CN109251648A - The method of nano-cellulose chemical modification aqueous woodware paint containing hemicellulose - Google Patents
The method of nano-cellulose chemical modification aqueous woodware paint containing hemicellulose Download PDFInfo
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- CN109251648A CN109251648A CN201810917420.4A CN201810917420A CN109251648A CN 109251648 A CN109251648 A CN 109251648A CN 201810917420 A CN201810917420 A CN 201810917420A CN 109251648 A CN109251648 A CN 109251648A
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- CN
- China
- Prior art keywords
- cellulose
- nano
- holocellulose
- containing hemicellulose
- water
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- Granted
Links
- 239000001913 cellulose Substances 0.000 title claims abstract description 108
- 229920002678 cellulose Polymers 0.000 title claims abstract description 108
- 229920002488 Hemicellulose Polymers 0.000 title claims abstract description 76
- 239000003973 paint Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000007385 chemical modification Methods 0.000 title claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002023 wood Substances 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000009996 mechanical pre-treatment Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 238000012545 processing Methods 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 16
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 16
- 229960002218 sodium chlorite Drugs 0.000 claims description 16
- 239000006210 lotion Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000391 magnesium silicate Substances 0.000 claims description 7
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 7
- 235000019792 magnesium silicate Nutrition 0.000 claims description 7
- -1 graphite alkene Chemical class 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 238000002481 ethanol extraction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000035440 response to pH Effects 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 230000002459 sustained effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims 2
- 235000021419 vinegar Nutrition 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 239000004922 lacquer Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229920001046 Nanocellulose Polymers 0.000 abstract 4
- 238000005299 abrasion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000012362 glacial acetic acid Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000002121 nanofiber Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 241000208140 Acer Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001934 delay Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010010219 Compulsions Diseases 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
含有半纤维素的纳米纤维素化学改性水性木器漆的方法，涉及一种改性水性木器漆的方法。是要解决现有纳米材料改性水性木器涂料存在纳米粒子分散性差，导致水性漆膜力学性能差的问题。方法：一、含半纤维素的纳米纤维素水液的制备：将纤维素原料依次进行抽提处理和去木质素处理，得到综纤维素，然后进行机械预处理或化学机械混合预处理，得到含半纤维素的纳米纤维素水液；二、纳米纤维素原位化学改性水性木器漆。该方法能显著改善水性木器涂料的附着力、耐磨性、硬度、抗冲击性等机械性能，延长水性木器涂料的使用寿命，拓宽水性木器涂料的应用范围，提高木材产品的附加值。本发明用于水性木器漆领域。
The invention discloses a method for chemically modifying water-based wood lacquer with nanocellulose containing hemicellulose, and relates to a method for modifying water-based wood lacquer. The purpose is to solve the problem of poor dispersion of nanoparticles in the existing nanomaterial-modified waterborne wood coatings, resulting in poor mechanical properties of waterborne paint films. Method: 1. Preparation of nanocellulose aqueous solution containing hemicellulose: extracting and delignifying the cellulose raw material in turn to obtain holocellulose, and then performing mechanical pretreatment or chemical-mechanical mixing pretreatment to obtain Nanocellulose aqueous solution containing hemicellulose; 2. In-situ chemical modification of nanocellulose water-based wood paint. The method can significantly improve the mechanical properties such as adhesion, abrasion resistance, hardness and impact resistance of the water-based wood coating, prolong the service life of the water-based wood coating, broaden the application range of the water-based wood coating, and increase the added value of wood products. The invention is used in the field of water-based woodware paint.
Description
Technical field
The present invention relates to a kind of methods of modified water-soluble woodcare paint.
Background technique
Wood surface covering with paint is the main means of wood protection and decoration.Solvent-based paints, oil paint are always in the past
The mainstream of furniture industry paint kind of site operation class.However, recently as the reinforcement of people's environmental consciousness, the appearance of state compulsion policy,
Solvent type and oil paint with high VOC release feature are applied and are substantially limited, and the environment with low VOC release feature
Friendly water-borne wood coating is increasingly interest in industry, and becomes the main trend of woodwork coating development.But it is unluckily
It is water-borne wood coating on the market because of the problems such as solid content is low, weak between component and its with substrate effect power, causes paint film hard
The mechanical performances such as degree, wearability, adhesive force, impact resistance and anti-ultraviolet ageing performance are generally applied not as good as the oiliness of technology maturation
Material, therefore the modification of aqueous woodware paint is imperative.
In recent years, more to the modified method of water-borne wood coating using nano material.1. modifying nanometer cellulose is aqueous
The method of coating, but the dispersion abutment surface activating agent regulation of nano-cellulose, complicated components and paint film property are by the table of small molecule
Face activating agent influences big；And only the adhesive force of coating, wearability and anti-ultraviolet ageing performance are changed by nano-cellulose addition
It is apt to without positive effect.2. improve the mechanical properties such as hardness, the wearability of water-borne wood coating using nano-cellulose rhabdolith,
But since nano-cellulose rhabdolith draw ratio is low, paint film mechanical property is caused to improve unobvious.3. using nano-cellulose and
The method that nano silicon dioxide sol and water-dispersion type resin compounded prepare super-hydrophobic woodwork coating, but nano-cellulose load is received
Rice silica first carries out modifying super hydrophobicity, so that it is huge with the polarity difference of water-dispersion type resin, two-phase compatibility is poor, boundary
The nano material of face poor compatibility, modifying super hydrophobicity is easily reunited, cause coating every mechanical property improve it is not good enough in addition under
Drop.
