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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2024 , Vol. 36 >Issue 4: 486 - 500

DOI: https://doi.org/10.7536/PC230727

Review

The Bioplastics from Plant Tesources

  • Wang Lei 1 ,
  • Zheng Ruihang 1 ,
  • Qiu Yongkang 1 ,
  • Guo Bin , 1, 2, 3, * ,
  • Li Panxin 2, 3
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  • 1 College of Science, Nanjing Forestry University, Nanjing 210037, China
  • 2 Agricultural and Forest Products Processing Academician Workstation of Henan Province, Luohe 462600, China
  • 3 Post-Doctoral Research Center of Nanjiecun Group, Luohe 462600, China
*e-mail:

Received date: 2023-07-31

  Revised date: 2023-09-30

  Online published: 2024-02-26

Supported by

Jiangsu Government Scholarship for overseas studies, the Nanjing Forestry University Yong top talent program, Postgraduate Research &Practice Innovation Program of Jiangsu Province(SJCX22_0318)

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Abstract

in order to alleviate the environmental pollution and energy crisis caused by petroleum-based plastics,biodegradable plastics are gradually becoming the focus and hot spot of the development of the plastics industry.plant resources include a variety of available components,such as lignin,cellulose,vegetable oil,terpenes,etc.these natural polymers or small molecules can be used to prepare bioplastics,with the advantages of renewable,non-toxic,completely degradable and so on.This review includes two types of direct and indirect utilization(including chemical modification,biochemical modification and microbial fermentation)for plant resources,and focuses on the recent progress of eight plant components(cellulose,lignin,hemicellilose,starch,plant protein,vegetable oil,terpenes and tannins)in the field of bioplastics,and discusses in detail application characteristics of These natural plant components.Finally,the trend in future is also proposed。

Contents

1 Introduction

2 Cellulose

2.1 Nanocellulose or cellulose nanofibers

2.2 cellulose derivative

3 Lignin

3.1 Direct utilization

3.2 Indirect utilization(chemical modification)

4 Hemicellilose

4.1 Xylan

5 Starch

5.1 Direct utilization

5.2 Indirect utilization

6 Plant protein

6.1 Direct utilization

6.2 Indirect utilization(chemical cross-linking)

7 Plant oil

7.1 Microbial fermentation

7.2 Chemical modification

8 Terpenoids

8.1 Direct utilization

8.2 Indirect utilization(chemical modification)

9 Tannin

9.1 Direct utilization

9.2 Indirect utilization(chemical modification)

10 Conclusion and outlook

Key words： plant resources; bioplastics; cellulose; lignin

Cite this article

Wang Lei , Zheng Ruihang , Qiu Yongkang , Guo Bin , Li Panxin . The Bioplastics from Plant Tesources[J]. Progress in Chemistry, 2024 , 36(4) : 486 -500 . DOI: 10.7536/PC230727

1 Introduction

The development of environment-friendly plastics based on renewable resources to replace petroleum-based plastics is an urgent problem to be solved in today's society[1⇓~3]。 Bioplastics are expected to solve this problem,which is a hot research topic in this field in recent years.Bioplastics are mainly prepared from biomass(such as cellulose,starch,lignin,etc.)[4][5][6]。 Compared with petroleum-based plastics,bioplastics have the advantages of renewability and degradability,and can be widely used in food packaging and daily commodities[7]。
Plant resources include a variety of available components,such as lignin,cellulose,vegetable oil and terpenes.These natural macromolecules or small molecules can be used to prepare bioplastics,which are renewable,non-toxic and completely degradable.They also reduce dependence on fossil fuels,reduce carbon emissions,contribute to environmental protection and promote sustainable development[8][9]。 At present,According to the molecular weight of the components used in plants,they can be divided into two categories,namely,plant-derived macromolecular compounds and small molecular compounds.according to the different application methods,it can be divided into direct and indirect utilization,and indirect utilization includes chemical modification,biochemical modification and microbial fermentation[10]。 As shown in Table 1,this paper systematically introduces the research status and progress of eight main components of plant resources(cellulose,lignin,hemicellulose,starch,plant protein,vegetable oil,terpenoids,tannin)in bioplastics according to different application modes,and looks forward to the future development trend。
表1 Application and Classification of Plant Resources in Bioplastics

Table 1 Classification of bioplastics based on plant resources

Application

Plant resources		 Direct utilization Indirect utilization
Chemical modification Biochemical modification Microbial fermentation
Plant derived macromolecules Cellulose √
Lignin √ √
Hemicellulose √ √
Starch √ √ √ √
Plant protein √ √
Plant derived small molecules Plant oil √ √
Terpenoids √ √
Tannin √ √

2 Cellulose

Cellulose is a macromolecular polysaccharide composed of glucose,which is abundant in renewable resources such as wood,cotton,hemp,straw,wheat straw and bagasse,and the content of Cellulose in cotton is close to 100%[11]。 cellulose molecular chain contains a large number of hydroxyl groups,which can undergo various esterification and etherification reactions to obtain Cellulose derivatives with special properties[12]。 in recent years,the application of cellulose in bioplastics has focused on cellulose nanofibers(CNF)or cellulose nanocrystals(CNC)obtained by chemical modification,as well as cellulose derivatives(such as methyl cellulose,carboxymethyl cellulose,etc.),which are highlighted in this section[13]。

2.1 CNF or CNC

CNF or CNC is nanoscale cellulose,which is nanoscale fiber or crystal extracted from natural cellulose[14]。 CNF is a kind of filamentous cellulose fiber with a diameter of 5~20 nm and a length of hundreds of nanometers to tens of microns,which is widely used in textile,papermaking,biomedical and other fields.CNC is a nanorod material with natural chirality,which has unique optical properties to form cholesteric liquid crystals,and has applications in optoelectronics,information storage,food,textile,paper,medicine and environment。

