CN113831697A - Application of lignin in preparation of degradable chemical foaming material - Google Patents
Application of lignin in preparation of degradable chemical foaming material Download PDFInfo
- Publication number
- CN113831697A CN113831697A CN202111202821.XA CN202111202821A CN113831697A CN 113831697 A CN113831697 A CN 113831697A CN 202111202821 A CN202111202821 A CN 202111202821A CN 113831697 A CN113831697 A CN 113831697A
- Authority
- CN
- China
- Prior art keywords
- lignin
- degradable
- parts
- foaming
- packaging material
- Prior art date
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- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 100
- 238000005187 foaming Methods 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000126 substance Substances 0.000 title abstract description 8
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000005022 packaging material Substances 0.000 claims abstract description 20
- 239000004626 polylactic acid Substances 0.000 claims description 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- -1 polybutylene terephthalate-adipate Polymers 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 240000008042 Zea mays Species 0.000 claims description 7
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 7
- 235000005822 corn Nutrition 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 238000005886 esterification reaction Methods 0.000 claims description 7
- 239000002667 nucleating agent Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 230000010933 acylation Effects 0.000 claims description 6
- 238000005917 acylation reaction Methods 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 229920002961 polybutylene succinate Polymers 0.000 claims description 5
- 239000004631 polybutylene succinate Substances 0.000 claims description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 4
- 229920002522 Wood fibre Polymers 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004156 Azodicarbonamide Substances 0.000 claims description 2
- OPMIUWAMBOLZMJ-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].C1(=CC=CC=C1)[Zn+].C1(=CC=CC=C1)[Zn+].C1(=CC=CC=C1)[Zn+] Chemical compound P(=O)([O-])([O-])[O-].C1(=CC=CC=C1)[Zn+].C1(=CC=CC=C1)[Zn+].C1(=CC=CC=C1)[Zn+] OPMIUWAMBOLZMJ-UHFFFAOYSA-K 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 2
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims 1
- 239000010907 stover Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 229920000728 polyester Polymers 0.000 abstract description 4
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 abstract 1
- 229920001896 polybutyrate Polymers 0.000 abstract 1
- 239000003513 alkali Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229920001610 polycaprolactone Polymers 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 239000006261 foam material Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000017858 demethylation Effects 0.000 description 2
- 238000010520 demethylation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- RWYKESRENLAKMN-UHFFFAOYSA-N 1-[4-[1-[4-[2-[4-[5-(1,2-dihydroxypropyl)-3-(hydroxymethyl)-7-methoxy-2,3-dihydro-1-benzofuran-2-yl]-2-methoxyphenoxy]-3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)propoxy]-3-hydroxy-5-methoxyphenyl]-3-hydroxy-2-[4-[4-(4-hydroxy-3,5-dimethoxyphenyl)-1,3,3a,4,6, Chemical compound O1C=2C(OC)=CC(C(O)C(C)O)=CC=2C(CO)C1C(C=C1OC)=CC=C1OC(CO)C(C=1C=C(OC)C(O)=CC=1)OC(C(=C1)OC)=C(O)C=C1C(C(CO)OC=1C(=CC(=CC=1)C1C2COCC2C(O1)C=1C=C(OC)C(O)=C(OC)C=1)OC)OC(C(=C1)OC)=CC=C1C(O)C(CO)OC1=CC=C(C=CCO)C=C1OC RWYKESRENLAKMN-UHFFFAOYSA-N 0.000 description 1
- SIMBZHVWZSIJHZ-UHFFFAOYSA-N O=C1CC=C(C=C1)S(=O)(=O)C1=CC=CC=C1 Chemical group O=C1CC=C(C=C1)S(=O)(=O)C1=CC=CC=C1 SIMBZHVWZSIJHZ-UHFFFAOYSA-N 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004630 polybutylene succinate adipate Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—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
- 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
-
- 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
Abstract
The invention relates to the field of packaging materials, in particular to application of lignin in preparation of a degradable chemical foaming material. According to the invention, the lignin is applied to the degradable foaming packaging material, and can effectively replace degradable resin, so that the cost is reduced; the modified esterified lignin can act on other aromatic polyesters such as PBAT or PBST, so that the bonding strength between degradable resins is further improved, the performance of the material is improved, the using amount of the lignin can be further improved, and the cost is further reduced.
Description
Technical Field
The invention relates to the field of packaging materials, in particular to application of lignin in preparation of a degradable chemical foaming material.
