Composite bioplastic of aminopolyphenol embedded with furfural-p-hydroxybenzoic acid-silanone and use thereof

Abstract

Provided are a composite bioplastic of aminopolyphenol embedded with furfural-p-hydroxybenzoic acid-silanone and the use thereof. The preparation of the plastic comprises the following steps: S1, reacting and modifying lignin-based aminopolyphenol and derivatives in biogas residue under the action of Bacillus aryabhattai; S2, forming furfural, p-hydroxybenzoic acid and derivatives under the action of metabolic enzymes from Bacillus aryabhattai; and S3, subjecting aminopolyphenol embedded with furfural, p-hydroxybenzoic acid, methylsilane and silanone to a bioplasticization reaction, wherein the Bacillus aryabhattai has the taxonomic name of Bacillus aryabhattai, which is deposited at the China Center for Type Culture Collection under the deposit number CCTCC NO: M20232038, with the deposit date of 01 November 2023. Compared with the prior art, the present invention enables the preparation of polyester bioplastics by means of subjecting aminopolyphenol from wet biogas residue to hybrid silanization-enzymatic modification, followed by reacting the modified aminopolyphenol with p-hydroxybenzoic acid, p-hydroxybenzoic acid, etc., under the action of aldolase. The polyester bioplastics have a lower cost than PBAT and PBST, and have good mechanical properties and good biodegradation properties. Compared with non-degradable plastics, the polyester bioplastics are low carbon and more environmentally friendly, and have a broader range of applications.

Description

Amino polyphenol chimeric furfural-sugar aldehyde-silane ketone composite bioplastics and use thereof TECHNICAL FIELD

[0001] The present application relates to the field of biotechnology, in particular to amino polyphenol chimeric furfural-sugar aldehyde-silane ketone composite bioplastics and use thereof. BACKGROUND

[0002] The biogas residue cellulose after cassava fuel ethanol production is abundant in quantity, widely sourced, renewable, biocompatible, low in price, and can be developed into cellulose-based high molecular materials. However, due to the salt content of wet biogas residue, the highly developed hydrogen bond network and partial crystalline structure of biogas residue fibers, it is not easy to dissolve in water and general organic solvents, which limits the development and application as functional materials. The preparation method of a modified PBAT biodegradable plastic and an antistatic plastic disclosed in CN114015204A patent; the modified calcium carbonate for filling biodegradable plastics and its preparation method disclosed in CN107446164A patent; the PHA modified TPS / PBAT biodegradable resin and its preparation method disclosed in WO2020088214A patent, and the chain extender and preparation method of the TPS / PLA / PBAT blended modified biodegradable resin disclosed in WO2020083049A1 patent, are basically limited to the preparation of PBAT composite bioplastics, and there is a situation of high cost and long biodegradation period. The patent with application number CN202210109988 discloses that the lactone is used as a ring-opening polymerization monomer, the norbornene-based initiator is used as a ring-opening polymerization initiator and a ring-opening metathesis polymer, and the Grubbs catalyst is used as a ring-opening metathesis polymerization initiator and catalyst. Coupling biocatalytic polymerization and metal catalytic polymerization is applied to a micro-control reaction platform. By adjusting the conditions of the two-step reaction, the steps of effective synthesis do not interfere with each other, and a structure-controllable comb polyester polyol can be prepared, and bioplastics can be polymerized again. The application still has a limited application. SUMMARY

[0003] The present application overcomes the deficiencies of the prior art and provides amino polyphenol chimeric furfural-sugar aldehyde-silane ketone composite bioplastics and use thereof. Amino polyphenol in biogas residue after cassava saccharification and ethanol production is modified by reaction under the action of Bacillus aryabhattai and its metabolic enzymes. Furfural-sugar aldehyde is obtained by enzymatic hydrolysis of biogas residue lignin. Amino polyphenol chimeric furfural is subjected to sol-gel reaction, and then composite biodegradable bioplastics tray and foam cushion material are prepared.