2.1.1 Unmodified

Reshmy et al.Extracted CNC from jackfruit(Artocarpus heterophylus)peel by acid hydrolysis,and mixed it with different plasticizers(glycerol,polyethylene glycol,polyvinyl alcohol,triethyl citrate)and a new filler,mastic(gum obtained from mastic tree),to prepare films by solution casting[15]。 It was found that the surface morphology was improved by different plasticizers,and more stable hydrogen bonding was formed among CNC,plasticizer and filler through self-assembly during film formation。
Liu et al.Hydrolyzed bagasse with concentrated sulfuric acid to obtain CNC,and prepared polyvinyl alcohol(TPVA)and CNC-TPVA by melt blending,and then blended TPVA and CNC-TPVA with poly(butylene terephthalate)and poly(lactic acid)composites(COM)respectively to explore the effect of CNC on UV aging properties[16]。 It was found that the interfacial compatibility between CNC and PVA was good,and CNC did not affect the crystallinity of PVA,but reduced the plasticizing effect of PVA.Compared with CNC-TPVA-COM,the cross section roughness,hydrogen bond strength and aging resistance of CNC-TPVA-COM are improved。
Reducing the average coefficient of thermal expansion and improving the thermal dimensional stability is another feature of CNF to improve the performance of bioplastics.Guan et al.Reported a polymeric structural material derived from plant CNF.Under the control of Ca2+,the Ca2+in CNF hydrogel interacted with carboxyl groups,and hydrogen bonds were formed between the hydroxyl groups on the surface of CNF,thus forming a reversible interaction network between CNFs[17]。 This all-green material significantly improves the bending strength(~300 MPa)and modulus(~16 000 MPa),and the average thermal expansion coefficient is only 7×10-6K-1,which is less than 10%of that of petrochemicals,indicating that its size is almost unchanged when heated,and it has better thermal dimensional stability than plastics 。
CNF can also be used to reinforce bioplastics.Ulrich et al.Studied the properties of CNF-reinforced K-carrageenan/alginate film(Kc/Alg)[18]。 the results show that the addition of CNF enhances the mechanical and thermal stability of the membrane.the maximum tensile strength of the composite film was 58.9 MPa without adding plasticizer.the Kc/Alg/CNF composite film can be used as coating materials for packaging,drug carriers and nutrients.In addition,for PBAT/TPS composite bioplastics,the reinforcement effect is obvious after adding CNF.Fourati et al.Studied the effect of CNF content on the properties of PBAT/TPS composite system and found that the tensile strength and modulus were improved with the addition of CNF,and the best properties were achieved at 8 wt%CNF[19]。 Therefore,the ternary PBAT/TPS/CNFs blends can help to improve the properties of this type of biodegradable plastics。
In addition,CNF can also be used to improve impact toughness.Katagiri et al.Prepared samples by changing the stacking sequence of CNF dispersion layers and hydrophobic treatment,and then inserting CNF dispersion layers into carbon fiber reinforced plastic(CFRP)prepreg,and carried out pendulum impact test[20]。 the results show that when the CNF dispersion layer is inserted below the surface prepreg,the impact value increases by 6%compared with the CFRP without CNF dispersion according to the impact waveform。
Therefore,CNC or CNF prepared from waste plant resources can play a role in strengthening,toughening,improving aging resistance and thermal dimensional stability in bioplastics,and is cheap and does not affect biodegradability。

2.1.2 Fatty acid modification

the purpose of fatty acid modification is to improve the hydrophobicity and dispersibility of CNC.Huang et al.Used cassava residue as raw material to prepare CNC and then modified it with stearic acid.the modified CNC was added to polylactic acid(PLA)film-forming solution at the concentrations of 0 wt%,0.5 wt%,1.0 wt%,1.5 wt%and 2.0 wt%.The study found that when the addition amount was 1.0 wt%,the modified CNC was uniformly dispersed in PLA and co-crystallized to form a stable network structure.The tensile strength of the composite film was increased by 40.03%,and the elastic modulus was increased by 55.65%[21]。

2.1.3 Graft modification

In recent years,the method of grafting small molecules or oligomers on the surface of cellulose for bioplastics has been widely used[22]。 isocyanate small molecules have active Isocyanate groups,which can efficiently react with hydroxyl groups in cellulose to achieve the purpose of reinforcement and hydrophobicity after grafting[23]。
Pinheiro et al.Extracted CNC from monocuba fiber by acid hydrolysis,then grafted it with octadecyl isocyanate,and added different concentrations of modified CNC(3 wt%,5 wt%and 7 wt%)to PBAT[24]。 the results show that the addition of modified CNC enhances the thermal,rheological and mechanical properties of the composite without affecting the biodegradability.As shown in fig.1,Morelli et al.Grafted CNC with phenylbutyl isocyanate,and added the modified CNC to PBAT by melt extrusion to obtain the composite[25]。 the results showed that the elastic modulus of the composite was increased by 55%and the water vapor permeability was decreased by 63%compared with pure PBAT,and the biodegradability of PBAT was not affected。
图1 纤维素纳米晶与苯基丁基异氰酸酯的反应[25]

Fig. 1 Reaction formula of CNC with phenylbutyl isocyanate[25]

In addition,low molecular weight polybutadiene glutarate was also grafted on the surface of CNC,and the elastic modulus of PBAT increased by 50%after adding the grafted CNC[26]。 Dynamic mechanical thermal analysis shows that CNC/PBAT composites maintain their high modulus even at temperatures well above the glass transition temperature of PBAT,and the storage modulus of the composites is about 200%higher than that of pure PBAT at 608℃.Therefore,the grafted CNC can effectively improve the properties of the bioplastic matrix to achieve the purpose of reinforcement and hydrophobicity。

2.1.4 Other modification

Acetylation modification is also a common modification method in recent years.Barbosa et al.Used acetylated nanocellulose(CNS)as a reinforcing agent added to PBAT to study the effect of the interaction between CNS and PBAT on the mechanical and thermal properties[27]。 It was found that the acetylated CNS could be uniformly dispersed in PBAT and form a strong interaction,the maximum elastic modulus reached 86.9 MPa,and the maximum degradation temperature was 385℃。
In addition,Zhang Chunmei et al.Modified CNC with polyethylene glycol(PEG)and then melt-blended with PLA to obtain CNC-PEG/PLA composites,and studied their non-isothermal crystallization behavior at different heating rates[28]。 It was found that the thermal stability of CNC-PEG composite was higher than that of pure PLA due to the presence of PEG group in CNC-PEG.Kissinger formula was used to fit the non-isothermal crystallization process of the composites,and the crystallization activation energy of PLA decreased with the increase of CNC-PEG content,which was related to the plasticization effect of PEG part on PLA。

2.2 Cellulose derivative

Methylcellulose(MC)is obtained by introducing methyl groups into cellulose through etherification,and is often used as a viscosity modifier in paints,building materials,and foods or to prepare water-absorbing resins[29][30]。 It is also used in bioplastic films.Lyytik Lyytikäinen et al.Mixed MC,ethyl(hydroxyethyl)cellulose(EHEC),natural microfibrillated cellulose(MFC)and nanocellulose to prepare films[31]。 the effects of membrane composition and drying temperature on oxygen permeability and oil resistance were studied.It was found that with the increase of MFC content,the oxygen barrier performance of the film was improved,but when the film was dried at 50℃,the oxygen barrier performance of the film with MFC was poor.the oil resistance and grease resistance of all samples were more than 24 H,but the surface oil diffusion of different samples was quite different。
Carboxymethyl cellulose(CMC),which is obtained by carboxymethylation of cellulose,also has the advantages of biodegradability,non-toxicity and biocompatibility.Gao et al.Proposed a method of adding CMC to quaternized hemicellulose(QH)to prepare blend films[32][33]。 the results show that the surface of the film becomes dense,uniform and smooth after the addition of CMC.the transparency of the blend film increases with the increase of CMC content,and the maximum tensile strength can reach 65.2 MPa,which is due to the strong hydrogen bonding between CMC and QH,which significantly enhances the mechanical properties。
Xu et al.Blended bamboo-based CMC with polyvinyl alcohol(PVA)and crosslinked it with glutaraldehyde to prepare a liquid membrane[34]。 it was found that the liquid film could be quickly formed on the soil surface by spraying It on the soil.Bamboo and wood mulching film has strong mechanical properties(18.2 MPa),good light transmittance(74.2%),moisture absorption rate(141%)and soil water retention properties,and about 64%of the film can be biodegraded in the soil within 60 days without post-treatment。
Li et al.Used polyanionic sodium carboxymethyl cellulose(CMC)and polycationic chitosan(CS)to prepare polyelectrolyte composite membranes,and studied the effects of acetic acid buffer with different concentrations and pH values on the membrane performance[35]。 The results showed that all the membranes were compact in the surface layer and porous in the inner layer.The membranes prepared in 0.1 mol·L-1acetic acid buffer had an irregular porous surface,while the membranes prepared in 0.5 and 1.0 mol·L-1acetic acid had an apparently compact surface,which had a tunable pure water permeability and was able to effectively(∼99%)remove oil droplets from oil-in-water emulsions 。
κ-carrageenan in seaweed is a potential reinforcing material for improving the mechanical properties of bioplastics.Abdullah et al.Addedκ-carrageenan to CMC/starch to prepare films,and studied its effects on the properties of CMC/starch[36]。 the results showed that the strength of the membrane could be increased to 15.7 MPa with higherκ-carrageenan concentration.FT-IR spectra showed that CMC/starch matrix interacted withκ-carrageenan to form strong hydrogen bonds.Thermogravimetric analysis showed that the bioplastic with 25 wt%carrageenan had the least mass loss and better thermal stability。