Background
With the continuous development of human life, the environmental pollution is particularly serious, wherein the foam packaging material can cause serious pollution to the natural environment, and the traditional foam material substrate such as polystyrene and the like has poor performance and is not easy to recycle due to thermosetting plastics. Therefore, in recent years, the degradable foaming materials have been extensively studied, and commonly used degradable resins such as polycaprolactone PCL, polyglycolic acid PGA, polybutylene succinate PBS, polybutylene succinate adipate PBSA, polybutylene terephthalate adipate PBAT, polybutylene succinate/terephthalate PBST, polylactic acid PLA, and the like. Although the degradable foaming material can effectively solve the environmental problem, the price is extremely high, and the market can really adopt the degradable foaming material to replace the traditional foaming material, so that the problem of high price of the degradable foaming material is urgently needed to be solved.
Lignin is a well-established renewable biomass resource, widely present in almost all plant-based biomass materials, and an important component of cell walls. In the prior art, lignin is mainly derived from black liquor generated in the cooking stage of pulping and papermaking, and most of the black liquor is mainly burnt to provide energy for a pulp mill, so that the waste of lignin resources is caused. With the sustainable development and the rise of green chemical concepts, the related research on the conversion of lignin into high value-added chemicals is receiving wide attention. However, due to the characteristics of complex structure, large polydispersity, low chemical functional group content, etc., only 1% of the total lignin in the industry is converted into valuable industrial products. Therefore, finding a new utilization way of lignin and converting the lignin into high value-added chemicals or preparing high-performance materials by a material technology has become a key research point at home and abroad.
The Chinese patent application, application number 201410494397.4, discloses a degradable foam material and a preparation method thereof, wherein the degradable foam packaging material is prepared from plant fibers and degradable resin, so that the cost can be effectively reduced, and the performances such as toughness and the like can be improved; application number 201710267423.3 discloses a preparation method of a high-rate full-biodegradable material, which comprises the steps of preparing a blend of PLA and PBAT by using an internal mixer, adding an epoxy chain extender and a nucleating agent, and obtaining a polylactic acid foam material with a foaming rate of 60-80 in a physical foaming mode. However, in the prior art, plant fibers are used as a filler, and due to the structural and polarity mismatch with degradable resins, the melt strength can be greatly reduced, so that the foaming ratio and the product performance of a product are influenced; without the use of fillers, this would result in an excessively high product cost. Therefore, it is highly desirable to develop a natural biomass raw material that is low in cost and has good compatibility with degradable resins. The lignin is a thermoplastic natural aromatic polymer with glass transition temperature in nature, and can be converted into natural aromatic polyester by a proper modification mode due to a large number of benzene ring structures contained in the structure of the lignin. Has good compatibility with PBAT or PBST resin which is also aromatic polyester. Therefore, the present invention acts lignin on the degradable resin to increase the substitution amount of the resin while increasing the compatibility, thereby reducing the cost.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing the application of lignin in preparing degradable foam packaging materials aiming at the defects of the prior art.
In order to solve the technical problems, the invention discloses application of lignin in preparation of degradable foam packaging materials.
The lignin is any one or combination of several of alkali lignin, soda lignin, organic solvent lignin and enzymatic hydrolysis lignin, or modified lignin prepared by modifying any one of alkali lignin, soda lignin, organic solvent lignin and enzymatic hydrolysis lignin; wherein, the modification is any one or combination of more of acylation, esterification, etherification, epoxidation, phenolization, alkylation, demethylation, amination, vulcanization and unsaturated functionalization; preferably, the lignin is any one or two of esterified lignin and acylated lignin.
Wherein the particle size d50 of the lignin is 2-10 μm.
The specific modification methods of acylation, esterification, etherification, epoxidation, phenolization, alkylation, demethylation, amination, vulcanization and unsaturated functionalization are the ones in the prior art, i.e. the modification methods provided in the prior art are all applicable to the present application.
Preferably, the degradable foam packaging material further comprises the following components: a degradable resin; wherein the degradable resin is a mixture of one or two of polybutylene terephthalate-adipate (PBAT) and polybutylene succinate/terephthalate (PBST) and polylactic acid (PLA).
Further preferably, the weight part ratio of the PLA to any one or more of PBAT and PBST is 7: 3-5: 5.
Wherein, the degradable foaming packaging material also comprises the following components: a foaming agent; wherein the foaming agent is any one or a combination of more of azodicarbonamide, ammonium bicarbonate, sodium bicarbonate (sodium bicarbonate and sodium dihydrogen carbonate), 4' -oxo-diphenyl sulfonyl hydrazide OBSH, toluene sulfonyl phthalein semicarbazide and urea; preferably, the foaming agent is 4,4' -oxybis-benzenesulfonyl hydrazide OBSH.
