CN107118393B - Modified cellulose/lactic acid composite material preparation method - Google Patents
Modified cellulose/lactic acid composite material preparation method Download PDFInfo
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- CN107118393B CN107118393B CN201710255781.2A CN201710255781A CN107118393B CN 107118393 B CN107118393 B CN 107118393B CN 201710255781 A CN201710255781 A CN 201710255781A CN 107118393 B CN107118393 B CN 107118393B
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- polylactic acid
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 179
- 239000001913 cellulose Substances 0.000 title claims abstract description 179
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title abstract description 67
- 239000004310 lactic acid Substances 0.000 title abstract description 34
- 235000014655 lactic acid Nutrition 0.000 title abstract description 34
- 239000004626 polylactic acid Substances 0.000 claims abstract description 84
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000000835 fiber Substances 0.000 claims abstract description 54
- 239000003513 alkali Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 32
- 238000004898 kneading Methods 0.000 claims abstract description 27
- 240000008042 Zea mays Species 0.000 claims abstract description 25
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 25
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 25
- 235000005822 corn Nutrition 0.000 claims abstract description 25
- 229920005610 lignin Polymers 0.000 claims abstract description 24
- 238000005906 dihydroxylation reaction Methods 0.000 claims abstract description 21
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 230000032050 esterification Effects 0.000 claims abstract description 13
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 230000021523 carboxylation Effects 0.000 claims abstract description 7
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 66
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 35
- 230000007062 hydrolysis Effects 0.000 claims description 34
- 238000006460 hydrolysis reaction Methods 0.000 claims description 34
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 33
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 22
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims 4
- 239000004917 carbon fiber Substances 0.000 claims 4
- 238000010298 pulverizing process Methods 0.000 claims 4
- 239000012141 concentrate Substances 0.000 claims 3
- 230000007935 neutral effect Effects 0.000 claims 3
- 239000002243 precursor Substances 0.000 claims 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 239000010907 stover Substances 0.000 abstract description 19
- 238000000227 grinding Methods 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 238000007598 dipping method Methods 0.000 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 abstract 2
- 235000010980 cellulose Nutrition 0.000 description 122
- 239000000243 solution Substances 0.000 description 44
- 238000010792 warming Methods 0.000 description 19
- 239000002893 slag Substances 0.000 description 16
- 238000001914 filtration Methods 0.000 description 14
- 241000196324 Embryophyta Species 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000007171 acid catalysis Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005070 sampling Methods 0.000 description 7
- 239000001257 hydrogen Chemical group 0.000 description 6
- 229910052739 hydrogen Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- -1 bad dispersibility Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 240000008564 Boehmeria nivea Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 244000198134 Agave sisalana Species 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000008946 Fibrinogen Human genes 0.000 description 1
- 108010049003 Fibrinogen Proteins 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940012952 fibrinogen Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011174 green composite Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000003356 suture material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/32—Cellulose ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Sustainable Development (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Modified cellulose/lactic acid composite material preparation method, belongs to biomass energy chemical technology field, by corn stover through sour hydrolyzed hemicellulose, then pre-processes through alkali soluble lignin, prepares cellulose presoma；Cellulose presoma grinding dispersion is prepared into fibrillating fibre element, then handles to obtain deshydroxy cellulose through fire retardant dipping, low-temperature oxidation；Deshydroxy cellulose is broken up, then prepares Carbon fibe through low-temperature carbonization；Fibrillating fibre is prepared into carboxylated cellulose through hypochlorite oxidation, then prepares esterified cellulose with polyethylene glycol；Mixer and polylactic acid kneading mixing is added in dehydroxylation cellulose, carbon fibre and esterified cellulose, then prepares modified cellulose/lactic acid composite material through open mill homogenizing dispersion.The present invention to cellulose modified processing, specifically breaks up crushing, fire retardant dipping, low-temperature oxidation, high temperature cabonization, carboxylation esterification process using machinery using distinct methods, improve cellulose intensity, mobility and with polylactic acid interface compatibility.
Description
Technical field
The invention belongs to biomass energy chemical technology fields, are related to the preparation of modified cellulose/lactic acid composite material
Method, and in particular to machinery breaks up crushing, fire retardant dipping, low-temperature oxidation, high temperature cabonization, carboxylation esterification etc. to cellulose modified
Method, and mixer and polylactic acid kneading mixing is added in dehydroxylation cellulose, carbonized celulose and esterified cellulose, then pass through
Open mill homogenizing dispersion prepares modified cellulose/lactic acid composite material method.