[0004] To achieve the above-mentioned purpose, amino polyphenol chimeric furfural-sugar aldehyde-silane ketone composite bioplastics are designed, and the preparation method comprises the following steps:

[0005] S1, lignin amino polyphenol and derivatives in biogas residue react and modify under the action of Bacillus aryabhattai;

[0006] S2, form furfural and sugar aldehyde and derivatives under the action of Bacillus aryabhattai metabolic enzyme;

[0007] S3, amino polyphenol chimeric furfural, sugar aldehyde, methyl silane, silane ketone for biological plasticization reaction;

[0008] [According to the rules 91 correction 14.02.2025] The classification name of Bacillus aryabhattai is Bacillus aryabhattai, the preservation address is China Center for Type Culture Collection, the preservation number is CCTCC NO: M20232038, the preservation time is November 1, 2023, and the preservation address is Wuhan University, School of Life Sciences, Wuhan, Hubei Province, China 430072.

[0009] In the step S1, the biogas residue after cassava saccharification for ethanol production is selected.

[0010] The specific method of step S1 is as follows: under the action of Bacillus aryabhattai and its metabolic enzyme, according to CFU 1.0 / kg biogas residue, at temperature 40-50℃, pH 7.0-8.5, time 20-35min, the hydrophilic hydroxyl group (-OH) of the biogas residue changes the -SiO2 into Si (OC2H5) 4+H2O; chimeric aromatic ring R-N-O reaction; chimeric silicon, oxygen and phosphorus Si-O-P-O-Si silanization reaction modification.

[0011] In the step S1, the culture medium of Bacillus aryabhattai and its metabolic enzyme includes trace amounts of phosphorus salt, potassium salt, HOC2H5, proteose peptone 0.3%, sodium chloride, wherein the mass percentage is as follows: phosphorus salt 0.03%, potassium salt 0.02%, HOC2H5 0.1%, proteose peptone 0.03%, sodium chloride 1.00%.

[0012] In the step S2, under the action of Bacillus aryabhattai and its metabolic enzyme, the O - , COO - on the surface of lignin in the biogas residue after cassava saccharification for ethanol production will adsorb N atoms and P ions, cyclize and enzymatically hydrolyze into furfural and sugar aldehyde .

[0013] In the step S3, under the action of aldehyde condensing enzyme of Bacillus aryabhattai and its metabolism, lignin polyphenol and amino polyphenol chimeric furfural, furfural superhydrophobic polyesterization reaction is carried out, sol-gel reacts at room temperature for 2-3h, vacuum drying at 50℃, and the contact angle of superhydrophobicity is changed from 0°, 60° to 156° by using scanning electron microscope.

[0014] To achieve the above object, the use of amino polyphenol chimeric furfural-sugar aldehyde-silane ketone composite bioplastics is designed, and the biopolymer and modified biogas residue amino polyphenol are homogenized and extruded at a ratio of 0.5:1-0.5:3, and then granulated and pressed into degradable trays, which have higher rigidity and bearing capacity than wood and full plastic, are resistant to sunlight aging, and can be used as soil conditioner or recycled after degradation.

[0015] The biopolymer is the product of steps S1, S2 and S3; and the modified biogas residue amino polyphenol is the product of step S1.

[0016] Under the action of Bacillus aryabhatta and its metabolized acetalase, the biogas residue after cassava saccharification and ethanol production, chimeric furfural-sugar aldehyde and silane ketone are foamed to produce a packaging foam cushion material at a ratio of 1:1:1 and 2:1:1, and the relative density is 20% of PE plastic, the mechanical properties are similar to wood, the elastic modulus is 6300-11500 Mpa, the bending strength is 41-80 Mpa, and the material can be recycled and used.

[0017] Compared with the prior art, the wet biogas residue amino polyphenol is modified by hybrid silanization enzyme hydrolysis, and is prepared into polyester bioplastics by reacting with sugar aldehyde and sugar aldehyde under the action of acetalase, which has lower cost than PBAT and PBST, good mechanical properties, good biodegradability, is low-carbon and environmentally friendly compared with non-degradable plastics, and has wider application. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a schematic diagram of the diisocyanate of the present application. The diisocyanate is formed by enzymatic hydrolysis, condensation and isomerization of the enzymatic hydrolysis furfural-sugar aldehyde of the biogas residue lignin.

