 (en) * | 2014-12-23 | 2016-06-30 | Dow Global Technologies Llc | Treated porous material |
| SE540731C2 (en) | 2015-06-26 | 2018-10-23 | Stora Enso Oyj | Manufacturing method for a film or a film product comprising an amphiphilic polymer |
| SE539714C2 (en) * | 2016-03-11 | 2017-11-07 | Innventia Ab | Method of producing shape-retaining cellulose products, and shape-retaining cellulose products therefrom |
| FI20165904A (fi) | 2016-11-28 | 2018-05-29 | Teknologian Tutkimuskeskus Vtt Oy | Elastomeeriset vaahtokuitumateriaalit ja niiden valmistus |
| JP7350730B2 (ja) * | 2017-10-17 | 2023-09-26 | セルテック アーベー | Ｃｎｆ及びアニオン性ゲル化多糖を含むバイオ複合材料 |
| WO2019125417A1 (en) | 2017-12-19 | 2019-06-27 | Halliburton Energy Services, Inc. | Pickering foam drilling fluids |
| JP2021531369A (ja) | 2018-07-10 | 2021-11-18 | セルテック アーベー | セルロース繊維及びグルテンの多孔性材料 |
| SE544302C2 (en) * | 2019-12-18 | 2022-03-29 | Stora Enso Oyj | Coated paper or paperboard and a method for manufacturing a coated paper or paperboard |
| EP3868789A1 (en) | 2020-02-18 | 2021-08-25 | The Hong Kong Research Institute of Textiles and Apparel Limited | Method for preparing water repellent textile substrates and products thereof |
| CN111705542B (zh) * | 2020-05-27 | 2022-02-15 | 仙鹤股份有限公司 | 一种贴片电容器纸的制备方法 |
| AU2022287908A1 (en) | 2021-06-09 | 2023-12-14 | Soane Materials Llc | Articles of manufacture comprising nanocellulose elements |
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| CN1272049A (zh) * | 1997-08-21 | 2000-11-01 | 哈特奇桑公司 | 海绵状材料及其生产方法与应用 |
| JP2012021081A (ja) * | 2010-07-14 | 2012-02-02 | Univ Of Tokyo | セルロースナノファイバー分散液の製造方法、セルロースナノファイバー分散液、セルロースナノファイバー成形体、及びセルロースナノファイバー複合体 |
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| US3311115A (en) | 1963-10-29 | 1967-03-28 | Buckeye Cellulose Corp | Low density aerosol filter |
| AT403296B (de) * | 1995-08-11 | 1997-12-29 | Chemiefaser Lenzing Ag | Verfahren zur herstellung eines celluloseformkörpers |
| FR2794762B1 (fr) | 1999-06-14 | 2002-06-21 | Centre Nat Rech Scient | Dispersion de microfibrilles et/ou de microcristaux, notamment de cellulose, dans un solvant organique |
| AU2001233260A1 (en) * | 2000-03-09 | 2001-09-17 | Hercules Incorporated | Stabilized microfibrillar cellulose |
| US8975301B2 (en) | 2005-12-12 | 2015-03-10 | Eth Zurich | Ultrastable particle-stabilized foams and emulsions |
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| GB0818419D0 (en) * | 2008-10-08 | 2008-11-12 | Imp Innovations Ltd | Nanocomposites |
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| WO2010073678A1 (ja) * | 2008-12-26 | 2010-07-01 | 王子製紙株式会社 | 微細繊維状セルロースシートの製造方法および前記微細繊維状セルロースシートに樹脂含浸した複合体 |
| WO2010134868A1 (en) * | 2009-05-18 | 2010-11-25 | Swetree Technologies Ab | Method of producing and the use of microfibrillated paper |
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- 2013-07-10 WO PCT/SE2013/050889 patent/WO2014011112A1/en active Application Filing
- 2013-07-10 EP EP13816642.6A patent/EP2872244A4/en not_active Withdrawn
- 2013-07-10 CN CN201380037253.XA patent/CN104640620B/zh not_active Expired - Fee Related
- 2013-07-10 CA CA2878276A patent/CA2878276A1/en not_active Abandoned
- 2013-07-10 JP JP2015521582A patent/JP6297548B2/ja not_active Expired - Fee Related
- 2013-07-10 IN IN141DEN2015 patent/IN2015DN00141A/en unknown
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| CN109641061A (zh) * | 2016-07-08 | 2019-04-16 | 切卢特克股份公司 | 包含纤维素纳米纤维(cnf)以及包括闭孔的多孔固体材料药物载体 |
| CN109641061B (zh) * | 2016-07-08 | 2022-09-27 | 切卢特克股份公司 | 包含纤维素纳米纤维(cnf)以及包括闭孔的多孔固体材料药物载体 |
Also Published As
| Publication number | Publication date |
|---|---|
| US9556325B2 (en) | 2017-01-31 |
| HK1209680A1 (zh) | 2016-04-08 |
| EP2872244A1 (en) | 2015-05-20 |
| EP2872244A4 (en) | 2016-03-09 |
| US20150158995A1 (en) | 2015-06-11 |
| JP2015523443A (ja) | 2015-08-13 |
| CA2878276A1 (en) | 2014-01-16 |
| IN2015DN00141A (zh) | 2015-06-12 |
| WO2014011112A1 (en) | 2014-01-16 |
| CN104640620B (zh) | 2016-10-05 |
| JP6297548B2 (ja) | 2018-03-20 |
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