Background technique
Polylactic acid (PLA) is a kind of native starch plastics,
And it is extensive on commercial market to be that biopolymer " pioneer " not only prepares raw material sources, and having can
Sustainable development.Polylactic acid has good biocompatibility, degradation absorbability and plasticity, in developing new polymers
Material has become today of hot spot, and polylactic acid has broad application prospects.PLA can be made into fiber suture material, this seam
Zygonema has certain mechanical strength, has not only been able to satisfy slot apertures intensity requirement, but also suction can be slowly decomposed with wound healing and by body
It receives, without taking out stitches, is particularly suitable for the wound suture of human body deep tissue.Currently, basic synthetic route is to hand over vinegar open loop with third
Polymerization obtains PLA.Since the third friendship vinegar depends on import, price is very high, and resulting materials are mainly used for field of biomedicine, such as
Fixed nail, stick, mould material in orthopaedics, the cell in organizational project are grown falsework material, are controlled and be sustained with dispensing object
The load of agent stops material.But the major obstacle of PLA merchandized handling is production technology complexity, long flow path, product cost is high.Institute
To reduce the cost of PLA material preparation, it will be greatly promoted the production and application of PLA commodity.
Plant fiber is nature natural macromolecular material the most abundant, the cellulose grown every year in nature (with
The form presence of natural plant fibre) up to hundred billion tons of total amount, in today that natural resources day by day lacks, make full use of plant fine
The features such as potentiality and its density for tieing up resource are small, intensity is high, rigidity is high, flexibility is good, insulation, heat-insulated, surfaces versus rough,
And can be recycled, is degradable, reproducible feature, be used to replace man-made vitreous fibres or mineral filler etc. prepare thermoplasticity and
Same with thermosetting compound material has vast potential for future development.
Plant fiber is prepared with polylactic acid compound, the composite material being prepared into can be described as " Green Composites ", former
Material originates completely from reproducible non-oil resource, can degradable be carbon dioxide and water and under certain conditions, can be with
Fundamentally solve environmental problem caused by the insufficient raw material as caused by petroleum resources exhaustion and waste.
But plant fiber itself has hydrophily and hygroscopicity, and poly-lactic acid material itself has hydrophobicity and brittleness is big, resistance to
It is hot poor etc., cause the interface compatibility between plant fiber and poly-lactic acid material poor, cellulose/poly-lactic acid material is resistance to
Hygrothermal Properties are poor, and Fiber Aspect Ratio is very big, and easily winding is reunited in poly-lactic acid material, bad dispersibility, and cellulose/polylactic acid is compound
Impact resistance intensity, the heat resistance of material are also bad.So preparation brittleness is small, heat-resist, excellent in cushion effect, at low cost
Cellulose/lactic acid composite material technology is urgently to be resolved.
It is domestic at present to have carried out numerous studies development around the preparation of cellulose/lactic acid composite material and application,
Many innovative techniques are achieved, have established solid foundation for China's cellulose/lactic acid composite material production domesticization.Such as:
CN101314668 discloses a kind of polylactic acid and modified cellulose blend and preparation method and heat-proof macromolecule material, is blended
Object is mainly formed by 70~10 parts by weight polylactic acid and 30~90 part by weight modified cellulose blendings.Polylactic acid/the modified fibre
Element compared with matrix polylactic acid, have higher heat resistance, there is certain transparency simultaneously.CN102605555A discloses one kind
For the heavy metal ion adsorbed compound membrane preparation method of modified cellulose/polylactic acid nano fiber, have simple, quick, high
The features such as imitating, be at low cost, environmentally friendly；Product obtained can be used for heavy metal ion and the recycling of radionuclide adsorbing separation and waste water
The fields such as processing, can be degradable and environmental-friendly after product use.CN102906123A is used based in the presence of NCC particle
The method that the ring-opening polymerisation in situ of L~lactide forms NCC~PLA supermolecule nano composite material prepares a kind of biological material
Material, the material are hydrophobic and compatible with a variety of synthesis and natural polymer, and relative to PLA its gas barrier property, rheology
Performance and mechanical performance and dimensional stability more preferably, and have potential source biomolecule compatibility and recuperability.