Wherein the degradable foaming packaging material comprises the following components in parts by weight:
100 parts of degradable resin;
1-100 parts of lignin;
5-30 parts of foaming agent.
Preferably, the weight part ratio of the degradable resin to the lignin is 100 parts: 30-100 parts of a solvent; further preferably 100 parts: 30-60 parts; more preferably 100 parts: 50 parts of the raw materials.
Further preferably, the degradable foaming packaging material further comprises any one or a combination of several of a compatilizer, a filler and a nucleating agent.
Wherein the compatilizer is any one or combination of two of epoxy chain extender and isocyanate chain extender; wherein the epoxy chain extender is preferably a Basff chain extender with the model number ofADR-4400, or ADR-4468; wherein, the isocyanate chain extender includes but is not limited to toluene diisocyanate chain extender (TDI).
Wherein the filler is any one or combination of more of calcium carbonate, calcium sulfate, starch, talcum powder, montmorillonite and wood fiber; preferably, the mesh number of the calcium carbonate and the calcium sulfate is 2000-3000 meshes; the mesh number of the wood fiber is 600-1500 meshes.
Wherein the nucleating agent is any one or the combination of more of phenyl zinc phosphate (TMC-200) and sebacic acid diphenyl dihydrazide (TMC-300).
Wherein the degradable foaming packaging material comprises the following components in parts by weight:
wherein, the weight portions of the compatilizer, the filler and the nucleating agent are not 0 at the same time.
Further preferably, the degradable foaming packaging material comprises the following components in parts by weight:
wherein, the weight portions of the compatilizer, the filler and the nucleating agent are not 0 at the same time.
The preparation method of the degradable foaming packaging material is also within the protection scope of the invention and comprises the following steps:
s1: according to the formula ratio, mixing the dried materials, placing the mixture in parallel double screws, carrying out high-temperature shearing at the temperature of 150-170 ℃, and carrying out extrusion pre-foaming through a microporous template of the double screws;
s2: placing the pre-foamed material in a secondary forming device at the temperature of 160-165 ℃ under the pressure of 1 multiplied by 105~2×105Foaming under Pa, and cooling and shaping at 30-80 deg.C.
In the step S1, the aperture of the double-screw micropore template is 0.1-0.9 mm.
Has the advantages that: compared with the prior art, the invention has the following advantages:
according to the invention, the lignin is applied to the degradable foaming packaging material, and can effectively replace degradable resin, so that the cost is reduced; the modified esterified lignin can act on other aromatic polyesters such as PBAT or PBST, so that the bonding strength between degradable resins is further improved, the performance of the material is improved, the using amount of the lignin can be further improved, and the cost is further reduced.
Detailed Description
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified. In the invention, the lignin is modified by the prior art, the same modification is carried out, different modification methods have little influence on the lignin, and the following esterification, epoxidation, phenolization and acylation are common modification methods in the field.
In the following examples, the lignin used includes unmodified lignin and modified lignin, and the particle size d50 is 3 to 8 μm.
The PLA used in the following examples was NatureWorks 4032D, USA, and PBAT was Xinjiang Lantun river TH 801T.
Examples 1 and 2, comparative examples 1 and 2
The formula is as follows: the dosage of the PBAT and the lignin is shown in Table 1 according to the weight portion of 70 portions of PLA, 20 portions of OBSH and 20 portions of epoxy chain extender ADR-44003 portions.
The preparation method comprises the following steps:
s1: according to the formula ratio, mixing the dried materials, placing the mixture in parallel double screws, carrying out high-temperature shearing at the temperature of 155-165 ℃, carrying out the rotation speed of the screws at about 40rpm, and carrying out extrusion pre-foaming through a microporous template (the aperture is 0.6mm) of the double screws;
s2: placing the pre-foamed material in secondary forming equipment (a vulcanizing machine) at the temperature of 160-165 ℃ under the pressure of 1 multiplied by 105~2×105Foaming under Pa, and cooling and shaping at 30-50 ℃ to obtain the product.
Two important properties of the obtained foam material, namely, density and impact strength, are detected, and the detection results are shown in table 1.
