CN110256824A - A kind of complete biodegradable film and preparation method thereof that lignin calcium is compound - Google Patents
A kind of complete biodegradable film and preparation method thereof that lignin calcium is compound Download PDFInfo
- Publication number
- CN110256824A CN110256824A CN201910589427.2A CN201910589427A CN110256824A CN 110256824 A CN110256824 A CN 110256824A CN 201910589427 A CN201910589427 A CN 201910589427A CN 110256824 A CN110256824 A CN 110256824A
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- CN
- China
- Prior art keywords
- lignin
- calcium
- complete biodegradable
- biodegradable film
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 113
- 239000011575 calcium Substances 0.000 title claims abstract description 60
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 60
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 29
- 229920003023 plastic Polymers 0.000 claims abstract description 22
- 239000004033 plastic Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000003413 degradative effect Effects 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 239000002023 wood Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 16
- -1 tetramethylene adipate Chemical compound 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 12
- 159000000007 calcium salts Chemical class 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920002961 polybutylene succinate Polymers 0.000 claims description 6
- 239000004631 polybutylene succinate Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims description 4
- 239000004626 polylactic acid Substances 0.000 claims description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical group CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical group OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 229920000704 biodegradable plastic Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 229920001896 polybutyrate Polymers 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920008262 Thermoplastic starch Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004628 starch-based polymer Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
- A01G13/02—Protective coverings for plants; Coverings for the ground; Devices for laying-out or removing coverings
- A01G13/0256—Ground coverings
- A01G13/0268—Mats or sheets, e.g. nets or fabrics
- A01G13/0275—Films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Biodiversity & Conservation Biology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- Biological Depolymerization Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a kind of complete biodegradable films that lignin calcium is compound, in parts by weight include following component: 50-95 parts of degradative plastics；5-45 parts of lignin calcium；0.5-5 parts of plasticizer；0.5-3 parts of lubricant.The invention also discloses the preparation methods of the compound complete biodegradable film of above-mentioned lignin calcium.The present invention uses lignin calcium composite biological degradation plastic, both the effective recycling waste wood element resource of papermaking and biorefinery industry, the presence in turn avoiding residual acid in conventional lignin extraction method processes bring adverse effect to biodegradable plastic, while reducing biodegradable plastic cost, the processing performance and mechanical property of material are improved.
Description
Technical field
The present invention relates to Biodegradable film and its preparations, and in particular to a kind of complete biodegradable that lignin calcium is compound
Film and preparation method thereof.
Background technique
Plastic film plays irreplaceable role in packaging and agriculture Covering domain, with traditional non-degradable or portion
Degradable film is divided to compare, complete biodegradable film can be degradable by the microorganism in nature within the shorter period,
Not residual plastic fragment greatly reduces the adverse effect to ecological environment, therefore it is current for developing complete biodegradable film
The Main way of plastic film pollution problem is solved in the world.
A variety of polyester and polycarbonate-based plastics such as poly terephthalic acid/tetramethylene adipate (PBAT), polylactic acid
(PLA), polycaprolactone (PCL), poly butylene succinate (PBS), poly-succinic/tetramethylene adipate (PBSA), poly- hydroxyl
Base alkanoic acid ester (PHA), fatty poly-ester carbonate (APC) etc. have been demonstrated with completely biodegradable energy, under field conditions (factors)
Carbon dioxide and water can be generated by multiple-microorganism and the intracorporal enzyme catabolism of animals and plants.But it is thin with traditional nondegradable plastics
Film is compared, the film production higher cost prepared by such plastics, it usually needs thermoplastic starch is added thereto as filler
To reduce cost, but the fine dispersion in material matrix is difficult to when content of starch is higher, and remaining plasticiser such as glycerol
Etc. cause film bag product surface small molecule be precipitated stickness, reduce practical application value.