CN103044871A discloses a kind of by the concentrated sulfuric acid and poly ethyldiol modified cellulose and the compound method of polylactic acid, the party
Method it is convenient and simple for operation it is easy, preparation process is time-consuming short, solve uniformly dispersed in polylactic acid of nano-cellulose and ask
Topic.CN103145964A discloses a kind of preparation side of nano-crystalline cellulose/polylacticacid/polyethylene acid/polyethylene glycol composite phase change graft copolymer
Method, the present invention can be used for preparing nano-crystalline cellulose/polylacticacid/polyethylene acid/polyethylene glycol composite phase change graft copolymer.CN103387688A
A kind of preparation method of cellulose nano-fiber/polylactiacid acid composite membrane is disclosed, this method removes wood first with chemical method
Quality and most of hemicellulose, Hyarogen-bonding between cellulose is reduced under water run-inflation effect, then uses mechanical treatment system
Obtained the lignocellulosic nanofibrils of uniform, the netted entanglement of appearance and size, product can be used as flexible display, Electronic Paper, too
Positive energy battery, flexible circuit, substitute of glass matrix etc..CN103450361A discloses carboxymethyl cellulose grafted polylactic acid
Amphiphilic polymer and the preparation method and application thereof.Carboxymethyl cellulose grafted polylactic acid is formed in water phase using dialysis process
The self-assembled nanometer spherical micelle of amphiphilic polymer, and anti-dilution stability is good.CN103709448A discloses one kind
The blend material of cellulose and polylactic acid is molten with certain density N~methyl morpholine~N~oxide (NMMO) aqueous solution
Cellulose and polylactic acid are added constant temperature blending in NMMO solution and dissolve to obtain cellulose and polylactic acid mixed solution by agent, and should
The mold compound of mixed solution is precipitated through precipitating reagent, and resulting blend is granulated and is dried in vacuo, and obtains cellulose and poly- cream
Sour blend material.CN103992493A discloses the preparation side of a kind of modified ramie nano-cellulose and polylactic acid laminated film
Method, using hardwood xylan to ramie nano-cellulose carry out hydrophobic modification and with the compound method for preparing film of polylactic acid,
This method is easy to operate, and production cost is low, and raw material is cheap and easy to get, and film obtained has very high tensile strength and extension at break
Rate, while good air permeability, biodegradable, quality is stablized, and has good flexibility and biocompatibility, can be used for food
The fields such as packaging material, agricultural film and industrial product packaging film.CN104031366A discloses a kind of coupling of cellulose and receives
Rice metal oxide enhancing poly-lactic acid material and preparation method thereof, this method processing step is few, and reaction condition is mild, production process
Middle energy consumption is small, easy to operate；The product prepared using this method mainly has effect on environment small, meet environmental protection requirement and
The features such as mechanical property is good.CN104258466A disclose using esterifying agent prepare modified nanometer cellulose and with polylactic acid it is compound
Porous support is prepared, the porous support is compared with porous support prepared by pure polylactic acid, and mechanical property improves, and nano-cellulose
Strongly hydrophilic be conducive to the absorption and growth of cell.CN104292439A discloses a kind of prepare by grafting processing method and changes
Property sisal cellulose nano whisker and with the compound method for preparing Biocomposite material of polylactic acid.CN104532480A discloses one
Kind nano micro crystal cellulose enhancing polylactic-co-glycolic acid electrospinning film and its preparation method and application, and electrostatic spinning prepares electrospinning
The method of film can not only effectively reinforcing material intensity and bioactivity, the healing of wound can be advantageously promoted.
CN104693464A, which is disclosed, a kind of to be prepared lignin nano-cellulose and is used for enhancing using sour water solution~high pressure homogenization method
The preparation method of polymeric lactic acid compound film, the present invention is compound by the nano-cellulose containing lignin and polylactic acid for the first time, lignin
Introducing solves the problems, such as that nano-cellulose is low with the bad caused mechanical property of polylactic acid matrix compatibility, improves phase interface
Adhesive attraction.CN104725803A disclose a kind of polyglycolic acid~cuprammonium regenerated cellulose~lactic acid composite material and its
Preparation method has higher tensile strength and bending strength relative to polyglycolic acid~lactic acid composite material, is more suitable for
Processed and applied.CN104830037A discloses a kind of polylactic acid/nano cellulose degradable food packaging material, and feature exists
In: using polylactic acid, microcrystalline cellulose, polyethylene glycol, sulfuric acid, sodium hydroxide as raw material, preparing polylactic acid/nano cellulose can drop
Solve packaging material for food.Present invention process route is completely environmental-friendly, and experimental implementation is relatively easy.