In short, above-mentioned published method stated inorganic nano particle modified water-borne wood coating when there are nanoparticles
Molecular dispersivity difference causes coating mechanical property, light transmittance to improve not good enough problem；And organic nanofibers element is mostly rodlike nanometer
Cellulose crystals, draw ratio is low, improves to the mechanical property of coating limited；Even if nano-cellulose and SiO2、TiO2, (oxygen
Change) graphene is compound, and that there is also it is poor with polymeric matrix compatibility for used method, bad dispersibility in a polymer matrix
Causing the mechanical property of coating improves not good enough problem.
Summary of the invention
The present invention is to solve existing nano-material modified water-borne wood coatings there are nanoparticle bad dispersibility, leads to water
The problem of property paint film poor mechanical property, provide a kind of side of nano-cellulose chemical modification aqueous woodware paint containing hemicellulose
Method.
The present invention contains the method for the nano-cellulose chemical modification aqueous woodware paint of hemicellulose, comprising the following steps:
One, the preparation of the nano-cellulose aqueous containing hemicellulose:
Cellulosic material is successively stripped to processing and delignification processing, obtains holocellulose, is then carried out mechanical
Pretreatment or chemical machinery mixing pretreatment, obtain the nano-cellulose aqueous containing hemicellulose；
The specific steps of processing are extracted described in step 1 are as follows:
Cellulosic material is ground into 90~120 mesh powder, Benzene-ethanol extraction is then carried out and handles 10~12h.The benzene alcohol
For toluene and the dehydrated alcohol mixture that 2:1 is formed by volume.
The specific steps of the processing of delignification described in step 1 are as follows:
1. extracting treated cellulose powder is immersed in the sodium chlorite solution that mass concentration is 1%~1.2%, use
Glacial acetic acid adjusts solution ph to 4~5, then 1~1.5h of magnetic force heating stirring in 75~80 DEG C of thermostat water baths；
2. 1. cellulose powder that step is obtained immerses in the sodium chlorite solution that mass concentration is 1%~1.2%, use
Glacial acetic acid adjusts solution ph to 4~5, then 1~1.5h of magnetic force heating stirring in 75~80 DEG C of thermostat water baths；
3. repeating step 2. 5~6 times, removes lignin substantially, then carried out obtained liquid with Buchner funnel
Filter, washing finally obtain holocellulose until filtered fluid is in neutrality；
Or the specific steps of the processing of delignification described in step 1 are as follows:
Extracting treated cellulose powder is immersed in the hydrogen peroxide solution that mass concentration is 30%~35%, silicon is added
Sour magnesium (making stabilizer with magnesium silicate), 48~52h of magnetic agitation, removes lignin substantially at room temperature；Then it will obtain
Liquid is filtered with Buchner funnel, is washed, until filtered fluid is in neutrality, finally obtains holocellulose；The wherein matter of magnesium silicate
Amount is the 1%~1.5% of hydrogen peroxide solution quality.
Mechanical pretreatment described in step 1, specific steps are as follows:
1. holocellulose is added in the beaker of 250mL, the mass fraction that deionized water is added to holocellulose is 0.1%
~0.3%
2. then with 30~40min of high-pressure homogeneous mechanical processing of 600bar to get the nano-cellulose containing hemicellulose
Aqueous dispersions, wherein hemicellulose accounts for the 20%~30% of holocellulose quality；
Chemical machinery mixing pretreatment described in step 1, specific steps are as follows:
1. holocellulose is added in the beaker of 250mL, the mass fraction that deionized water is added to holocellulose is 0.1%
~0.3%, sodium bromide and TEMPO reagent are then sequentially added, then under magnetic stirring, with the addition speed of 2.5~3mL/min
Sodium hypochlorite is added in degree, and recycling the sodium hydroxide that concentration is 0.5mol/L to adjust pH value is 10~10.5, sustained response to pH
Value does not change；It is comprehensive fiber that wherein sodium bromide quality, which is the quality of 12%~13%, the TEMPO reagent of holocellulose quality,
The 1%~2% of quality amount, the quality of sodium hypochlorite are the 25%~35% of holocellulose quality；
2. adding deionized water and sodium chlorite after being filtered, being washed, pH value is adjusted to 4~5, then with glacial acetic acid
It in 70~80 DEG C of 1~2h of magnetic agitation, filtered, washed, obtain carboxylated cellulose element；Wherein deionized water and holocellulose
Mass ratio is (95~105): 3, the quality of sodium chlorite is the 25%~35% of holocellulose quality；
3. and then be made into again 0.1%~0.3% carboxylated cellulose element aqueous dispersions, then through 14000~16000rpm
High-speed mixer 20~30min of mechanical dispersion, the nano-cellulose aqueous dispersions containing hemicellulose, wherein hemicellulose is made
Account for the 10%~20% of holocellulose quality.