TABLE 1
Density g/cm3 | Impact Strength/KJ/m2 | ||
Comparative example 1 | 30 parts of PBAT and 0 part of lignin | 0.50 | 4.51 |
Example 1 | 30 parts of PBAT and 20 parts of alkali lignin | 0.34 | 4.62 |
Example 2 | 30 parts of PBAT and 20 parts of esterified alkali lignin | 0.33 | 6.39 |
Comparative example 2 | 30 parts of PBAT and 20 parts of corn straw fiber | 0.44 | 5.41 |
As can be seen from Table 1, the PBAT can be effectively replaced by the alkali lignin in the invention, the density can be effectively reduced by replacing 20 parts of the unmodified alkali lignin in example 1, and the impact strength is also kept at a level equivalent to that in comparative example 1; in example 2, the esterified alkali lignin is adopted, so that the impact strength can be further improved and reaches 6.39KJ/m2Also, the improvement is 41.6% compared to pure PBAT. Further compared with the corn straw fiber in the comparative example 2, the density of the foaming material prepared from the alkali lignin adopted in the example 2 is lower, namely the foaming ratio is higher, and the impact strength is improved to a certain extent; compared with other plant fibers, the esterified lignin adopted by the invention has better performance than other plant fibers.
Example 3
In the same manner as in example 2, only the esterified alkali lignin was replaced with the epoxidized alkali lignin, the phenolated alkali lignin and the acylated alkali lignin, respectively, and the results of the detection are shown in table 2.
TABLE 2
Density g/cm3 | Impact Strength/KJ/m2 | |
Alkali lignin | 0.34 | 4.62 |
Esterified alkali lignin | 0.33 | 6.39 |
Epoxy alkalized lignin | 0.33 | 4.11 |
Phenolated alkali lignin | 0.35 | 4.71 |
Acylated alkali lignin | 0.32 | 6.31 |
As can be seen from table 2, after the lignin is modified differently, the lignin has little influence on the density of the foam material, that is, the foaming ratio has no great influence; but the impact strength of the lignin is influenced to a certain extent after different modifications are carried out on the lignin, wherein the effect after acylation and esterification is better, because the lignin can have a structure similar to PBAT after the modification through acylation and esterification, the compatibility of the lignin and the PBAT is increased, and the impact strength of the lignin is better than that of the unmodified lignin and other modified lignin.
Example 4
As in example 1, only the alkali lignin was replaced with soda lignin, organosolv lignin and enzymatic lignin, respectively, and the densities thereof were 0.36g/cm3、0.35g/cm3、0.33g/cm3(ii) a The impact strength is respectively 4.3KJ/m2、4.1KJ/m2、4.5KJ/m2The results show that lignin pretreated by different methods has no great influence on the foaming ratio and the impact strength.
Example 5
The amount ratio of the degradable resin to the lignin was changed as in example 1, and is shown in Table 3.
TABLE 3
As can be seen from table 3, the addition of lignin contributes to the improvement of the expansion ratio for the unmodified lignin, but when the amount of lignin exceeds 30 parts, the change in density is low. Meanwhile, the addition of lignin is also beneficial to the improvement of the impact strength within the use amount of 20 parts, but the impact strength is reduced when the use amount of lignin is 20 parts.
Example 6
The ratio of the amount of the degradable resin to the amount of the esterified alkali lignin was changed as in example 2, and is shown in Table 4.
TABLE 4
As can be seen from table 4, the addition of esterified lignin contributes to the increase of the foaming ratio, and the overall change tendency thereof is similar to that of unmodified alkali lignin. Meanwhile, the addition of lignin is also beneficial to the improvement of the impact strength, but when the amount of the lignin is 50 parts, the impact strength is rather reduced, and compared with the unmodified lignin, the amount of the lignin can be further increased after the esterification modification.
Example 7
The amount ratio of PLA to PBAT was varied as in example 1, and is shown in Table 5.
TABLE 5
PLA | PBAT | Density g/cm3 | Impact Strength/KJ/m2 |
70 (example 1) | 30 | 0.34 | 4.62 |
60 | 40 | 0.38 | 4.60 |
50 | 50 | 0.42 | 4.37 |
40 | 60 | 0.47 | 4.28 |
As can be seen from Table 5, the density of the resulting foamed material increased with the reduction in the amount of PLA, indicating that the amount of PLA was advantageous for foaming; meanwhile, as the amount of PBAT is increased, the impact strength can also be improved.
Example 8
Just different fillers were added as in examples 1 and 2, respectively, as shown in table 6.
TABLE 6
As can be seen from table 6, in the case of adding the filler, the impact performance is still improved to a certain extent except that the calcium carbonate causes a slight increase in density and a slight decrease in foaming ratio; and when the corn stalk fiber and the esterified alkali lignin are used simultaneously, the effect is better than that of the corn stalk fiber and the unmodified lignin.