Patent documents above provides advanced experimental data for cellulose/lactic acid composite material preparation in China and answers
With foundation.But cellulose in polylactic acid using there are the problem of still do not solve thoroughly, there is also some problems:
1, there are a large amount of hydroxyl and hydrogen bond actions in plant fiber, make it have stronger polarity and water imbibition, are difficult
Good interface compatibility is formed with there are the non-polar polymer of a large amount of C~H keys, bad dispersibility, and polylactic acid base when melting
Body material is poor to the wellability of plant fiber, weaker so as to cause composite material interface adhesion, although at present around solution
Compatibility has carried out a lot of research work, solves part and is kneaded preparation problem, but activity hydroxy and hydrogen bond in cellulose
In the presence of still resulting in the presence of phase interface between polylactic acid and cellulose in lactic acid composite material product, defect substantially
Still without solution.
2, fiber is easy to reunite in resin matrix, and dispersibility is to be improved.
3, cause cost to increase substantially during preparing crystallite, nano-crystal cellulose, be unfavorable for the industrialization of product, and
And a large amount of spent acid waste liquids can be generated in preparation process, unnecessary pollution is caused to environment.
4, cellulosic material in the prior art is largely commercial chemicals, fails that biomass abundant is made full use of to provide
Source substantially increases production cost, is unfavorable for industrialized production.
Therefore urgently a kind of new technical solution solves the problems, such as this in the prior art.
Summary of the invention
The object of the present invention is to provide modified cellulose/lactic acid composite material preparation methods, using distinct methods pair
Cellulose modified processing,
Improve cellulose intensity, mobility and with polylactic acid interface compatibility.Polylactic acid is added in modified cellulose, overcomes
Polylactic acid is reduced and is produced into there is predicament is applied brought by the defects such as expensive, poor toughness, thermal distorsion temperature be low
This, makes it possible polylactic acid in the more massive application of industrial circle.
In order to achieve the above object, the invention proposes the following technical solutions:
A kind of preparation method of modified cellulose/lactic acid composite material, which is characterized in that the preparation method includes as follows
Step:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C~150 DEG C, after constant temperature alkali process 1h~3h, is cooled to 50 DEG C~60
DEG C, it filters, separation obtains alkali soluble slag and filtrate, and filtrate is transferred to adhesive workshop, and it is viscous to be used to prepare lignin-base phenolic resin
Mixture；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: kneading mixing
In mass ratio it is 100:(10~60 by fibrillating fibre element and polylactic acid in step 3) it is added in mixer, it rises
Temperature is to 120 DEG C~180 DEG C, kneading mixing 30min~60min, discharging, is transferred to temperature and is in 120 DEG C~180 DEG C open mills,
It is kneaded homogenizing 30min~60min and obtains fibrillating fibre element/lactic acid composite material through sampling machine moulding process.
Preferably, thermostat temperature described in step 2 is 120 DEG C, and the alkali process time is 180min.
Preferably, fibrillating fibre element and polylactic acid described in step 4 are that 100:50 is added to mixer in mass ratio
In, 180 DEG C are warming up to, kneading mixing 60min.
A kind of preparation method of modified cellulose/lactic acid composite material, which is characterized in that the preparation method includes as follows
Step:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C~150 DEG C, after constant temperature alkali process 1h~3h, is cooled to 50 DEG C~60
DEG C, it filters, separation obtains alkali soluble slag and filtrate, and filtrate is transferred to adhesive workshop, and it is viscous to be used to prepare lignin-base phenolic resin
Mixture；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: heat treatment dehydroxylation
Concentration is used to carry out impregnation for the ammonium chloride solution of 5wt% the fibrillating fibre element that step 3 obtains, very
Rotary furnace is added after sky is dry, under the conditions of 180 DEG C~250 DEG C, is heat-treated 10min~60min, obtains modified de- of dehydroxylation
Hydroxyl cellulose；
Step 5: kneading mixing
It is in mass ratio 100:(10~60 by the modified deshydroxy cellulose of dehydroxylation obtained in step 4 and polylactic acid)
It is added in mixer, is warming up to 120 DEG C~180 DEG C, kneading mixing 30min~60min, discharging, being transferred to temperature is 120 DEG C
In~180 DEG C of open mills, it is kneaded homogenizing 30min~60min, through sampling machine moulding process, obtains modified deshydroxy cellulose/poly- cream
Sour composite material.