Lignin is the maximum natural aromatic macromolecule of reserves in plant, have rich reserves, it is renewable, cheap easily
It obtains, is biodegradable, being easy to many advantages, such as derivatization.As the by-product being difficult to be utilized in biorefinery and paper industry,
A large amount of lignin are burned to be energized or directly abandons, and a large amount of wasting of resources is caused.Modified, the system by lignin and degradation plastic
Standby film still can not only reduce the dosage of plastic matrix material with complete biodegradable, the use of lignin, reduce
The cost of film article, can also using lignin degradation generate humic acid the characteristics of, reach improvement soil the effect of, in agricultural
Production field is played a positive role.Lignin is largely present in biorefinery and the waste liquid of paper industry, generallys use acid out
Method precipitation and separation lignin (CN103145998B), thus in the lignin powder made have remaining free acid,
And free acid meeting catalytic degradation plastics depolymerization in the process of degradative plastics, show as the reduction and melting of material molecule amount
The raising of index, leads to the blown film processing performance and mechanical property degradation of material, therefore avoids separating in acid condition
Lignin has important practical significance.
Summary of the invention
The technical problems to be solved by the invention are to provide a kind of complete biodegradable film that lignin calcium is compound, the film
With lower melt index.
The present invention also technical problems to be solved are to provide the preparation method of above-mentioned film.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A kind of complete biodegradable film that lignin calcium is compound includes following component in parts by weight:
The compound complete biodegradable film of above-mentioned lignin calcium preferably includes following component in parts by weight:
Wherein, the degradative plastics is poly terephthalic acid/tetramethylene adipate (PBAT), polylactic acid (PLA), gathers
Caprolactone (PCL), poly butylene succinate (PBS), poly-succinic/tetramethylene adipate (PBSA), polyhydroxyalkanoates
(PHA), any one or the combination of several of them in fatty poly-ester carbonate (APC).Preferably poly terephthalic acid/adipic acid fourth
Diol ester (PBAT).
Wherein, the plasticizer is triacetyl glycerine, any one or a few in citric acid ester plasticizer
Combination.Preferably citric acid ester plasticizer.
Wherein, the lubricant is monoglyceride, any one or the combination of several of them in ethylene bis stearamide.It is preferred that
For ethylene bis stearamide.
Wherein, the lignin calcium is prepared as follows:
(1) it is 7-9 (preferably pH=8) by lignin suspension modulation pH value with acid, is removed using solid-liquid separating method
Insoluble impurities obtains lignin liquor；
(2) calcium salt is added into step (1) described lignin liquor under stirring, system is warming up to 40~60 DEG C
Continue 2~3h of stirring (preferably 2.5h) under (preferably 50 DEG C), stirring rate maintains 200-2000rpm (preferably 1000rpm), obtains
To solid-liquid mixing system, it is separated by solid-liquid separation；
(3) by the resulting solid washing of step (2), dry, crushing, even-grained lignin calcium is obtained.
In step (1), the lignin suspension is alkali lignin suspension, enzymolysis xylogen suspension, papermaking wood
Any one or the combination of several of them in quality suspension, preferably alkali lignin suspension, wherein content of lignin be 10~
300g/L (preferably 100g/L).
In step (1), the acid is any one or the combination of several of them of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, preferably salt
Acid.
In step (1) or (2), the solid-liquid separating method is filtering or centrifugation, wherein filtering uses 300 mesh or more
Nylon-type filter cloth, filter bag are filtered.
In step (2), the calcium salt is the group of one or more of calcium chloride, calcium nitrate, calcium oxide, calcium hydroxide
It closes, is added in lignin liquor in the form of calcium salt solid or calcium saline solution, the concentration of the calcium saline solution is 1~
40wt% (preferably 20wt%)；Calcium salt dosage is 1~50% (preferably 20%) of lignin gross mass in lignin liquor.
In step (3), the washing is washed using one of water, methanol, ethyl alcohol, acetone or a variety of mixed solvents
It washs.
In step (3), the drying, using vacuum drying mode, drying temperature is 40~80 DEG C (preferably 60 DEG C), dry
Time is 2~for 24 hours (preferably 12h).
In step (3), one or more of described crushing, including mechanical crushing, ball milling, air-flow crushing combination are crushed
The granularity of lignin calcium is 100-800 mesh (preferably 500 mesh) afterwards.