3 Lignin

Lignin contains the most abundant aromatic compounds on earth,with three main structures:guaiacyl propane,syringyl propane,and p-hydroxyphenylpropane[37]。 Lignin has abundant functional groups,such as benzene ring,carbonyl group,methoxyl group,etc.,which can provide bioplastics with excellent properties such as ultraviolet absorption,antibacterial,antioxidant and water resistance[38]。

3.1 Direct utilization

Adding lignin directly to bioplastics is the most convenient way,which has the effects of reinforcement,oxidation resistance,antibacterial and ultraviolet resistance。

3.1.1 Reinforcing agent

Aromatic structures in lignin can provide hardness and strength to plastics.Ortiz et al.Combined lignin,epoxidized linseed oil,and bio-based diamines derived from fatty acid dimers to prepare an all-bio-based epoxy resin[39]。 It was found that the glass transition,Young's modulus and thermal degradation temperature increased with the increase of lignin content in the resin,and the effect was more obvious with the increase of lignin content。
Yu et al.Prepared biocomposites containing lignin and cellulose by mixing and dissolving corncob and wheat straw in benzyltrimethylammonium hydroxide aqueous solution[40]。 It was found that the biocomposite had a tensile strength of 96.7 MPa and an ultraviolet absorption of more than 81.8%。
lignin can also improve mechanical properties by improving compatibility.Nair et al.Mixed high Lignin content nanofibrils(NCFHL)with PLA to form a composite film by casting and hot pressing[41]。 It was found that lignin significantly improved the compatibility between NCFHL and PLA.the results of atomic force microscope-infrared spectroscopy show that there is an effective coupling between the two at the nanoscale.Compared with pure PLA,the modulus and strength of the composite film increased by 88%and 111%,respectively,and the water vapor permeability decreased by 52%with the addition of 10 wt%NCFHL。

3.1.2 Antioxidant

Yang et al.Prepared polymer membranes based on lignin nanoparticles(LNP),chitosan(CH)and polyvinyl alcohol(PVA)by solvent casting,and studied the properties of binary(CH/PVA)and ternary(LNP/CH/PVA)composite membranes[42]。 It was found that the antioxidant activity of the ternary composite membrane with 3 wt%LNP was 4.5 times higher than that of the binary system,and the addition of LNP also improved the tensile strength and Young's modulus,and inhibited the growth of bacteria。
Ji et al.Prepared a biodegradable chitosan-based film containing lignin and trace ramie fiber by casting method and studied its properties[43]。 the results showed that the antioxidant activity of the film increased by 288%and the water absorption decreased by 41.2%with the addition of 20 wt%lignin,and the tensile strength increased by 29.6%with the addition of 20 wt%ramie fiber。
Lignin isolated from grape seeds(GS-L)also has high antioxidant activity.Vostrejs et al.Added 1 wt%~10 wt%GS-L to poly(3-hydroxybutyrate)(PHB)and polyhydroxyalkanoate(PHA),and studied their antioxidant properties[44]。 the results showed that when the content of GS-L was 1~5 wt%,it had obvious antioxidant activity,while the oxygen permeability and carbon dioxide permeability decreased。

3.1.3 Antibacterial agent

lignin can also play an antibacterial role in bioplastics.He et al.Studied the effect of grafting modification of lignin with polyhexamethylene guanidine(PHMG)on the properties of lignin/poly(butylene succinate-co-butylene terephthalate)(PBST)composites[45]。 the results show that the composite has good mechanical properties,the tensile strength is 20.69 MPa and the elongation at break is 414.88%.antibacterial experiments showed that lignin and lignin/PHMG had a lasting synergistic Antibacterial effect on Escherichia coli and Staphylococcus aureus。
Rizal et al.Studied the effect of unpurified and purified LNP on the antibacterial property of bioplastic film[46]。 the results showed that the purified LNP membrane was superior to the unpurified LNP membrane in terms of surface roughness,hydrophobicity and antibacterial property.Among them,the LNPs membrane with 5%purity had the best performance,and had better inhibition effect on Escherichia coli and Staphylococcus aureus,and all the membranes were completely degraded after 40 days of burial in the soil。

3.1.4 Anti-ultraviolet agent

The benzene ring structure in lignin also makes it have good ultraviolet absorption ability.Abbadessa et al.Prepared films by compounding softwood sulfate lignin(S-lignin)and lignin nanoparticles(S-LNPs)with polysuccinate(PBS),respectively[47]。 It was found that S-LNPs had better UV absorption properties compared with S-lignin,which was related to the higher specific surface area of nanoparticles.In addition,Hararak et al.Coated lignin-based polymer with polyethyleneimine or chitosan on PE film layer by layer,and the anti-UV performance was significantly improved with the increase of the number of layers[48]。

3.2 Indirect utilization (chemical modification)

Chemical modification of lignin for the preparation of bioplastics is also one of the research hotspots in recent years.Aromatic rings and hydroxyl groups in Lignin can be chemically modified.Recently,there are many studies on the modification of Lignin by grafting with small molecules,demethylation,hydroxypropylation and lignin salt,which are by-products of papermaking.These methods can improve the reactivity,effectively improve the compatibility between different components and improve the performance[38,49] 。

3.2.1 Graft modification

In order to improve the compatibility between lignin and polyurethane matrix,Zhang et al.Added the graft modified lignin into vegetable oil-based polyurethane[50]。 It was found that octadecyl isocyanate modified lignin was more compatible with polyurethane matrix than butyric anhydride modified lignin,and high lignin content(30 wt%)increased Young's modulus and thermal stability,and increased dielectric constant compared with pure polyurethane。
Lignin was grafted with maleic anhydride(MAPE)and urea(Ur)respectively,and then freeze-dried and melt-extruded with high density polyethylene(HDPE)to obtain composites[51]。 It was found that the tensile strength of the composites modified by MAPE and Ur increased by 9.45%and 14.06%,respectively.Both of them inhibited the crystallization of HDPE,and the crystallinity of Ur grafted composite was only 16.25%.SEM showed that the grafted lignin had better dispersion in the plastic matrix。

3.2.2 Demethylation

The purpose of lignin demethylation is to increase the content of phenolic hydroxyl groups,which is beneficial to the rapid completion of phenolic polycondensation.Li et al.Used sodium sulfite as a catalyst to demethylate alkali lignin,and studied the structure of lignin-based phenolic resin by13C-NMR and FT-IR,as well as its physical properties and demethylation mechanism[52]。 the results showed that with the demethylation of lignin,the methoxyl content decreased from 1.93 mmol/G to 1.09 mmol/G,and the phenolic hydroxyl content increased from 0.56 mmol/G to 0.82 mmol/g.the lignin-based phenolic resin had faster curing speed and shorter gel time.In addition,the bonding strength increased from 0.92 MPa to 1.07 MPa after lignin demethylation。