Preferably, thermostat temperature described in step 2 is 120 DEG C, and the alkali process time is 180min.
Preferably, heat treatment temperature described in step 4 is 220 DEG C, heat treatment time 60min.
Preferably, dehydroxylation modified cellulose and polylactic acid described in step 5 are that 100:50 is added to mixing in mass ratio
In machine, 180 DEG C are warming up to, kneading mixing 60min.
A kind of preparation method of modified cellulose/lactic acid composite material, which is characterized in that the preparation method includes as follows
Step:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C~150 DEG C, after constant temperature alkali process 1h~3h, is cooled to 50 DEG C~60
DEG C, it filters, separation obtains alkali soluble slag and filtrate, and filtrate is transferred to adhesive workshop, and it is viscous to be used to prepare lignin-base phenolic resin
Mixture；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: heat treatment dehydroxylation
Concentration is used to carry out impregnation for the ammonium chloride solution of 5wt% the fibrillating fibre element that step 3 obtains, very
Rotary furnace is added after sky is dry, under the conditions of 180 DEG C~250 DEG C, is heat-treated 10min~60min, obtains modified de- of dehydroxylation
Hydroxyl cellulose；
Step 5: cellulose charing process
Step 4 is obtained into the modified deshydroxy cellulose pulverizer grinding dispersion of dehydroxylation to length and is less than 10um, is crushed
After be transferred to revolution retort, carbonization reaction 60min~120min under the conditions of 450 DEG C~600 DEG C of temperature, be made Carbon fibe；
Step 6: kneading mixing
In mass ratio it is 100:(10~60 by Carbon fibe and polylactic acid that step 5 obtains) it is added in mixer, it heats up
To 120 DEG C~180 DEG C, kneading mixing 30min~60min, discharging, being transferred to temperature is to mix in 120 DEG C~180 DEG C open mills
Refining homogenizing 30min~60min obtains Carbon fibe/lactic acid composite material through sampling machine moulding process.
Preferably, thermostat temperature described in step 2 is 120 DEG C, and the alkali process time is 180min.
Preferably, heat treatment temperature described in step 4 is 220 DEG C, heat treatment time 60min.
Preferably, carbonation reaction temperature described in step 5 is 500 DEG C, and the carburizing reagent time is 120min；Step 6
Described in Carbon fibe and polylactic acid be in mass ratio that 100:50 is added in mixer, be warming up to 180 DEG C, kneading mixing
60min。
A kind of preparation method of modified cellulose/lactic acid composite material, which is characterized in that the preparation method includes as follows
Step:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C~150 DEG C, after constant temperature alkali process 1h~3h, is cooled to 50 DEG C~60
DEG C, it filters, separation obtains alkali soluble slag and filtrate, and filtrate is transferred to adhesive workshop, and it is viscous to be used to prepare lignin-base phenolic resin
Mixture；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: cellulose is carboxy-modified
By the element of fibrillating fibre obtained in step 3,1:(6~14 are calculated as with Kg/L weight/volume by butt solid-liquid)
The liquor natrii hypochloritis of effective chlorine 10% is added, it is 8~12 that concentrated hydrochloric acid adjustment pH, which is added, is 35 DEG C~50 DEG C in reaction temperature
Under the conditions of carry out carboxylation reaction, isothermal reaction 30min~180min, filtering is first washed with distilled water 2 times, then with ethanol washing 2
After secondary, it is sent into the drying box that temperature is 70 DEG C~80 DEG C and is dried in vacuo, obtain carboxylated cellulose；
Step 5: cellulose esterification modification
The carboxylated cellulose that step 4 is obtained, the mass ratio by carboxylated cellulose, polyethylene glycol and toluenesulfonic acid are
100:(10~100): (2~10) are added in reaction kettle, then by carboxylated cellulose and solvent toluene solid-liquid with Kg/L weight/body
Product ratio be calculated as 1:(4~12) ratio be added solvent toluene, be warming up to solvent toluene recycling effluent, temperature be 110.6 DEG C of items
Under part, constant temperature esterification reaction, until it is anhydrous to flow back, esterification terminates, and separates solvent toluene, and solid send drying box, is in temperature
It is dried in vacuo under the conditions of 70 DEG C~80 DEG C, obtains esterified cellulose；
Step 6: kneading mixing
In mass ratio it is 100:(10~60 by esterified cellulose obtained in step 5 and polylactic acid) it is added to mixer
In, 120 DEG C~180 DEG C, kneading mixing 30min~60min are warming up to, discharging, being transferred to temperature is 120 DEG C~180 DEG C mills
In machine, homogenizing 30min~60min is kneaded through sampling machine moulding process and obtains esterified cellulose/lactic acid composite material.