Cellulosic material described in step 1 be biomass material powder that granularity is 100 mesh or more (such as wood powder,
Agricultural crop straw powder, waste and old paper, leaf, bast fiber raw material etc.)；
Two, nano-cellulose in-situ chemical modified water-soluble woodcare paint:
1. after the nano-cellulose aqueous containing hemicellulose that isophorone diisocyanate and step 1 are obtained mixes
It stirs evenly and (accounts within 0.5% of solid content in water paint), be subsequently poured into four mouthfuls of burnings of the drying with blender, condenser pipe
In bottle, it is heated to 65~70 DEG C of 1~2h of reaction；
2. polypropylene glycol -2000 is then added into reaction system, 65~70 DEG C of 1.5~2h of reaction are kept；
3. the acetone soln by mass concentration for 15%~25% 1,4-butanediol is slowly dropped in reaction system, control
The rate of addition of the acetone soln of 1,4-butanediol processed makes system temperature control at 70-80 DEG C, reacts 1.5~2h；
4. a small amount of N-Methyl pyrrolidone of dihydromethyl propionic acid is dissolved, it is then added in reaction system, controls
Reaction temperature is 65~75 DEG C, is lower than 100mPaS with the viscosity of acetone control reaction solution, reacts 3.5~4h；
5. adding triethylamine in reaction system, 15~20min of neutralization reaction；Wherein isophorone diisocyanate,
Nano-cellulose aqueous, polypropylene glycol -2000, the acetone soln of 1,4- butanediol, dihydromethyl propionic acid containing hemicellulose and
The mass ratio of triethylamine is (50~60): (10~20): (45~60): (15~20): (5~8): (3~5).
6. then dispersing reaction solution with high speed disperser, it is former to obtain the nano-cellulose dispersed graphite alkene containing hemicellulose
Position chemical modification aqueous polyurethane emulsion, as nano-cellulose dispersed graphite alkylene modified water-soluble woodwork coating.
It is stirred continuously in the modifying process of step 2.
Water-and acrylate lotion can be continuously added in the lotion 6. obtained, obtain that aqueous polyurethane acrylate is blended
Lotion.Water-and acrylate lotion is added and obtains another water-borne wood coating, the performance of two kinds of coating is different: aqueous poly- ammonia
The advantages of ester lotion is single component woodwork coating, and the coating after being blended has both both aqueous polyurethane and acrylate.
Beneficial effects of the present invention:
The invention proposes a kind of, and the nano-cellulose dispersed graphite alkene in-situ chemical modified water-soluble with hemicellulose is wooden
The method of device paint, feature are as follows:
1. hemicellulose segment is short, it is grafted in nano-cellulose long-chain-segment, forms " brush " shape, large specific surface area；②
Contain hydroxy functional groups more more than cellulose on hemicellulose, can preferably in aqueous stable dispersion, and have bigger
Hydroxyl reactivity.
And then generate following advantage:
1. the presence of hydroxy functional group abundant improves dispersion stabilization of the nano-cellulose in aqueous, conducive to receiving
Rice cellulose is better dispersed in polymeric matrix, and then the performance of modified water-soluble paint film；2. hydroxyl abundant is conducive to nanometer
The lotion colloidal polymer of cellulose and water paint forms stronger phase by " hydrogen bond " or " chemical bond " between polar functional group
Interaction, to preferably enhance the performance of aqueous paint film；3. the nano-cellulose of " brush " shape can be with the polymer matrix bodily form
It is combined at dendroid shape, enhances the molecular network structure of polymeric matrix using huge specific surface area and chemistry/hydrogen bond action,
And then theoretically promote the mechanical strength of paint film；4. retaining hemicellulose, reduces the extraction step of nano-cellulose, make technique
Process simplification；5. hemicellulose is coated on around nano-cellulose, short texture, when making mechanically decoupled extraction nano-cellulose,
It is easier to scatter " nano-cellulose of hemicellulose cladding ", less energy consumption, and avoids the " shearing of nano-cellulose strand
Cause short " problem, conducive to the higher nano-cellulose of draw ratio, the potential specific surface area for improving nano-cellulose, Jin Erxian is obtained
Write enhancing paint film polymer performance.
This method can significantly improve the mechanical performances such as adhesive force, wearability, hardness, the impact resistance of water-borne wood coating,
The service life for extending water-borne wood coating, widens the application range of water-borne wood coating, improves the added value of Wood products.Its
Middle adhesive force be increased to by III level before modified it is II grades modified, wearability by before modified 40% mass loss rate improve
To modified 25%~35% mass loss rate, tensile strength is increased to modified 3.3 by 2.3MPa before modified~
3.9MPa, hardness are increased to modified hardness HB grades by B grades of hardness before modified, and impact resistance is by 2.1J/m before modified2
Toughness be increased to modified 2.6~3.2J/m2Toughness, glossiness only have dropped 2~4% (by
86.2% drops to 82~84%).
The applicable water paint type of this method: aqueous polyurethane, waterborne polyurethane modified acrylate, water-base epoxy tree
Rouge, aqueous epoxy resins modification acrylate etc..