3.2.3 Hydroxypropylation

Due to the poor compatibility between lignin and PLA,Choi et al.Modified ethanol lignin(EOL)by hydroxypropylation to improve the interfacial compatibility,and studied the effect of the structure of EOL on the change of thermal properties[53]。 the results show that the thermal properties of hydroxypropylated EOL depend on the structural characteristics of the initial EOL and the degree of polymerization of propylene oxide.Hydroxypropylation of EOL extracted under relatively mild conditions enhances the thermoplasticity and improves the dispersion and interfacial compatibility of EOL in PLA matrix。
Lee et al.Used methanol-insoluble high molecular weight softwood kraft lignin as raw material for hydroxypropylation catalyzed by NaOH,and further reacted with sebacic acid or polybutadiene(dicarboxyl-terminated)to prepare biopolyesters[54]。 It was found that the polyether chain was extended due to the hydroxypropylation reaction,and the decomposition temperature of hydroxypropylated lignin was 217℃and 367℃,and the decomposition temperature of biopolyester prepared with sebacic acid and polybutadiene(dicarboxyl terminated)was 380℃and 453℃,respectively,which indicated that the thermal properties of biopolyester were significantly improved。

3.2.4 Lignin salt

Lignosulfonate(LSS)and alkali lignin(AL)are derived products from pulping and papermaking.Zadeh et AL.Added AL and LSS at different concentrations to enzyme-modified soy protein isolate(SPI)membranes to improve performance[55]。 the free radical scavenging activity test showed that the value of the membrane containing LSS was 28%and 6%higher than that of the membrane based on AL,respectively;However,the free radical scavenging activity of AL itself was significantly higher than that of LSS,indicating that the activity of lignin would be affected by the interaction with SPI.in addition,the film containing AL has a strong absorption In the UV region,and the addition of both lignins can improve the tensile strength and thermal stability of the film。
Ferdosian et al.Synthesized lignin-based epoxy resin by depolymerizing sulfate lignin(DKL)or depolymerizing organic solvent lignin(DOL)with epichlorohydrin under alkaline condition in the presence of phase transfer catalyst,and then reacted with curing agent 4.4[4]-diaminodiphenylmethane(DDM)or diethylenetriamine(DETA)reacts to form a crosslinked structure.It is found that the total activation energy of DOL and DKL based epoxy resins cured by DETA is higher than that cured by DDM,indicating that aromatic amines have better curing activity for lignin-based epoxy resins than aliphatic amines[56]。 the activation energy of DKL based epoxy resin was lower than that of DOL based epoxy resin during the whole curing process,which may be due to the fact that the chemical structure of DKL contains more hydroxyl groups,which promotes the curing process。

4 Hemicellulose

Hemicellulose exists in the primary and secondary cell walls of land plants,freshwater plants and some algae,and is a polymer composed of different types of monosaccharides,including xylose,arabinose and galactose[57][58]。 in recent years,bioplastics based on hemicellulose have been widely used because of their renewability,degradability,and high transparency In the visible to near-infrared region[59][60]。 Among them,xylan is reported more,and this part focuses on it。

4.1 Xylan

4.1.1 Direct utilization

Mixing xylan With starch-based plastics can not only improve the properties of starch-based plastics,but also maintain the complete biodegradability.Macedo et al.Compounded xylan with starch and glycerol to prepare bioplastics.with the increase of xylan addition,the hydrophilicity increased[61]。 When the xylan content was 5 wt%and 10 wt%,the bioplastics had better mechanical properties,and the tensile strength was 2.35 and 2.56 MPa,respectively.in addition,it can be completely biodegraded after being buried In soil for 30 days.Abe et al.Studied the biodegradability and ecotoxicity of xylan/starch bioplastics with different formulations under composting conditions[62]。 It was found that all bioplastics began to degrade within 3 days,and the sample with 25 wt%xylan/75 wt%starch disappeared within 13 days.the ecotoxicity test showed that the degradation had no inhibitory effect on the growth of microorganisms,and the seed germination rate was 100%。

4.1.2 Chemical modification of xylan

Xylan can also be chemically modified to make bioplastics[63]。 Jia et al.Proposed a double crosslinking strategy to prepare xylan plastics(XP)with high toughness,biocompatibility and biodegradability by etherification and hot pressing[64]。 It was found that the tensile strength,toughness and modulus of XP could reach 55 MPa,2.2 MJ/m3and 1700 MPa,respectively,by chemical and physical double crosslinking,which were superior to those of reported xylan-based films and some general-purpose plastics.Dynamic mechanical analysis shows that XP is thermoplastic,and 2D/3D shapes can be repeatedly prepared by thermoforming and adjusting the reversible hydrogen bonds of water molecules.In addition,XP is non-toxic,has low thermal expansion coefficient and excellent optical properties,and can be completely degraded within 60 days 。
As shown in Figure 2,Polunin et al.Modified xylan(X-MA)with maleic anhydride and then grafted and copolymerized with basu oil-based acrylic monomer(BBM)to obtain X-MA/PBBM,which was then mixed with carnauba wax(CW)to prepare bioplastics[65]。 It was found that the storage modulus and Young's modulus of the blend containing 40 wt%CW were 475 MPa and 248 MPa,respectively,which were close to those of LDPE。
图2 BBM与马来酸酐改性木聚糖接枝共聚反应[65]

Fig. 2 Graft Copolymerization of BBM and X-MA[65]

5 Starch

starch is a polysaccharide composed of glucose units,which widely exists in seeds,roots,stems and other tissues of plants.According to different sources,it can be divided into cereal,potato and legume Starch[66,67]。 Bioplastics are currently prepared by fermentation processes using natural starches,biochemically or chemically modified starches,and starches as carbon sources。

5.1 Direct utilization

Natural starch has crystalline and semi-crystalline structure,and can be transformed into amorphous state under the combined action of high temperature,shear force and plasticizer,which is called thermoplastic starch(TPS)[68]。 In general,it is an efficient and convenient way to prepare starch-based bioplastics by using thermoplastic starch as the main matrix and adding other components to adjust its properties。
Niu et al.Prepared biodegradable composite films with potato starch,glycerol and gelatin[69]。 the effects of different ratios on The mechanical and barrier properties were studied.The results showed that the film prepared by 2.5 wt%starch,2.0 wt%glycerol and 1.5 wt%gelatin exhibited excellent properties,with tensile strength of 4.47 MPa,elongation at break of 109.91%,and transmittance at 500 nm of 41.21%.FTIR and SEM also confirmed that starch,glycerol and gelatin had good compatibility。
In order to improve the degradability of starch-based plastics,Zoungranan et al.Prepared bioplastics by adding natural ingredients extracted from kola tree to cassava starch and corn starch,respectively,and evaluated the biodegradability through soil burial experiments[70]。 It was found that the addition of natural ingredients extracted from kola tree significantly improved the degradability of bioplastics compared with pure cassava or corn bioplastics.in addition,cassava bioplastic degrades faster than corn bioplastic,which is due to the higher concentration of microorganisms In cassava bioplastic(20%)than corn bioplastic(10%)。
in order to improve the mechanical and water resistance of TPS and endow it with antibacterial properties,our research group proposed a new method to replace part of glycerol In TPS with low-cost and renewable rosin(R)[71]。 It was found that compared with pure TPS,the tensile strength of rosin modified 80R-TPS increased from 1.42 MPa to 4.61 MPa,and the flexural strength increased from 0.40 MPa to 8.33 MPa,which were 3.25 and 20 times,respectively.the surface contact angle increased from 30.8ºto 68.0º,and the equilibrium moisture content decreased from 9.253%to 6.249%after 970 H,indicating that the water resistance was improved significantly。
Different kinds of starch can also be used to prepare bioplastics after mixing.Shafqat et al.Mixed banana peel starch,corn starch and rice starch,used potato peel powder and wood flour as fillers,and used glycerol and sorbitol as plasticizers to study the effects of fillers and plasticizers on the properties of bioplastics[72]。 the results showed that the sample containing glycerol had the lowest tensile strength and Young's modulus,the sample containing sorbitol had the highest tensile strength and Young's modulus,and the sample using glycerol-sorbitol combination as plasticizer had intermediate results.the addition of filler prevents the absorption of water;In addition,the biodegradability of the sample can be improved by the addition of plasticizer。