Preferably, thermostat temperature described in step 2 is 120 DEG C, and the alkali process time is 180min.
Preferably, for the liquor natrii hypochloritis of effective chlorine 10% described in step 4 with concentrated hydrochloric acid tune pH to 11, carboxylation is anti-
Answering temperature is 45 DEG C, reaction time 120min；Carboxylated cellulose described in step 5: polyethylene glycol: the matter of toluenesulfonic acid
For amount than being 100:60:2.5, the carboxylated cellulose and solvent toluene solid-to-liquid ratio are 1:5；Esterification fiber described in step 6
Element and polylactic acid are that 100:50 is added in mixer in mass ratio, are warming up to 180 DEG C, kneading mixing 60min.
Through the above design, the present invention can be brought the following benefits:
(1) in acid-catalyzed hydrolysis hemicellulose process, not only cellulose is purified, while also obtaining hydrolysis half
Cellulose is effectively applied to the production of furfural.
(2) in alkali soluble lignin process, the impurity of fiber surface can be removed under the corrasion of lye；Lignin
It is also sloughed simultaneously in alkali soluble solution preocess.In addition, the cellulose on plant fiber can be changed into alkali cellulose, generation profit rises swollen
Change phenomenon, so that fiber be made to become rich in gloss, elasticity, and can make in plant fiber that the degree of polymerization is lower to be partly dissolved.
In addition, lye can weaken the hydrogen bond action between cellulosic molecule, the intermolecular distance of increased fiber element, table in increased fiber element
Face increases the accessibility of cellulose, changes convenient for the chemistry of cellulose so that various reagents are easier to penetrate into inside fibre structure
Property.
(3) it is crushed in dispersion step in cellulose, the path length of cellulose shortens, convenient for cellulose during chemical modification
Abundant reaction, can also reduce cellulose from wind.
(4) before the heat treatment, it is impregnated through aqueous ammonium chloride solution, improves the yield of charcoal, reinforcing fiber element intensity.
(5) in heat treatment dehydroxylation process, under preference temperature, cellulose can not only slough free water and combine water
Molecule, while cellulose sloughs the hydroxyl on own cellulose chain under low-temperature oxidation effect, realizes that the dehydroxylation of cellulose changes
Property.
(6) by the oxidation of sodium hypochlorite, the hydroxyl in fibrinogen is effective in the carboxy-modified process of cellulose
Ground is converted into carboxyl, to carry out esterification modification to it.
(7) in cellulose esterification modified process, ester is converted by carboxylation and esterification experiment by the hydroxyl in cellulose
Base effectively reduces the presence of hydroxyl and hydrogen bond in fiber, improves the lipophilicity of cellulose, substantially improve cellulose with
The interface compatibility of polylactic acid, while the chain length and the degree of polymerization of cellulose are reduced, improve its dispersion in polylactic acid
Property, effectively improve cellulose/lactic acid composite material performance.
(8) it in In-situ reaction process, is used as filler to prepare modified cellulose lactic acid composite material after cellulose modified, mentions
The high tensile strength and bending strength of composite material, increases the thermal stability and shock resistance of composite material entirety.
The present invention is raw material using the corn stover that cheap, raw material is easy to get, and is utilized respectively hemicellulose therein
Element, lignin and cellulose.The present invention to extract the waste residue of hemicellulose and lignin as raw material, using machinery break up crushing,
Fire retardant dipping, low-temperature oxidation, high temperature cabonization, carboxylation esterification the methods of, reduce cellulose in hydroxyl and hydrogen bond, improve its with
The interface compatibility problem of polylactic acid produces the modified cellulose/lactic acid composite material haveing excellent performance, and improves cost performance.