Detailed description of the invention
Fig. 1 is the nano-cellulose SEM figure containing hemicellulose that 1 step 1 of embodiment obtains；
Fig. 2 is that the nano-cellulose chemical modification aqueous woodware paint containing hemicellulose that embodiment 1 obtains covers with paint, lacquer, colour wash, etc. timber photograph
Piece；Wherein left is unmodified paint film photo, and the right side is modified paint film photo；
Fig. 3 is the nano-cellulose TEM figure containing hemicellulose that 2 step 1 of embodiment obtains；
Fig. 4 is that the nano-cellulose chemical modification aqueous woodware paint containing hemicellulose that embodiment 2 obtains covers with paint, lacquer, colour wash, etc. timber photograph
Piece；Wherein left is unmodified paint film photo, and the right side is modified paint film photo.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: present embodiment contains the nano-cellulose chemical modification aqueous woodware paint of hemicellulose
Method, comprising the following steps:
One, the preparation of the nano-cellulose aqueous containing hemicellulose:
Cellulosic material is successively stripped to processing and delignification processing, obtains holocellulose, is then carried out mechanical
Pretreatment or chemical machinery mixing pretreatment, obtain the nano-cellulose aqueous containing hemicellulose；
The mechanical pretreatment, specific steps are as follows:
1. being 0.1%~0.3% by the mass fraction that deionized water is added to holocellulose in holocellulose；
2. then with 30~40min of high-pressure homogeneous mechanical processing of 600bar to get the nano-cellulose containing hemicellulose
Aqueous dispersions, wherein hemicellulose accounts for the 20%~30% of holocellulose quality；
The chemical machinery mixes pretreatment, specific steps are as follows:
1. being 0.1%~0.3% by the mass fraction that deionized water is added to holocellulose in holocellulose, then successively
Sodium bromide and TEMPO reagent is added, then under magnetic stirring, sodium hypochlorite is added with the addition speed of 2.5~3mL/min,
Adjusting pH value again is 10~10.5, and sustained response to pH value does not change；Wherein sodium bromide quality is holocellulose quality
The quality of 12%~13%, TEMPO reagent is the 1%~2% of holocellulose quality, and the quality of sodium hypochlorite is holocellulose matter
The 25%~35% of amount；
2. after being filtered, being washed, adding deionized water and sodium chlorite, pH value is adjusted to 4~5, then 70~80
DEG C 1~2h of magnetic agitation, is filtered, is washed, and carboxylated cellulose element is obtained；Wherein the mass ratio of deionized water and holocellulose is
(95~105): 3, the quality of sodium chlorite is the 25%~35% of holocellulose quality；
3. and then be made into again 0.1%~0.3% carboxylated cellulose element aqueous dispersions, then through 14000~16000rpm
High-speed mixer 20~30min of mechanical dispersion, the nano-cellulose aqueous dispersions containing hemicellulose, wherein hemicellulose is made
Account for the 10%~20% of holocellulose quality.
Two, nano-cellulose in-situ chemical modified water-soluble woodcare paint:
1. after the nano-cellulose aqueous containing hemicellulose that isophorone diisocyanate and step 1 are obtained mixes
It stirs evenly, is subsequently poured into the four-hole boiling flask of the drying with blender, condenser pipe, be heated to 65~70 DEG C of 1~2h of reaction；
2. polypropylene glycol -2000 is then added into reaction system, 65~70 DEG C of 1.5~2h of reaction are kept；
3. the acetone soln by mass concentration for 15%~25% 1,4-butanediol is slowly dropped in reaction system, control
The rate of addition of the acetone soln of 1,4-butanediol processed makes system temperature control at 70-80 DEG C, reacts 1.5~2h；
4. a small amount of N-Methyl pyrrolidone of dihydromethyl propionic acid is dissolved, it is then added in reaction system, controls
Reaction temperature is 65~75 DEG C, is lower than 100mPaS with the viscosity of acetone control reaction solution, reacts 3.5~4h；
5. adding triethylamine in reaction system, 15~20min of neutralization reaction；
6. then dispersing reaction solution with high speed disperser, it is former to obtain the nano-cellulose dispersed graphite alkene containing hemicellulose
Position chemical modification aqueous polyurethane emulsion, as nano-cellulose dispersed graphite alkylene modified water-soluble woodwork coating.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: at extracting described in step 1
The specific steps of reason are as follows:
Cellulosic material is ground into 90~120 mesh powder, Benzene-ethanol extraction is then carried out and handles 10~12h；The benzene alcohol
For toluene and the dehydrated alcohol mixture that 2:1 is formed by volume.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first embodiment in that: it is gone described in step 1 wooden
The specific steps of element processing are as follows:
1. extracting treated cellulose powder is immersed in the sodium chlorite solution that mass concentration is 1%~1.2%, use
Glacial acetic acid adjusts solution ph to 4~5, then 1~1.5h of magnetic force heating stirring in 75~80 DEG C of thermostat water baths；
2. 1. cellulose powder that step is obtained immerses in the sodium chlorite solution that mass concentration is 1%~1.2%, use
Glacial acetic acid adjusts solution ph to 4~5, then 1~1.5h of magnetic force heating stirring in 75~80 DEG C of thermostat water baths；
3. repeating step 2. 5~6 times, removes lignin substantially, then carried out obtained liquid with Buchner funnel
Filter, washing finally obtain holocellulose until filtered fluid is in neutrality.It is other same as the specific embodiment one.