The preparation method of the compound complete biodegradable film of above-mentioned lignin calcium, includes the following steps:
The degradative plastics of formula ratio, lignin calcium, plasticizer and lubricant are sufficiently mixed to obtain in high mixer pre- by S1
Mixing, revolving speed are 800-1200rpm (preferably 1000rpm), and incorporation time is 10-20min (preferably 15min)；
S2 is granulated after mixing premix by double screw extruder, obtains modified particle, double screw extruder temperature is
130-180 DEG C (preferably 160 DEG C)；
For S3 by modified particle Blown Film, film-forming temperature is 130-180 DEG C (preferably 150 DEG C), and gained film thickness is 5-
100 μm (preferably 20 μm).
This patent proposes the lignin suspension that flocculates using calcium precipitation, and separation and Extraction obtains under neutrality to weak basic condition
To lignin calcium salt solid, without dissociate residual acid, and the carboxylic acid group that lignin molecule itself contains in obtained lignin calcium
Also it chelates to form coordinate bond with calcium ion, the acidity of filler is significantly reduced, especially suitable for the compound of degradative plastics.
The utility model has the advantages that compared to the prior art the present invention, has the advantage that
(1) present invention uses lignin calcium and the compound plastic film for preparing fully biodegradable of biodegradable plastic,
To solve packaging and agricultural film bring white pollution problems.The present invention had both been effectively utilized reproducible Liginon Resource,
Reduce the wasting of resources in biorefinery and paper industry, and the dosage of plastic matrix material can be reduced, effectively reduces
The material cost of film, is conducive to marketing, thus has good environment, resource and economic benefit.
(2) it since the method that traditional acid out extracts lignin will lead to the residual acid for existing in lignin and being difficult to remove, is dropping
In the process for solving plastics, residual acid meeting catalytic degradation degradative plastics shows as the reduction and melting of plastics molecular weight polymeric
The raising of index causes the blown film processing performance and mechanical property degradation of material, and present invention calcium salt is in alkalescent into
Property under the conditions of flocculation separation lignin, avoid the residual of free acid, while calcium salt and the self-contained carboxyl of lignin molecule
Coordination, further reduced the acidity of filler, thus the obtained lignin calcium filler of the present invention especially suitable for degradative plastics
It is compound.
(3) traditional alkali-soluble acid analysis method extraction lignin needs to expend a large amount of alkali and acid, while generating a large amount of exploitation values
It is worth lower salt, while the waste water of peracid high content of salt is also more intractable, therefore extraction cost is higher, and uses calcium salt flocculence
Extract the dosage that acid is then greatly saved in lignin, while reducing the content of salt in waste water, have apparent cost advantage and
Environmental benefit.
Detailed description of the invention
Fig. 1 is the outside drawing of lignin calcium；
Fig. 2 is the X-ray energy spectrogram of lignin calcium
Fig. 3 is the infrared spectrogram of lignin calcium；
Fig. 4 is the grain size distribution of lignin calcium.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
Embodiment 1
The specific preparation method of Biodegradable film the following steps are included:
(1) it is 8 by the alkali lignin suspension modulation pH value that content of lignin is 50g/L with sulfuric acid, uses 300 mesh filter clothes
It is filtered to remove insoluble impurities, obtains alkali lignin solution；Chlorination is added into the alkali lignin solution under stirring
Calcium solid (the addition quality of calcium chloride is 10% of lignin quality in alkali lignin solution), stirring rate 500rpm will
System, which is warming up at 50 DEG C, to be continued to stir 2h, is obtained solid-liquid mixing system, is carried out solid-liquid at 8000rpm using ultracentrifuge
Separation, time 20min, gained precipitating are washed with methanol/water solution (methanol v: water v=6:4), are then placed in precipitating
Vacuum oven is dry, and condition is dry 8h at 60 DEG C, uses the lignin calcium after spherical grinder mill-drying, milling time
For 2h, revolving speed is 600rpm to get can be used for the lignin calcium of compound complete biodegradable film (granularity is 500 mesh)；
(2) 60 parts by weight PBAT, 10 parts of PLA, lignin calcium, 3 parts of lemons described in 30 parts of steps (1) are added in high mixer
Lemon acid tributyl, 2 parts of monoglycerides are mixed 20min, are obtained premix with the revolving speed of 800rpm；By premix through twin-screw extrusion
Machine melting extrusion is granulated, and setting temperature is 160-170 DEG C, and revolving speed 200rpm obtains modified plastics particle；By modified plastics grain
Son is blow molded into the film with a thickness of about 20 μm at 160-170 DEG C, obtains the compound complete biodegradable film of lignin calcium.