Specific embodiment
Embodiment one
A kind of preparation method of modified cellulose/lactic acid composite material, the preparation method include the following steps:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C, after constant temperature alkali process 180min, is cooled to 50 DEG C~60 DEG C, filtering,
Separation, obtains alkali soluble slag and filtrate, filtrate is transferred to adhesive workshop, is used to prepare lignin-base aerodux；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: kneading mixing
In mass ratio it is that 100:50 is added in mixer by fibrillating fibre element in step 3 and polylactic acid, is warming up to
180 DEG C, kneading mixing 30min~60min, discharging, being transferred to temperature is homogenizing 60min to be kneaded, through making in 180 DEG C of open mills
Model machine moulding process obtains fibrillating fibre element lactic acid composite material.
Embodiment two
A kind of preparation method of modified cellulose/lactic acid composite material, the preparation method include the following steps:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C, after constant temperature alkali process 180min, is cooled to 50 DEG C~60 DEG C, filtering,
Separation, obtains alkali soluble slag and filtrate, filtrate is transferred to adhesive workshop, is used to prepare lignin-base aerodux；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, obtains cellulose presoma, it will by crushing
The crushing of its machine, which is broken up to fibre length, is less than 1cm, obtains fibrillating fibre element；
Step 4: heat treatment dehydroxylation
Concentration is used to carry out impregnation for the ammonium chloride solution of 5wt% the fibrillating fibre element that step 3 obtains, very
Rotary furnace is added after sky is dry, under the conditions of 220 DEG C, is heat-treated 60min, obtains the modified deshydroxy cellulose of dehydroxylation；
Step 5: kneading mixing
The modified deshydroxy cellulose of dehydroxylation obtained in step 4 and polylactic acid are added in mass ratio for 100:50
In mixer, 180 DEG C, kneading mixing 60min are warming up to, discharging, being transferred to temperature is to be kneaded in 120 DEG C~180 DEG C open mills
It is homogenized 30min~60min, through sampling machine moulding process, obtains modified deshydroxy cellulose/lactic acid composite material.
Embodiment three
A kind of preparation method of modified cellulose/lactic acid composite material, the preparation method include the following steps:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with quality by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into concentration, is transferred to furfural workshop, is dehydrated through sulfuric acid catalysis xylose
Prepare furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that quality is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C, after constant temperature alkali process 180min, is cooled to 50 DEG C~60 DEG C, filtering,
Separation, obtains alkali soluble slag and filtrate, filtrate is transferred to adhesive workshop, is used to prepare lignin-base aerodux；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: heat treatment dehydroxylation
Concentration is used to carry out impregnation for the ammonium chloride solution of 5wt% the fibrillating fibre element that step 3 obtains, very
Rotary furnace is added after sky is dry, under the conditions of temperature is 220 DEG C, is heat-treated 60min, the modified deshydroxy fiber of dehydroxylation is made
Element；
Step 5: cellulose charing process
Step 4 is obtained into the modified deshydroxy cellulose pulverizer grinding dispersion of dehydroxylation to length and is less than 10um, is crushed
After be transferred to revolution retort, carbonization reaction 120min under the conditions of 500 DEG C of temperature, be made Carbon fibe；
Step 6: kneading mixing
In mass ratio it is that 100:50 is added in mixer by Carbon fibe and polylactic acid that step 5 obtains, is warming up to 180
DEG C, kneading mixing 60min, discharging, being transferred to temperature is to be kneaded homogenizing 30min~60min in 120 DEG C~180 DEG C open mills,
Through sampling machine moulding process, Carbon fibe/lactic acid composite material is obtained.