Specific embodiment 4: the present embodiment is different from the first embodiment in that: it is gone described in step 1 wooden
The specific steps of element processing are as follows:
Extracting treated cellulose powder is immersed in the hydrogen peroxide solution that mass concentration is 30%~35%, silicon is added
Sour magnesium, 48~52h of magnetic agitation, removes lignin substantially at room temperature；Then obtained liquid is carried out with Buchner funnel
It is filtered, washed, until filtered fluid is in neutrality, finally obtains holocellulose；Wherein the quality of magnesium silicate is hydrogen peroxide solution quality
1%~1.5%.It is other same as the specific embodiment one.
Specific embodiment 5: the present embodiment is different from the first embodiment in that: fiber described in step 1
Plain raw material is the biomass material powder that granularity is 100 mesh or more.It is other same as the specific embodiment one.
Specific embodiment 6: the present embodiment is different from the first embodiment in that: the biomass material powder
For wood powder, agricultural crop straw powder, waste and old paper, leaf or bast fiber.It is other same as the specific embodiment one.
Specific embodiment 7: the present embodiment is different from the first embodiment in that: in the modifying process of step 2
It is stirred continuously.It is other same as the specific embodiment one.
Specific embodiment 8: the present embodiment is different from the first embodiment in that: lotion obtained in step 2
In also continue be added water-and acrylate lotion, obtain be blended aqueous polyurethane acrylate lotion.Other and specific embodiment party
Formula one is identical.
Specific embodiment 9: the present embodiment is different from the first embodiment in that: isophorone two in step 2
Isocyanates, the nano-cellulose aqueous containing hemicellulose, polypropylene glycol -2000, the acetone soln of 1,4- butanediol, dihydroxy first
The mass ratio of base propionic acid and triethylamine is (50~60): (10~20): (45~60): (15~20): (5~8): (3~5).Its
It is same as the specific embodiment one.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1:
The present embodiment contains the method for the nano-cellulose chemical modification aqueous woodware paint of hemicellulose, including following step
It is rapid:
One, the preparation of the nano-cellulose aqueous containing hemicellulose: cellulosic material is successively stripped to processing, removes wood
Quality processing, obtains holocellulose fiber, then carries out mechanical pretreatment, obtain the nano-cellulose aqueous containing hemicellulose；
The specific steps of processing are extracted described in step 1 are as follows:
Cellulosic material is ground into 100 mesh powder, Benzene-ethanol extraction is then carried out and handles 10h.The benzene alcohol is by toluene
With dehydrated alcohol by volume 2:1 composition.
The specific steps of the processing of delignification described in step 1 are as follows:
1. extracting treated cellulose powder is immersed in the sodium chlorite solution that mass concentration is 1%, glacial acetic acid is used
Solution ph is adjusted to 4.5, then the magnetic force heating stirring 1h in 75 DEG C of thermostat water baths；
2. 1. cellulose powder that step is obtained immerses in the sodium chlorite solution that mass concentration is 1%, glacial acetic acid is used
Solution ph is adjusted to 4.5, then the magnetic force heating stirring 1h in 75 DEG C of thermostat water baths；
3. repeating step 2. 5 times, remove lignin substantially, be then filtered obtained liquid with Buchner funnel,
Washing finally obtains holocellulose until filtered fluid is in neutrality；
Mechanical pretreatment described in step 1, specific steps are as follows:
1. holocellulose is added in the beaker of 250mL, the mass fraction that deionized water to holocellulose is added is
0.3%；
2. then with the high-pressure homogeneous mechanical processing 30min of 600bar to get the nano-cellulose moisture containing hemicellulose
Dispersion liquid, wherein hemicellulose accounts for the 25% of holocellulose quality；
Cellulosic material described in step 1 is the wood powder that granularity is 100 mesh or more.
Two, nano-cellulose in-situ chemical modified water-soluble woodcare paint:
1. weighing the nano-cellulose water containing hemicellulose that 56g isophorone diisocyanate and 10ml step 1 obtain
Liquid is poured into after mixing evenly in the four-hole boiling flask of the drying with blender, condenser pipe, is heated to 65 DEG C of reaction 1h；
2. weighing polypropylene glycol -2000 50g, it is added in above-mentioned reaction system, keeps 65 DEG C of reaction 1.5h；
3. the acetone soln for the 1,4-butanediol that gross mass is 17g is weighed, wherein 10.5g containing 1,4-butanediol, then delays
Slowly it is added drop-wise in reaction solution, the rate of addition for controlling acetone controls system temperature at 75 DEG C, reacts 1.5h；
4. weighing 5.8g dihydromethyl propionic acid and being dissolved with a small amount of N-Methyl pyrrolidone, it is added in reaction solution,
Reaction temperature is controlled at 70 DEG C, is lower than 100mPaS with the viscosity of acetone control reaction solution, reacts 3.5h；
5. weighing 4.3g triethylamine to be added in reaction system, neutralization reaction 15min；
6. dispersing aforesaid liquid with high speed disperser, the nano-cellulose dispersed graphite alkene original positionization containing hemicellulose is obtained
Learn modified aqueous polyurethane emulsion.