5.2 Indirect utilization

5.2.1 Microbial fermentation

5.2.1.1 Polyhydroxyalkanoate

Polyhydroxyalkanoate(PHA)is a polyester synthesized by microorganisms,which has good water resistance and biodegradability.Krueger et al.screened 72 strains of bacteria to grow in the medium with cassava starch hydrolysis by-products,and then screened 4 strains of Bacillus megaterium according to their growth and PHA production potential,with the highest yield of 4.97 G dry biomass/L[73]。 the process of producing PHA from starch residue by the strain can reduce the cost of PHA production and wastewater treatment。
Guzm Guzmán et al.Used the starch of potato peel as a carbon source to produce PHA using natural halophilic bacteria[74]。 the results showed that 38.92%of the strains showed PHA particles stained by Sudan black B,and 20 kinds of bacteria with PHA particles were fermented at the proportion of 65%-75%,and the yield was 0.174-0.889 G/L。
Sohail et al.Optimized PHA production with different strains using starch as carbon source[75]。 Optimal PHA production was found to occur within 24 to 48 H.PHA production reached a maximum at 24 H.PHA production decreased gradually after 48 H.According to the number of intracellular particles,size and PHA production,the most suitable strain for PHA production was found to be Bacillus agave。

5.2.1.2 Polyhydroxybutyrate

Polyhydroxybutyrate(PHB)is another microbially synthesized polyester,and Bomrungnok et al.Used Bacillus to produce PHB from starch in agricultural waste[76]。 the strain hydrolyzed cassava pulp and oil palm dry starch,and accumulated PHB up to 17 wt%of cell dry weight.theα-amylase(AmyA)of the strain showed high activity in The presence of cassava pulp starch and oil palm dry starch,and further saccharification of starch allowed the strain to grow and produce PHB directly from cassava pulp and oil palm dry starch。
Compared with other microorganisms,halophilic archaea have the advantage of Using soluble starch as a carbon source to produce PHB at high salinity(250 G/L NaCl).using starch as the sole carbon source,Karray et al.Isolated 33 strains of halophilic archaea from three enrichment cultures of high salt lakes in Tunisia by Nile red/Sudan black staining.After further isolation and detection,they found that the three strains had the best PHB production effect,reaching 9.25%,7.11%and 1.42%of the dry cell weight,respectively[77]。
From the above research,it can be seen that the advantage of using starch as carbon source to prepare bioplastic PHA or PHB through fermentation process lies in the low cost of raw materials,while the disadvantage lies in the long fermentation period,the need for screening of strains,and the need for optimization of the process,which is not conducive to large-scale industrial production。

5.2.2 Biochemical or chemical modification

Starch-based bioplastics have the disadvantages of low strength,hydrophilicity,poor thermal stability and high water vapor permeability,which can be remedied by biochemical or chemical modification.Transgenesis,etherification,esterification,oxidation,and cross-linking are commonly used methods[78]。

5.2.2.1 Transgene

natural starch includes both amylose and amylopectin,and The bioplastics prepared from amylose have good properties,but it is difficult to directly separate amylose from Natural starch.the direct production of amylose by transgenic microorganisms or crops opens up a new direction。
in recent years,the use of transgenic amylose to prepare bioplastics has been reported.Sagnelli et al.Used an amylose(AO)synthesized from transgenic barley with water and/or glycerol In an extrusion process to prepare bioplastics[79]。 It was found that the amylose was mainly of A-type crystallization,while the extruded AO sample showed Vh and B-type crystallization,and the breaking stress was increased by 6 times,and the breaking strain was increased by 2.5 times.the dynamic mechanical analysis showed that the storage modulus of the AO sample was also significantly increased.Subsequently,they used ordinary barley starch and AO as raw materials,glycerol as plasticizer and citric acid as crosslinking agent to improve mechanical properties[80]。 It was found that the breaking stress of crosslinked AO was 2 times higher than that of barley starch,the breaking strain was 1.6 times higher,the air permeability was equivalent to that of commercial Mater-Bi©plastic,and there was no difference in composting characteristics。

5.2.2.2 Oxidation

the oxidation of starch can convert The hydroxyl groups of glucose units into carbonyl groups,resulting in changes in properties.Oluwasina et al.Used cassava starch as raw material to prepare oxidized starch containing 15.68 wt%carbonyl and insoluble in water,and studied its effect on bioplastic film[81]。 the results showed that the water content and water solubility of the film decreased with the increase of the amount of oxidized starch,and the properties of the bioplastic film with oxidized starch were better than those without oxidized starch。

5.2.2.3 Acetylation

acetylated modified starch can improve hydrophobicity.Panrong et al.Used commercial Acetylated tapioca starch(AS)and tapioca starch AS raw materials to prepare films by blow molding[82]。 the results show that the addition of AS increases the surface hydrophobicity and water vapor permeability of the film,and the degree of substitution(DS)of AS affects the melt flow index,that is,the processability,thereby affecting the microstructure,mechanical and barrier properties of the film.Lipid oxidation when packaging soybean oil was effectively reduced by 38%due to the hydrophobic nature of the film matrix。

5.2.2.4 Crosslinking modification

crosslinking is an effective method to improve the properties of starch-based bioplastics.Glutaraldehyde,boric acid and epichlorohydrin in common Crosslinking agents are toxic,while citric acid(CA)is a natural non-toxic organic acid,which can be used to crosslink modified starch-based bioplastics.Yang et al.Prepared and characterized CA crosslinked oil palm empty fruit bunch fiber reinforced starch-based bioplastics[78]。 It was found that hydrogen bonds were formed between starch,fiber and CA,and the infrared spectrum confirmed that starch was esterified by CA.Scanning electron microscopy(SEM)showed that the fiber with a content of less than 10 wt%could be uniformly dispersed,and the addition of CA effectively promoted the compatibility between the fiber and starch,and improved the tensile strength and water resistance of the bioplastic。
Chakraborty et al.Prepared bioplastics with equal mass of mixed rice and potato starch and CA,and studied the effect of CA crosslinking on properties[67]。 The results show that the shape of the X-ray diffraction peak is broad,indicating that it is amorphous.The peak of 1716 cm-1in the infrared spectrum indicates the formation of ester bond after CA crosslinking.AFM showed that the surface roughness of bioplastics decreased with the increase of CA concentration 。
Different from the above crosslinking agents,photocrosslinking is also an effective method.Zhou et al.Used crosslinked shape memory polymers(SMPs)as inspiration,cassava starch as raw material,benzophenone(BP)as photocrosslinking agent,induced BP to decompose into free radicals under ultraviolet irradiation,and dehydrogenation on starch macromolecules to synthesize crosslinked starch films to obtain higher shape memory properties[83]。 the results showed that a three-dimensional crosslinked network was formed between the macromolecular chains of starch,which resulted In higher mechanical properties(tensile strength increased by 154%)and improved water resistance(water contact angle increased from 60ºto 87º)due to the reduction of free hydroxyl groups.in addition,the stable covalent bond has greatly improved the shape memory properties of the photocrosslinked film,with nearly 180ºbending recovery。