Embodiment 2
The specific preparation method of Biodegradable film the following steps are included:
(1) it is 7 by enzymolysis xylogen suspension modulation pH value with hydrochloric acid, is removed using 400 mesh filter-cloth filterings insoluble miscellaneous
Matter obtains enzymolysis xylogen solution；The aqueous solution of calcium nitrate is added into the enzymolysis xylogen solution under stirring,
In, the mass fraction of calcium nitrate is that 20% (the addition quality of calcium nitrate is lignin quality in enzymolysis xylogen solution
10%).Stirring rate is 800rpm, and system is warming up at 55 DEG C and continues to stir 2h, solid-liquid mixing system is obtained, uses hypervelocity
Centrifuge is separated by solid-liquid separation at 12000rpm, time 15min, gained precipitating ethanol/water solution (ethyl alcohol v: water v=
It 7:3) is washed, then that precipitating merging vacuum oven is dry, condition is dry 6h at 65 DEG C, is ground using spherical grinder
Lignin calcium after mill is dry, milling time 3h, revolving speed are 400rpm to get can be used for compound complete biodegradable film
Lignin calcium (granularity is 600 mesh)；
(2) 45 parts of PBAT, 30 parts of PBS, lignin calcium, 2 part of three acetic acid described in 25 parts of steps (1) are added in high mixer
Glyceride, 1 part of ethylene bis stearamide are mixed 10min, are obtained premix with the revolving speed of 1000rpm；By premix through double spiral shells
It is granulated after the mixing of bar extruder, setting temperature is 150-160 DEG C, and revolving speed 150rpm obtains modified particle；Modified particle is existed
It is blow molded into about 25 μm of thickness of film at 150-160 DEG C, obtains the compound complete biodegradable film of lignin calcium.
Comparative example 1
The preparation method is the same as that of Example 1 for Biodegradable film specific, unlike lignin be lignin by acid separation.
The lignin by acid separation is prepared as follows to obtain: sulfuric acid being added into alkali lignin suspension, adjusts pH
To 8, after being filtered to remove insoluble impurities, continue to use sulphur acid for adjusting pH to 3, separation of solid and liquid obtains lignin deposit, uses ethanol/water
Solution (ethyl alcohol v: water v=7:3) washing after merging vacuum oven is dry, grinds to obtain acid out wooden using spherical grinder
Element (granularity is 500 mesh).
Comparative example 2
The specific preparation method of Biodegradable film is with embodiment 2, the difference is that lignin is what common acid out extracted
Sulfuric acid is added in lignin into alkali lignin suspension, adjust pH to 8, after being filtered to remove insoluble impurities, continue to use sulfuric acid
PH to 3 is adjusted, separation of solid and liquid obtains lignin deposit, washed with ethanol/water solution (ethyl alcohol v: water v=7:3), and merging vacuum is dry
After dry case is dry, grind to obtain lignin by acid separation using spherical grinder (granularity is 500 mesh).
Comparative example 3
The preparation method is the same as that of Example 1 for Biodegradable film specific, unlike use the wood of acid out obtained in comparative example 1
Quality is mixed with the calcium chloride solid for being equivalent to 10% mass fraction of lignin as filler.
Comparative example 4
The specific preparation method of Biodegradable film is with embodiment 2, the difference is that using the wood of acid out obtained in comparative example 2
Quality is mixed with the calcium nitrate solid for being equivalent to 20% mass fraction of lignin as filler.
Performance test
Fig. 1~4 are the test results of the resulting lignin calcium of embodiment 1.X-ray energy spectrum as shown in Figure 2 analysis shows,
Contain the elements such as C, O, Ca in lignin calcium；In infrared spectroscopy as shown in Figure 3, belong to the characteristic peak of lignin free carboxy
(1691cm-1) disappear in the infrared spectroscopy of lignin calcium, and in 1588cm-1Place generates new characteristic peak, shows lignin
Ionic interaction occurs for carboxyl and calcium ion；The particle diameter distribution of lignin calcium is as shown in figure 4, d50=3.83 μm, d90=
10.05μm。
It is carried out using melt index and tensile strength of the tensilon to 1~4 material of above-described embodiment 1,2 and comparative example
Measurement, specific testing result are as shown in table 1.Compared with lignin, the compound Biodegradable film of lignin calcium shows lower
Melt index, be conducive to improve film blown film processing performance, tensile strength and elongation at break are all significantly improved.