Example 9
The formula is as follows: 60 parts of PLA, 40 parts of PBST, 50 parts of acylated lignin, 5 parts of OBSH, ADR-44682 parts, 20 parts of corn fiber (d50 is 1mm) and TMC-2000.007 parts;
the preparation process comprises the following steps:
s1: according to the formula ratio, mixing the dried materials, placing the mixture in parallel double screws, carrying out high-temperature shearing at the temperature of 160-170 ℃, carrying out the rotation speed of the screws at about 45rpm, and carrying out extrusion pre-foaming through a microporous template (the aperture is 0.8mm) of the double screws;
s2: placing the pre-foamed material in secondary forming equipment (a vulcanizing machine) at the temperature of 160-165 ℃ under the pressure of 2 multiplied by 105Foaming under Pa, and cooling and shaping at 30 ℃ to obtain the product.
The resulting foam had a density of 0.31g/cm3 and an impact strength of 7.87KJ/m2。
Example 10
The formula is as follows: 50 parts of PLA, 50 parts of PBST, 50 parts of esterified lignin, 10 parts of OBSH, 20 parts of ADR-44682 parts of corn fiber (d50 is 1mm) and 2000.004 parts of TMC;
the preparation process comprises the following steps:
s1: according to the formula ratio, mixing the dried materials, placing the mixture in parallel double screws, carrying out high-temperature shearing at the temperature of 160-170 ℃, carrying out the rotation speed of the screws at about 45rpm, and carrying out extrusion pre-foaming through a microporous template (the aperture is 0.6mm) of the double screws;
s2: placing the pre-foamed material in secondary forming equipment (a vulcanizing machine) at the temperature of 160-165 ℃ under the pressure of 2 multiplied by 105Foaming under Pa, and cooling and shaping at 30 ℃ to obtain the product.
The density of the resulting foamed material was 0.23g/cm3Impact strength of 6.87KJ/m2。
Comparative example 3
As in example 1, only 30 parts of PBAT were replaced by 30 parts of polycaprolactone PCL, and the resulting foam had a density of 0.35g/cm3Impact strength of 4.14KJ/m2。
Comparative example 4:
in the same manner as in example 1, only 30 parts of PBAT were replaced with 30 parts of polycaprolactone PCL, and 20 parts of alkali lignin were replaced with 20 parts of esterified alkali lignin, and the resulting foamed material had a density of 0.35g/cm3Impact strength of 4.10KJ/m2。
It can be seen from comparative examples 3 and 4 that when a degradable resin such as PCL is used, the impact strength is not as good as PBAT and PBST, but the expansion ratio of the foam is not greatly affected; and even after the esterified lignin is adopted, the performance of the esterified lignin is not effectively improved.
The invention provides the idea and method of application of lignin in preparing degradable foamed materials, and the method and way for implementing the technical scheme are many, the above description is only a preferred embodiment of the invention, it should be noted that, for those skilled in the art, without departing from the principle of the invention, several improvements and modifications can be made, and these should be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. The application of lignin in preparing degradable foaming packaging materials;
wherein the lignin is lignin modified by esterification and/or acylation;
wherein, the degradable foaming packaging material also comprises degradable resin; the degradable resin is a mixture of one or two of polybutylene terephthalate-adipate and polybutylene succinate/terephthalate and polylactic acid;
wherein, the degradable foaming packaging material also comprises any one or a combination of a plurality of foaming agents, compatilizers and nucleating agents;
wherein the degradable foaming packaging material comprises the following components in parts by weight:
in the degradable resin, the weight parts of any one or two of polybutylene terephthalate-adipate and polybutylene succinate/terephthalate composition and polylactic acid are 30: 70, or 40: 60, or 50: 50;
wherein the particle size d50 of the lignin is 2-10 μm.
2. The use of claim 1, wherein the foaming agent is any one or a combination of azodicarbonamide, ammonium bicarbonate, sodium bicarbonate, 4' -oxybis benzenesulfonylhydrazide, toluene sulfonphthalein semicarbazide and urea.
3. The use of claim 1, wherein the compatibilizer is one or a combination of epoxy chain extender and isocyanate chain extender.
4. The use of claim 1, wherein the nucleating agent is any one or a combination of phenyl zinc phosphate and sebacic acid diphenyl dihydrazide.
5. The use according to claim 1, wherein said degradable foamed packaging material further comprises a filler.
6. The use according to claim 5, wherein the weight ratio of the degradable resin to the filler is 100 parts: and 20 parts.
7. Use according to claim 5, wherein the filler is wood fibres.
8. Use according to any one of claims 5-7, characterized in that the filler is corn stover fiber.
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