5.2.2.5 Other modification

Other modifications mainly include the polycondensation of starch and furfural,and the grafting of polymers on the surface of starch.Zhang et al.Proposed to prepare a thermosetting starch-furfural resin by polycondensation of gelatinized starch and corn-derived furfural in the presence of acid and formaldehyde,and studied its properties[84]。 the results showed that the bioplastic had smooth appearance,no cracks and bubbles,and the glass transition temperature was as high as 129℃,the weight loss rate was only 12%at 200℃,and the overall performance was better than that of phenolic plastics。
The interfacial adhesion between natural starch and PHA can be improved by grafting modification of natural starch with polymer.Xu et al.Used dibromoperoxide(DCP)as an initiator to graft PHA onto starch in situ[85]。 It was found that the gel yield of PHA/starch/DCP blends increased with the increase of DCP concentration up to 2 wt%,and obvious plastic deformation was observed at the interface between the two phases,while the interface of PHA/starch blends was completely debonded.The improved interfacial adhesion after grafting was further confirmed by the decrease in adhesion coefficient（Af）obtained from the dynamic mechanical analysis.In addition,PHA/starch/DCP has higher thermal stability 。

6 Plant protein

bioplastics based on plant protein from renewable resources have good mechanical and gas barrier properties and film-forming ability.They are not only biodegradable,but also can be used as fertilizers in the degradation process.They are one of the promising Bioplastics[86,87]。

6.1 Direct utilization

It is a simple and efficient way to prepare bioplastics directly from plant protein.Gamero et al.Mixed soybean protein,wood fiber and glycerol to prepare bioplastics by injection molding[88]。 the effects of different contents of lignocellulose on the mechanical and water absorption properties of bioplastics were studied.The results showed that the mechanical properties of soybean protein based bioplastics were improved and the water absorption capacity was reduced by adding 5.0 wt%lignocellulose.However,low content of wood fiber(0.1 wt%~1.0 wt%)had no significant effect on bioplastics。
Carvajal-Pi Piñero et al.Prepared pea protein-based bioplastics by mixing and injection molding,and evaluated the effects of different processing parameters(mixing speed and time)on the properties of the final bioplastics[89]。 the results showed that the short and long mixing time and the high mixing speed(50 R/min)caused the inhomogeneity.However,moderate mixing speed(30 R/min)and short mixing time(1 and 10 min)are suitable for obtaining bioplastics with good mechanical properties。
In addition,Lee et al.Prepared a completely plant-based mixture of zein and lignin,which can be converted into macroscopic materials by 3D printing[90]。 Compared with PLA,the zein-lignin mixture can enhance the printability,which is suitable for rapid extrusion printing into the required 3D materials,and is more easily decomposed by bacteria in soil and compost。
In addition to the use of a single plant protein,two or more plant proteins are also used to prepare bioplastics.Jim Jiménez-Rosado et al.Selected soy protein isolate and pea protein isolate,used glycerol as plasticizer,blended and injected to obtain protein-based bioplastics,and studied the effects of two different mold temperatures(70 and 130℃)and different heat treatment times(0,4 and 24 H)on the properties[91]。 It was found that the processing conditions and heat treatment had a great influence on the properties,and the bioplastics prepared at 130℃had better mechanical and water resistance properties。
Patnode et al.Designed vegetable protein-based membranes with soy protein and zein[92]。 They demonstrated the application of computational protein-ligand docking methods to the design of protein-based membranes by modeling the intermolecular(non-covalent)interactions of modifiers with plant proteins.based on the prediction model,the films based on soybean and zein were prepared by adding plasticizers and reinforcing agents to the protein matrix,which had good mechanical properties,Young's modulus of 99~400 MPa,and flexible films with higher surface hydrophobicity(elongation of 2%~120%),which were consistent with the calculated results.Therefore,the method of computational protein ligand docking can be used to predict the change of physical properties after adding the modifier to the plant protein matrix and further guide the experiment。
They also combined computation and experiment to develop film materials based on plasticized latex derived from corn protein,soy protein,and vegetable oil-based monomer(POBM),and explored the synergy between the three components to establish and validate a quantitative structure-activity(QSAR)computational model[93]。 the results showed that the addition of POBM latex improved the mechanical and barrier properties of the protein-based film,and there was a synergistic effect between POBM latex and soybean-corn protein.In addition,the QSAR model results showed that the mechanical and barrier properties of the optimized soy-corn protein bioplastic film were significantly improved。
G Gómez-Heincke et al.Studied the properties of bioplastics by mixing rice protein,potato protein and wheat gluten protein with different concentrations of glycerol,and then thermal molding at 60~180℃[86]。 The results show that these bioplastics require higher temperatures for thermoforming than wheat gluten.Potato protein-based bioplastics show comparable Young's modulus to low density polyethylene and exhibit lower water absorption(down to 9 wt%)。

6.2 Indirect utilization (chemical crosslinking)

Chemical crosslinking is an effective method to improve The properties of plant protein-based bioplastics.the main crosslinking agents are aldehydes and phenolic compounds.Yamada et al.Reacted soybean protein with formaldehyde to prepare bioplastics[94]。 It was found that the flexural strength increased with the increase of formaldehyde concentration,and reached a maximum of 35 MPa when the formaldehyde concentration was 1 wt%,which was equivalent to the flexural strength of polyethylene.IR spectra showed the formation of methylene cross-links between basic amino acids such as lysine and arginine.the degradation experiment showed that the weight loss of the bioplastic was about 30%after 6 days。
In addition,Perez-Puyana et al.Used pea protein as raw material and formaldehyde,glyoxal and glutaraldehyde as crosslinking agents to obtain bioplastics by injection molding[95]。 the effects of the addition of aldehydes with different aliphatic chain lengths on the physicochemical(degree of crosslinking,color,And transparency),mechanical(bending and tensile behavior),and functional(water absorption capacity and biodegradability)properties of protein-based bioplastics were evaluated.the results show that the mechanical properties,especially the flexural properties,are improved with the addition of aldehydes,but this depends on the degree of crosslinking they produce.and the addition of aldehydes with different aliphatic chain lengths reduces the water absorption of plastics。
Caffeic acid(CA)is a phenolic compound that reacts with sulfhydryl and amino groups in polypeptides to form a multiple cross-linked network of C—S/C—N bonds in the protein matrix.Li et al.Proposed a new method to prepare strong and tough soy protein(SP)-based films,as shown in Figure 3.They used boric acid and diol as raw materials to synthesize nitrogen-coordinated boric acid diester(NB),which was dynamically crosslinked to form a network[96]。 Then CA was blended with SP and hydroxyapatite(HA)to form an inorganic-organic hybrid(CHA).It was found that the combination of dynamic covalent bonding and hydrogen bonding between NB and CHA significantly improved the mechanical properties of the composite film,with the tensile strength and toughness of 13.89 MPa and 14.72 MJ/m3,respectively,which increased by 361%and 489%,as well as water resistance,flame retardancy,ultraviolet protection and antibacterial activity 。
图3 氮配位硼酸二酯（NB）的合成路线[96]