Melt index, tensile strength and the elongation at break of 1 film of table
Claims (14)
1. a kind of complete biodegradable film that lignin calcium is compound, which is characterized in that in parts by weight include following component:
2. the compound complete biodegradable film of lignin calcium according to claim 1, which is characterized in that in parts by weight
Including following component:
3. the compound complete biodegradable film of lignin calcium according to claim 1 or 2, which is characterized in that described
Degradative plastics is poly terephthalic acid/tetramethylene adipate, polylactic acid, polycaprolactone, poly butylene succinate, polybutadiene
Acid/tetramethylene adipate, polyhydroxyalkanoates, any one or the combination of several of them in fatty poly-ester carbonate.
4. the compound complete biodegradable film of lignin calcium according to claim 1 or 2, which is characterized in that described
Plasticizer is triacetyl glycerine, any one or the combination of several of them in citric acid ester plasticizer.
5. the compound complete biodegradable film of lignin calcium according to claim 1 or 2, which is characterized in that described
Lubricant is monoglyceride, any one or the combination of several of them in ethylene bis stearamide.
6. the compound complete biodegradable film of lignin calcium according to claim 1 or 2, which is characterized in that described
Lignin calcium is prepared as follows:
(1) it is 7-9 by lignin suspension modulation pH value with acid, removes insoluble impurities using solid-liquid separating method, obtain wood
Quality solution；
(2) calcium salt is added into step (1) described lignin liquor under stirring, by system be warming up at 40~60 DEG C after
2~3h of continuous stirring, stirring rate maintain 200-2000rpm, obtain solid-liquid mixing system, be separated by solid-liquid separation；
(3) by the resulting solid washing of step (2), dry, crushing, even-grained lignin calcium is obtained.
7. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that in step (1),
The lignin suspension is alkali lignin suspension, enzymolysis xylogen suspension, any in papermaking lignin suspension
One or more of combinations, wherein content of lignin is 10~300g/L.
8. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that in step (1),
The acid is any one or the combination of several of them of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid.
9. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that step (1) or
(2) in, the solid-liquid separating method is filtering or centrifugation, wherein filtering using 300 mesh and the above nylon-type filter cloth, filter bag into
Row filtering.
10. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that step (2)
In, the calcium salt is the combination of one or more of calcium chloride, calcium nitrate, calcium oxide, calcium hydroxide, with calcium salt solid or
The form of calcium saline solution is added in lignin liquor, and the concentration of the calcium saline solution is 1~40wt%；Calcium salt dosage is
The 1~50% of lignin gross mass in lignin liquor.
11. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that step (3)
In, the washing is washed using one of water, methanol, ethyl alcohol, acetone or a variety of mixed solvents.
12. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that step (3)
In, the drying, using vacuum drying mode, drying temperature be 40~80 DEG C, drying time be 2~for 24 hours.
13. the compound complete biodegradable film of lignin calcium according to claim 6, which is characterized in that step (3)
In, one or more of described crushing, including mechanical crushing, ball milling, air-flow crushing combination, the granularity of lignin calcium after crushing
For 100-800 mesh.
14. the preparation method of claim 1 or the compound complete biodegradable film of the lignin calcium, which is characterized in that
Include the following steps:
S1 is sufficiently mixed the degradative plastics of formula ratio, lignin calcium, plasticizer and lubricant to obtain premix in high mixer,
Revolving speed is 800-1200rpm, incorporation time 10-20min；
S2 is granulated after mixing premix by double screw extruder, obtains modified particle, and double screw extruder temperature is 130-
180℃；
For S3 by modified particle Blown Film, film-forming temperature is 130-180 DEG C, and gained film thickness is 5-100 μm.
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| CN110615979A (en) * | 2019-10-31 | 2019-12-27 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
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