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 PDF

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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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cellulose
nano
holocellulose
containing hemicellulose
quality
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CN109251648B (en
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李永峰
董晓英
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Shandong Agricultural University
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Shandong Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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

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  • 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

The method of nano-cellulose chemical modification aqueous woodware paint containing hemicellulose, is related to a kind of method of modified water-soluble woodcare paint.It is to solve existing nano-material modified water-borne wood coating there are nanoparticle bad dispersibilities, leads to the problem of water paint film dynamic performance difference.Method: one, cellulosic material successively the preparation of nano-cellulose aqueous containing hemicellulose: is stripped to processing and delignification processing, obtain holocellulose, then mechanical pretreatment or chemical machinery mixing pretreatment are carried out, the nano-cellulose aqueous containing hemicellulose is obtained；Two, nano-cellulose in-situ chemical modified water-soluble woodcare paint.This method can significantly improve the mechanical performances such as adhesive force, wearability, hardness, the impact resistance of water-borne wood coating, extend the service life of water-borne wood coating, widen the application range of water-borne wood coating, improve the added value of Wood products.The present invention is used for aqueous woodware paint field.

Description

The method of nano-cellulose chemical modification aqueous woodware paint containing hemicellulose
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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