Fig. 1 is the nano-cellulose SEM figure in nano-cellulose aqueous that 1 step 1 of embodiment obtains containing hemicellulose,
The fibre diameter that the nano-cellulose containing hemicellulose that 1 step 1 of embodiment obtains is shown by Fig. 1 is 30nm~50nm model
It encloses, length is tens microns, and draw ratio is greater than 1000, shows the nanofiber containing hemicellulose that 1 step 1 of embodiment obtains
Plain fine structure is uniform, and draw ratio is big.
The modifying nanometer cellulose water-borne wood coating and unmodified woodwork coating that embodiment 1 is obtained are with 120g/m2
Quantity for spray maple surface is applied separately to by spraying method, at 30 DEG C after dry 72h, obtain that embodiment 1 obtains is received
Rice cellulose chemistry modified water-soluble woodwork coating paint film and unmodified woodwork coating paint film, outer viewing paint film light transmittance, surface
Flatness quite (Fig. 2), shows nano-cellulose to paint film appearance without negative effect；According to national standard GBT-17657-2013 " people
Make plate and face artificial board physicochemical property test method " test two kinds of paint films mechanical property, glossiness, the results showed that, implement
The hardness for the modifying nanometer cellulose water-borne wood coating paint film that example 1 obtains is increased to modified hardness by B grade before modified
HB grades, wearability is increased to modified 29% mass loss rate by 40% mass loss rate before modified, and adhesive force is by changing
III level before property is increased to II grades modified, and toughness is by 2.1J/m before modified2It is increased to modified 2.9J/
m2, tensile strength is increased to modified 3.7MPa by 2.3MPa before modified, and glossiness is dropped to by 86.2% before modified
Modified 84%；And as control, it is hard with the pure modifying nanometer cellulose water-borne wood coating paint film without hemicellulose
Degree improves B~HB grades by B grade before modified, and wearability is increased to modified 35% by 40% mass loss rate before modified
Mass loss rate, adhesive force are increased to by III level before modified III~II grades modified, and toughness is by before modified
2.1J/m2It is increased to modified 2.6J/m2, tensile strength is increased to modified 2.9MPa, gloss by 2.3MPa before modified
Degree is only dropped to 82% by 86.2%, shows that the method can be effectively improved the comprehensive performance of water-borne wood coating, purer nanofiber
The resultant effect of plain modified water-soluble woodcare paint is more preferable.
Embodiment 2:
The present embodiment contains the method for the nano-cellulose chemical modification aqueous woodware paint of hemicellulose, including following step
It is rapid:
One, the preparation of the nano-cellulose aqueous containing hemicellulose: cellulosic material is successively stripped to processing, removes wood
Quality processing, obtains holocellulose fiber, then carries out chemical machinery mixing pretreatment, obtains the nanofiber containing hemicellulose
Plain aqueous；
The specific steps of processing are extracted described in step 1 are as follows:
Cellulosic material is ground into 100 mesh powder, Benzene-ethanol extraction is then carried out and handles 10h.The benzene alcohol is by toluene
With dehydrated alcohol by volume 2:1 composition.
The specific steps of the processing of delignification described in step 1 are as follows:
Extracting treated cellulose powder is immersed in the hydrogen peroxide solution that mass concentration is 30%, magnesium silicate is added
(making stabilizer with magnesium silicate), magnetic agitation 48h, removes lignin substantially at room temperature；Then the liquid cloth that will be obtained
Family name's funnel is filtered, washs, until filtered fluid is in neutrality, finally obtains holocellulose；Wherein the quality of magnesium silicate is dioxygen
The 1% of aqueous solution quality.
Chemical machinery mixing pretreatment described in step 1, specific steps are as follows:
1. holocellulose is added in the beaker of 250mL, the mass fraction that deionized water to holocellulose is added is
0.3%, sodium bromide and TEMPO reagent are then sequentially added, then under magnetic stirring, is added with the addition speed of 2.5mL/min
Enter sodium hypochlorite, recycling the sodium hydroxide that concentration is 0.5mol/L to adjust pH value is 10, and sustained response to pH value does not become
Change；It is holocellulose quality that wherein sodium bromide quality, which is the quality of 12%.5%, the TEMPO reagent of holocellulose quality,
1.25%, the quality of sodium hypochlorite is the 30% of holocellulose quality；
2. adding deionized water and sodium chlorite after being filtered, being washed, pH value is adjusted to 4.5 with glacial acetic acid, is then existed
70 DEG C of magnetic agitation 1h, are filtered, are washed, and carboxylated cellulose element is obtained；Wherein the mass ratio of deionized water and holocellulose is
100:3, the quality of sodium chlorite are the 30% of holocellulose quality；
3. and then be made into again 0.3% carboxylated cellulose element aqueous dispersions, then the high-speed mixer machine through 15000rpm
Tool disperses 20min, the nano-cellulose aqueous dispersions containing hemicellulose is made, wherein hemicellulose accounts for holocellulose quality
18%.