Example IV
A kind of preparation method of modified cellulose/lactic acid composite material, the preparation method include the following steps:
Step 1: hydrolyzed hemicellulose
Corn stover is taken to be crushed, being crushed to length is 5cm~10cm, is with concentration by smashed corn stover
The sulfuric acid solution of 2wt% be in mass ratio 1:5 mixing, atmospheric pressure reflux hydrolyze 60min, be obtained by filtration after hydrolysis xylose solution and
Hydrolysis residue, it is 10wt%~20wt% that xylose solution, which is concentrated into mass concentration, furfural workshop is transferred to, through sulfuric acid catalysis xylose
Dehydration prepares furfural；
Step 2: alkali soluble lignin
The hydrolysis residue that step 1 obtains is mixed with the sodium hydroxide solution 1:5 in mass ratio that concentration is 5wt%, will be mixed
Material afterwards is transferred in reaction kettle, is warming up to 120 DEG C, after constant temperature alkali process 180min, is cooled to 50 DEG C~60 DEG C, filtering,
Separation, obtains alkali soluble slag and filtrate, filtrate is transferred to adhesive workshop, is used to prepare lignin-base aerodux；
Step 3: cellulose grinding dispersion
The alkali soluble slag that step 2 obtains is washed to neutrality, is dried in vacuo, is obtained cellulose presoma, pass through pulverizer
It is crushed to break up to fibre length and is less than 1cm, obtain fibrillating fibre element；
Step 4: cellulose is carboxy-modified
By the element of fibrillating fibre obtained in step 3,1:(6~14 are calculated as with Kg/L weight/volume by butt solid-liquid)
Be added effective chlorine 10% liquor natrii hypochloritis, be added concentrated hydrochloric acid adjustment pH be 11, reaction temperature be 45 DEG C under conditions of into
Row carboxylation reaction, isothermal reaction 120min, filtering are first washed with distilled water 2 times, then with after ethanol washing 2 times, and feeding temperature is
70 DEG C~80 DEG C of drying box vacuum drying, obtains carboxylated cellulose；
Step 5: cellulose esterification modification
The carboxylated cellulose that step 4 is obtained, the mass ratio by carboxylated cellulose, polyethylene glycol and toluenesulfonic acid are
100:60:2.5 is added in reaction kettle, then is calculated as 1:5 by carboxylated cellulose and solvent toluene solid-liquid with Kg/L weight/volume
Ratio be added solvent toluene, be warming up to solvent toluene recycling effluent, temperature be 110.6 DEG C under the conditions of, constant temperature esterification reaction,
Anhydrous to flowing back, esterification terminates, and separates solvent toluene, and solid send drying box, true under the conditions of temperature is 70 DEG C~80 DEG C
Sky is dry, obtains esterified cellulose；
Step 6: kneading mixing
It is in mass ratio that 100:50 is added in mixer by esterified cellulose obtained in step 5 and polylactic acid, heating
To 180 DEG C, kneading mixing 60min, discharging, be transferred to temperature and be in 120 DEG C~180 DEG C open mills be kneaded homogenizing 30min~
60min is formed through sampling machine, obtains esterified cellulose/lactic acid composite material.
The present invention is raw material using the corn stover that cheap, raw material is easy to get, and is utilized respectively hemicellulose therein
Element, lignin and cellulose.Using the waste residue for extracting hemicellulose and lignin as raw material, crushing, fire retardant are broken up using machinery
The methods of dipping, low-temperature oxidation, high temperature cabonization, carboxylation esterification, reduce the hydroxyl and hydrogen bond in cellulose, improve itself and polylactic acid
Interface compatibility problem, produce the modified cellulose/lactic acid composite material haveing excellent performance, improve cost performance.
The foregoing is merely presently preferred embodiments of the present invention, non-to limit the scope of the patents of the invention, other are with this
The equivalence changes of the patent spirit of invention should all belong to the scope of the patents of the invention.
Claims (8)
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| CN201710255781.2A CN107118393B (en) | 2017-04-19 | 2017-04-19 | Modified cellulose/lactic acid composite material preparation method |
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| CN108384211A (en) * | 2018-04-10 | 2018-08-10 | 佛山市熙华科技有限公司 | A kind of preparation method of environmental-protection ventilation laminated film |
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| CN108893871A (en) * | 2018-06-20 | 2018-11-27 | 北京服装学院 | A kind of high-performance biology group compound film and preparation method thereof |
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| CN113512280A (en) * | 2021-05-19 | 2021-10-19 | 青岛科技大学 | A kind of preparation method of nanocellulose-based plastic film |
| CN116444966B (en) * | 2023-04-27 | 2024-03-26 | 江阴锦昊昕新型面料科技有限公司 | Biodegradable reinforced fiber material and preparation method thereof |
| CN116903409A (en) * | 2023-07-20 | 2023-10-20 | 浙江大学 | Fertilizer additive based on sulfate lignin modification and its preparation method and use |
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