Fig. 3 Synthesis of nitrogen coordinated borate diester (NB)[96]

7 Vegetable oil

Vegetable oils are glycerides of higher fatty acids,which are widely available,renewable,non-toxic and biodegradable,and can be used as carbon sources for microbial fermentation.Their natural hydrophobicity and double bonds in unsaturated fatty acids have also been used in the study of bioplastics[97]。

7.1 Microbial fermentation

in recent years,vegetable oil has been used as a carbon source,and polyester PHA can be synthesized by microorganisms through fermentation In a nutrient substrate containing nitrogen or phosphate,with low cost and high conversion efficiency[98]。
Tian et al.used soybean oil and valerate as substrates,waste cooking oil and corn starch as substrates,and Used a Photobacterium(TLY01)to cultivate poly(3-hydroxybutyrate-co-3-hydroxyvalerate)(PHBV)in a bioreactor,with a potency of 16.28 G/L[99]。 When corn extract was used to replace tryptophan and yeast extract in the medium,and then the mixed substrate containing waste edible oil,corn starch and valerate was used to produce PHBV,the potency was 4.01 G/L。
Javaid et al.used Nile blue staining to screen five strains for PHA production,and Used rapeseed oil,mustard oil and glucose as substrates for computational analysis and comparison[100]。 The results showed that The three substrates could be used as carbon sources for PHA production.The chemical composition and type of PHA produced by strain 2 were further analyzed by infrared spectroscopy,and it was found that glucose only produced homopolymer PHB,while rapeseed oil and mustard oil could produce homopolymer PHB and copolymer PHB-PHV,and their crystallinity decreased from glucose to rapeseed oil and then to mustard oil。

7.2 Chemical modification

7.2.1 Epoxidized vegetable oil

the epoxidation modification of vegetable oil can improve the reaction activity and react with other components of bioplastics through ring-opening reaction,thus improving the properties of bioplastics[101]。
Cardon seed oil(CO)is a low-cost vegetable oil extracted from Cynara cardunculus seeds,which is epoxidized to obtain epoxidized seed oil(ECO),both of which can be used as plasticizers for PLA.Turco et al.Prepared PLA blend films containing 3%CO and ECO respectively by extrusion and compression molding,and studied the effects of these two bioplasticizers on the properties of the films[97]。 the results show that the glass transition temperature of PLA decreases with the addition of CO and ECO,and this effect is particularly evident in PLA-ECO films.However,the thermal stability and mechanical properties were significantly improved,especially in the PLA-ECO system,which showed stronger interaction and better compatibility。
Dominici et al.Studied the effect of epoxidized linseed oil(ELO)and maleic anhydride modified linseed oil(MLO)on the properties of a lignin/natural fiber commercial composite,（Arboform®）,as the matrix[102]。 It is found that the shock absorption energy generally increases for all samples.the addition of 2.5 wt%ELO can double the absorbed energy,and the addition of 5 wt%MLO can increase the absorbed energy by 118%.the tensile strength increased with the increase of ELO and MLO content。
Yang et al.Used palm oil(PO)and epoxidized palm oil(EPO)to modify starch-based bioplastics,and studied the effects of PO and EPO as hydrophobic components on the properties of starch-based bioplastics[98]。 the results show that the compatibility of EPO in starch matrix is better than that of PO,and the low concentration of oil(<3 wt%)significantly improves the tensile strength and elongation at break of bioplastics,while the high concentration of oil leads to the decrease of tensile properties due to phase separation.in comparison,EPO is more effective than PO in enhancing tensile properties due to the presence of epoxy groups。
Subsequently,they incorporated epoxidized palm oil(EPO)and epoxidized soybean oil(ESO)into starch/oil palm empty fruit bunch-based bioplastics,respectively,to improve mechanical and waterproof properties[101]。 the SEM results show that low content(0.75 wt%)of epoxidized oil(EO),especially ESO,can improve the compatibility,while high content(3 wt%)of EO can produce a lot of pores.Therefore,low content of EO can significantly improve the tensile strength,while high content of EO will have a negative impact on the tensile strength due to phase separation.In addition,EO reduces water absorption and solubility and also increases water vapor permeability。
In addition,they also prepared bioplastics by mixing ESO with starch modified by silane coupling agent 3-aminopropyltrimethoxysilane(APMS)[103]。 the infrared spectra showed that APMS inhibited the hydrogen bonding interaction between starch molecules.FESEM confirmed that starch and ESO had strong interaction and compatibility.The tensile strength of the bioplastic is increased from 5.78 MPa to 9.29 MPa,and the strengthening effect is obvious;In addition,bioplastics containing silicified starch exhibit higher thermal stability。

7.2.2 Acrylic epoxy vegetable oil

Acrylic epoxidized soybean oil(AESO)is obtained by acrylating epoxidized soybean oil,which can be further used to prepare thermosetting materials by free radical polymerization,but pure AESO has poor fluidity at room temperature.Chen et al.Synthesized vanillyl methacrylate(MVA)from vanillyl alcohol(VA)and methacrylic anhydride(MAA)by solvent-free method,and then blended MVA with AESO to obtain MVA-AESO thermosetting resin[104]。 It was found that the viscosity of MVA-AESO was much lower than that of pure AESO due to the addition of MVA,and the curing temperature was also reduced.Moreover,the flexible AESO network exhibits excellent flexural properties,storage modulus,glass transition temperature,and thermal stability。

7.2.3 Citric acid-epoxy vegetable oil oligomer

Yang et al.Systematically studied the effects of two"citric acid-epoxy vegetable oil oligomers"on the properties of corn starch-based bioplastics[105]。 For citric acid-epoxidized palm oil oligomer(CEPO),the addition of 0.75 wt%CEPO increased the tensile strength and Young's modulus of the sample from 3.67 MPa and 27.19 MPa to 6.90 MPa and 88.74 MPa,respectively,and the high content of CEPO toughened the composite,and the water sensitivity and permeability also decreased slightly.For citric acid-epoxidized soybean oil oligomer(CESO),the starch film has lower swelling degree and opacity,higher thermal properties and tensile strength[106]。 CESO is more compatible with starch than ESO.in addition,the content of CESO should not be too high,and the high content of CA in CESO will also cause the degradation of starch,resulting in the decline of film performance[107]。
To sum up,the application of vegetable oil in bioplastics is mainly based On epoxidation.on this basis,acrylic acid epoxidized vegetable oil introduces double bonds that can be polymerized by free radicals,while citric acid-epoxy vegetable oil oligomers increase the reaction sites of citric acid.Both methods can effectively improve the mechanical and water resistance properties of bioplastics。

8 Terpenoid

Terpenoids are hydrocarbons and their oxygenated derivatives with isoprene as the structural unit multiple,including monoterpenes,sesquiterpenes,etc[108]。 Turpentine is the main source of terpenes.Pinene and limonene in terpenes can be used to synthesize new chemicals such as spices,essences and medicines[109]。 in the field of bioplastics,terpenes can be used for plasticization,hydrophobicity and antibiosis,and the double bonds In terpenes can be subjected to photopolymerization or copolymerization。