Cellulosic material described in step 1 is the Wheat Straw powder that granularity is 100 mesh or more.
Two, nano-cellulose in-situ chemical modified water-soluble woodcare paint:
1. weighing the nano-cellulose water containing hemicellulose that 56g isophorone diisocyanate and 10ml step 1 obtain
Liquid is poured into after mixing evenly in the four-hole boiling flask of the drying with blender, condenser pipe, is heated to 65 DEG C of reaction 1h；
2. weighing polypropylene glycol -2000 50g, it is added in above-mentioned reaction system, keeps 65 DEG C of reaction 1.5h；
3. the acetone soln for the 1,4-butanediol that gross mass is 17g is weighed, wherein 10.5g containing 1,4-butanediol, then delays
Slowly it is added drop-wise in reaction solution, the rate of addition for controlling acetone controls system temperature at 75 DEG C, reacts 1.5h；
4. weighing 5.8g dihydromethyl propionic acid and being dissolved with a small amount of N-Methyl pyrrolidone, it is added in reaction solution,
Reaction temperature is controlled at 70 DEG C, is lower than 100mPaS with the viscosity of acetone control reaction solution, reacts 3.5h；
5. weighing 4.3g triethylamine to be added in reaction system, neutralization reaction 15min；
6. dispersing aforesaid liquid with high speed disperser, the nano-cellulose dispersed graphite alkene original positionization containing hemicellulose is obtained
Learn modified aqueous polyurethane emulsion.
7. continuously adding water-and acrylate lotion in the ratio of solid content 1:1 in the lotion 6. obtained, it is blended
Aqueous polyurethane acrylate lotion.
Fig. 3 is the nano-cellulose TEM figure in nano-cellulose aqueous that 2 step 1 of embodiment obtains containing hemicellulose,
The fibre diameter that the nano-cellulose containing hemicellulose that 1 step 1 of embodiment obtains is shown by Fig. 1 is 10nm or so, length
It is tens microns, draw ratio is greater than 1000, shows the nano-cellulose structure essence containing hemicellulose that 2 step 1 of embodiment obtains
Thin uniform, draw ratio is big.
The modifying nanometer cellulose water-borne wood coating and unmodified woodwork coating that embodiment 2 is obtained are with 120g/m2
Quantity for spray maple surface is applied separately to by spraying method, at 30 DEG C after dry 72h, obtain that embodiment 2 obtains is received
Rice cellulose chemistry modified water-soluble woodwork coating paint film and unmodified woodwork coating paint film, outer viewing paint film light transmittance, surface
Flatness quite (Fig. 4), shows nano-cellulose to paint film appearance without negative effect；According to national standard GBT-17657-2013 " people
Make plate and face artificial board physicochemical property test method " test two kinds of paint films mechanical property, glossiness, the results showed that, implement
The hardness for the modifying nanometer cellulose water-borne wood coating paint film that example 2 obtains is increased to modified hardness by B grade before modified
HB grades, wearability is increased to modified 26% mass loss rate by 40% mass loss rate before modified, and adhesive force is by changing
III level before property is increased to II grades modified, and toughness is by 2.1J/m before modified2It is increased to modified 3.0J/
m2, tensile strength is increased to modified 3.5MPa by 2.3MPa before modified, and glossiness is dropped to by 86.2% before modified
Modified 83%；And as control, it is hard with the pure modifying nanometer cellulose water-borne wood coating paint film without hemicellulose
Degree improves B~HB grades by B grade before modified, and wearability is increased to modified 35% by 40% mass loss rate before modified
Mass loss rate, adhesive force are increased to by III level before modified III~II grades modified, and toughness is by before modified
2.1J/m2It is increased to modified 2.6J/m2, tensile strength is increased to modified 2.9MPa, gloss by 2.3MPa before modified
Degree is only dropped to 82% by 86.2%, shows that the method can be effectively improved the comprehensive performance of water-borne wood coating, purer nanofiber
The resultant effect of plain modified water-soluble woodcare paint is more preferable.
Claims (9)
1. the method for the nano-cellulose chemical modification aqueous woodware paint containing hemicellulose, it is characterised in that this method include with
Lower step:
One, the preparation of the nano-cellulose aqueous containing hemicellulose:
Cellulosic material is successively stripped to processing and delignification processing, obtains holocellulose, then carries out mechanical pre- place
Reason or chemical machinery mixing pretreatment, obtain the nano-cellulose aqueous containing hemicellulose；
The mechanical pretreatment, specific steps are as follows:
1. being 0.1%~0.3% by the mass fraction that deionized water is added to holocellulose in holocellulose；
2. then with 30~40min of high-pressure homogeneous mechanical processing of 600bar to get the nano-cellulose moisture containing hemicellulose
Dispersion liquid, wherein hemicellulose accounts for the 20%~30% of holocellulose quality；
The chemical machinery mixes pretreatment, specific steps are as follows:
1. being 0.1%~0.3% by the mass fraction that deionized water is added to holocellulose in holocellulose, then sequentially add
Then under magnetic stirring sodium hypochlorite is added with the addition speed of 2.5~3mL/min, then adjust in sodium bromide and TEMPO reagent
Saving pH value is 10~10.5, and sustained response to pH value does not change；Wherein sodium bromide quality is the 12% of holocellulose quality
The quality of~13%, TEMPO reagent is the 1%~2% of holocellulose quality, and the quality of sodium hypochlorite is holocellulose quality
25%~35%；
2. after being filtered, being washed, adding deionized water and sodium chlorite, pH value is adjusted to 4~5, then in 70~80 DEG C of magnetic
Power stirs 1~2h, is filtered, is washed, and carboxylated cellulose element is obtained；Wherein the mass ratio of deionized water and holocellulose is (95
~105): 3, the quality of sodium chlorite is the 25%~35% of holocellulose quality；
3. and then be made into again 0.1%~0.3% carboxylated cellulose element aqueous dispersions, then the height through 14000~16000rpm
The nano-cellulose aqueous dispersions containing hemicellulose are made in 20~30min of fast blender mechanical dispersion, and wherein hemicellulose accounts for comprehensive
The 10%~20% of cellulose quality.
Two, nano-cellulose in-situ chemical modified water-soluble woodcare paint:
1. the nano-cellulose aqueous containing hemicellulose that isophorone diisocyanate and step 1 are obtained stirs after mixing
Uniformly, it is subsequently poured into the four-hole boiling flask of the drying with blender, condenser pipe, is heated to 65~70 DEG C of 1~2h of reaction；
2. polypropylene glycol -2000 is then added into reaction system, 65~70 DEG C of 1.5~2h of reaction are kept；
3. the acetone soln by mass concentration for 15%~25% 1,4-butanediol is slowly dropped in reaction system, control 1,
The rate of addition of the acetone soln of 4- butanediol makes system temperature control at 70-80 DEG C, reacts 1.5~2h；
4. a small amount of N-Methyl pyrrolidone of dihydromethyl propionic acid is dissolved, it is then added in reaction system, control reaction
Temperature is 65~75 DEG C, is lower than 100mPaS with the viscosity of acetone control reaction solution, reacts 3.5~4h；
5. adding triethylamine in reaction system, 15~20min of neutralization reaction；
6. then dispersing reaction solution with high speed disperser, the nano-cellulose dispersed graphite alkene original positionization containing hemicellulose is obtained
Learn modified aqueous polyurethane emulsion, as nano-cellulose dispersed graphite alkylene modified water-soluble woodwork coating.
2. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
It is characterized in that: extracting the specific steps of processing described in step 1 are as follows:
Cellulosic material is ground into 90~120 mesh powder, Benzene-ethanol extraction is then carried out and handles 10~12h；The benzene alcohol is first
Benzene and the dehydrated alcohol mixture that 2:1 is formed by volume.
3. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
It is characterized in that: the specific steps of the processing of delignification described in step 1 are as follows:
1. extracting treated cellulose powder is immersed in the sodium chlorite solution that mass concentration is 1%~1.2%, with ice vinegar
Acid-conditioning solution pH value is to 4~5, then 1~1.5h of magnetic force heating stirring in 75~80 DEG C of thermostat water baths；
2. 1. cellulose powder that step is obtained immerses in the sodium chlorite solution that mass concentration is 1%~1.2%, with ice vinegar
Acid-conditioning solution pH value is to 4~5, then 1~1.5h of magnetic force heating stirring in 75~80 DEG C of thermostat water baths；
3. repeating step 2. 5~6 times, removes lignin substantially, obtained liquid is filtered with Buchner funnel then, is washed
It washs, until filtered fluid is in neutrality, finally obtains holocellulose.
4. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
It is characterized in that: the specific steps of the processing of delignification described in step 1 are as follows:
Extracting treated cellulose powder is immersed in the hydrogen peroxide solution that mass concentration is 30%~35%, silicic acid is added
Magnesium, 48~52h of magnetic agitation, removes lignin substantially at room temperature；Then obtained liquid was carried out with Buchner funnel
Filter, washing finally obtain holocellulose until filtered fluid is in neutrality；Wherein the quality of magnesium silicate is hydrogen peroxide solution quality
1%~1.5%.
5. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
Be characterized in that: cellulosic material described in step 1 is the biomass material powder that granularity is 100 mesh or more.
6. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 5 containing hemicellulose,
Be characterized in that: the biomass material powder is wood powder, agricultural crop straw powder, waste and old paper, leaf or bast fiber.
7. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
It is characterized in that: being stirred continuously in the modifying process of step 2.
8. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
It is characterized in that: also continuing that water-and acrylate lotion is added in lotion obtained in step 2, obtain that aqueous polyurethane third is blended
Olefin(e) acid ester lotion.
9. the method for the nano-cellulose chemical modification aqueous woodware paint according to claim 1 containing hemicellulose,
Be characterized in that: isophorone diisocyanate in step 2, the nano-cellulose aqueous containing hemicellulose, polypropylene glycol -2000,
The mass ratio of the acetone soln of 1,4- butanediol, dihydromethyl propionic acid and triethylamine is (50~60): (10~20): (45~
60): (15~20): (5~8): (3~5).
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