8.1 Direct utilization

Mangeon et al.Studied the effect of linalool(a monoterpene),geraniol and geranyl acetate as plasticizers on the structure and properties of PHB[110]。 The results show that DSC measurements show a decrease in the Tgfrom 8.5 to-13°C,indicating the plasticizing effect of the terpene,while the elongation at break increases by more than 650%and the Young's modulus decreases.Dynamic mechanical analysis showed that the addition of terpene was beneficial to reduce E′and glass transition temperature,and this effect was more obvious in geranyl acetate,because the part containing ester group increased the free volume and molecular mobility 。
essential oils are mainly monoterpenes,sesquiterpenes and their oxygenated derivatives,which can reduce water vapor permeability.Wilbon et al.Studied the effects of rosemary Essential oil,cassava starch,surfactant concentration and film thickness on the properties of cassava starch film by response surface methodology[111]。 The results show that the film prepared under the optimal conditions has higher tensile strength(16.7 MPa),Young's modulus(2911.4 MPa),lower elongation at break(0.2%),lower water vapor permeability（0.8×10−14g/Pa sm）,lower solubility(33.24%)and opacity(16% )。
Modjinou et al.Studied the effect of cross-linking agent thiol on the properties by combining linalool with PHA through a light-induced thiol-ene reaction[112]。 the results showed that the elongation at break increased from 7%of PHA to 40%of PHA-linalool network after the use of crosslinking agent,and the increase of linalool content had strong anti-adhesion properties to Escherichia coli and Staphylococcus aureus。
Weems et al.Used the"click"reaction of terpenes and four-arm thiols to prepare thermosetting 3D printed structures by photopolymerization,and studied the reaction process and properties of UV-curable resins prepared from five terpenes(limonene,terpene,geraniol,nerol and linalool)[113]。 the results show that from the brittle elastomer,the loss effect changes to about 50%(Young's modulus is 0.4 MPa),and further to the thermoplastic behavior,the elastic modulus exceeds 20 MPa,and the loss effect changes to 180%。

8.2 Indirect utilization (chemical modification)

Sarkar et al.Synthesized copolymers of acyclic monoterpeneβ-myrcene(MY)and a series of methacrylates(with different side chain lengths)by emulsion polymerization,and studied the effect of side chain length on copolymerization[114]。 the results show that the kinetic rate of copolymerization decreases significantly with the increase of side chain length.the glass transition temperatures of all the synthesized copolymers were in the range of 230–270°C,depending on their composition.While polymethacrylate exhibits side-chain crystalline behavior,the copolymer with MY is a completely amorphous material。
to sum up,the application of terpenoids in bioplastics is generally less.as a renewable active monomer containing double bonds,terpenoids have great development space and potential To develop various new bioplastics through various new polymerization methods such As living radical polymerization。

9 Tannin

tannins are polyphenolic compounds obtained from plants and can be divided into two major groups,Condensed tannins and hydrolyzed tannins.condensed tannins consist of flavonoids(flavan 3-ols or flavan 3,4-diols),and hydrolyzable tannins consist of ellagic acid and gallic acid[115]。 Tannin can be used in bioplastics to improve mechanical,thermal stability and antibacterial properties。

9.1 Direct utilization

Konai et al.Extracted tannin from African Cuban balsam tree,sycamore fig,Shea tree and neem bark,used Vibrio niloticus as curing agent,mixed with banana straw fiber to prepare resin,and studied its performance[116]。 It was found that the four resins had good mechanical properties and thermal stability,with elastic moduli of 2.37×103,7.05×103,4.62×103and 2.65×103MPa,and thermal decomposition temperatures of 183,174,139 and 165°C,respectively 。
Wang et al.Prepared a bioplastic film by combining catechol derivative Arabian resin tannin(AMT)with soybean protein isolate(SPI)inspired by mussel[117]。 It is found that with the increase of AMT content,the tensile strength of the composite film reaches 7.64 MPa and the fracture strain reaches 145.6%.At the same time,in the ultraviolet region of 200~280 nm,all the films showed low ultraviolet transmittance,while almost 100%of the light was absorbed in the range of 320~400 nm,which was related to the phenylpropane and phenolic hydroxyl structures in AMT molecules。
Our research group explored the simultaneous extrusion and injection molding of tannin and glycerol to prepare TPS,and studied the effect of tannin content on the properties[118]。 the results showed that the synergistic effect of a small amount of tannin(2.5 wt%~7.5 wt%)and glycerol could improve the tensile strength and maintain a stable elongation at break,while tannin aggregation occurred at high tannin content,and the tensile strength and flexural strength were improved.In addition,the introduction of tannin also improved the thermal stability of TPS,and the biodegradability was slightly reduced,but it had antibacterial activity。
Cre Crešnar et al.Prepared two series of PLA-KL and PLA-TANN composites with different contents(0.5 wt%,1.0 wt%and 2.5 wt%)by extrusion using tannin(TANN)and kraft lignin(KL)as reinforcing agents[119]。 It was found that KL and TANN did not cause significant changes In wettability,but slightly increased hydrophilicity.the content of TANN and KL and their interaction with PLA directly affect the surface roughness and mechanical properties of the composites.in addition,they all have good oxidation resistance,which is enhanced with the increase of the content,and show obvious antibacterial effect on Escherichia coli。
Ainali et al.Prepared PLA-based composites filled with different contents of tannin(T)and KL,respectively[120]。 It was found that PLA/lignin had better thermal stability than pure PLA,while tannin had a catalytic effect,which would reduce the thermal stability of PLA.The calculated Eαvalue of PLA-T composite is lower than that of PLA-KL,that is,the decomposition rate constant is increased and the thermal degradation is accelerated 。

9.2 Indirect utilization (chemical modification)

In order to find a partial substitute for bisphenol-based epoxy resin,Shnawa prepared bio-based epoxy resin by glycidyl acylation of eucalyptus tannin with epichlorohydrin,and studied the difference between tannin epoxy resin(TE)and commercial epoxy resin(CE)[121]。 the results showed that TE showed a wide low exothermic peak,no significant crosslinking property and low curing enthalpy at different levels of amine curing agent.the maximum curing enthalpy of pure TE is 111 J/G,which is lower than that of pure CE.When 20%TE is added to CE,The maximum curing peak is 116.7℃and The curing enthalpy is 127.4 J/G,which is very close to that of pure CE.Therefore,a new green thermosetting resin can be obtained by partially replacing petrochemical-based CE with TE at a low addition level(e.g.,20%or less)。
Liao et al.First acetylated the hydroxyl group of tannin,and prepared the biocomposite plastics of PLA and acetylated tannin by in-situ graft copolymerization with dicumyl peroxide as initiator[122]。 It was found that compared with pure PLA,the molecular weight,Young's modulus,tensile strength,and composite viscosity of PLA with high acetylated tannin were increased,indicating that PLA and acetylated tannin had strong interfacial adhesion.In addition,the glass transition temperature,thermal stability,and hydrophobicity are improved。

10 Conclusion and prospect

in this paper,the application methods and characteristics of eight main components in plant resources,such as cellulose,in bioplastics were summarized.From the existing research work,the utilization of plant resources still has a large space for development,and the future development trend may be as follows:(1)Expand the scope of utilization.in addition to the contents discussed in this paper,lac,tannin,pine needle powder and other forest chemicals can also be used in the development of bioplastics.(2)mixing different types of plant components to improve the problems in application through synergistic effect;(3)in-depth study of the structure-activity relationship and mechanism of action between the molecular structure and overall performance of a plant component to improve performance parameters;(4)Select appropriate plant components for the development of bioplastics in specific fields such as packaging,automotive,construction and medical treatment;(5)Further improve the extraction and separation process of different plant components,reduce costs and improve their application in bioplastics.in a word,the development of bioplastics using plant resources has great prospects in the plastics industry and environmental protection,and plays an important role in the strategy of achieving green and sustainable development。

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