[0019] Figure 2 is a schematic diagram of the bis(trimethylsilyl)methyl propionate of the present application. The methyl propionate is formed by enzymatic hydrolysis and derivatization of furfural, sugar aldehyde, methyl silane and silane ketone.

[0020] Figure 3 is a schematic diagram of 1,2-cyclopentanediol of the present application. The furan ketone is derived from furfural, and the furan ring replaces the benzene ring. The prepared copolyester (PBSF) has stronger biodegradability than PBST.

[0021] Figure 4 is a schematic diagram of furfural (furfuraldehyde) of the present application. The prepared copolyester (PBSF) has stronger biodegradability than PBST.

[0022] Figure 5 is a schematic diagram of hydroxyphenylpropane (or called propane phenol) of the present application. The hydroxyphenylpropane is obtained by oxidative derivatization of lignin phenylpropane, and is produced from cassava raw materials. One of the reaction pathways is shown in Figure 6. The structure in Figure 6 can be further oxidized to become hydroxyphenylpropanol, hydroxybenzoic acid, and then hydroxybenzene dicarboxylic acid methyl ester.

[0023] Figure 6 is a schematic diagram of the hydroxybenzenedicarboxylic acid methyl ester of the present application. The hydroxybenzenedicarboxylic acid methyl ester is formed by hydrolysis of furfural, sugar aldehyde, and diisocyanate; it can also be generated from the structure in Figure 6.

[0024] Figure 7 is a schematic diagram of the biphenyl imide furfural of the present application. The biphenyl imide furfural is formed by isocyanate, furfural, and sugar aldehyde.

[0025] Figure 8 is a schematic diagram of the imidazole alkyl ketone of the present application, which can form a polyester under the action of enzymes. DETAILED DESCRIPTION

[0026] The present application will be further described below with reference to the accompanying drawings.

[0027] The amino polyphenol chimeric furfural-sugar aldehyde-silane ketone composite bioplastic in this embodiment, the preparation method comprises the following steps:

[0028] S1, the lignin amino polyphenol in the biogas residue and its derivatives are modified by reaction under the action of Bacillus aryabhattai;

[0029] S2, furfural, sugar aldehyde and derivatives are formed under the action of Bacillus aryabhattai metabolic enzymes;

[0030] S3, the amino polyphenol chimeric furfural, sugar aldehyde, methyl silane, and silane ketone are subjected to bioplasticization reaction;

[0031] The classification name of Bacillus aryabhattai is Bacillus aryabhattai, and the preservation address is China Center for Type Culture Collection, the preservation number is CCTCC NO: M20232038, and the preservation time is November 1, 2023.

[0032] In step S1, the biogas residue is selected from the biogas residue after saccharification of cassava for ethanol production.

[0033] The specific method of step S1 is as follows: under the action of Bacillus aryabhattai and its metabolic enzymes, according to CFU 1.0 / kg biogas residue, at a temperature of 40-50°C, pH 7.0-8.5, and for a time of 20-35 min, the hydrophilic hydroxyl group (-OH) of the biogas residue is changed to Si (OC2H5) 4+H2O; the R-N-O reaction of the chimeric aromatic ring is modified; and the Si-O-P-O-Si silanization reaction of the chimeric silicon, oxygen, and phosphorus is modified.

[0034] In step S1, the culture medium of Bacillus aryabhattai and its metabolic enzymes comprises trace amounts of phosphorus salt, potassium salt, HOC2H5, peptone 0.3%, and sodium chloride, and the mass percentages are as follows: phosphorus salt 0.03%, potassium salt 0.02%, HOC2H5 0.1%, peptone 0.03%, and sodium chloride 1.00%.

[0035] In step S2, under the action of Bacillus aryabhattai and its metabolic enzymes, the O - , COO - , N atom and P ion ring will be adsorbed and enzymatically hydrolyzed into furfural and sugar aldehyde .

[0036] In step S3, under the action of Bacillus aryabhattai and its metabolic aldehyde condensing enzyme, the super-hydrophobic polyesterization reaction of lignin polyphenol, aminophenol and furfural is carried out, the sol-gel is reacted at room temperature for 2-3h, vacuum dried at 50℃, and the contact angle of the super-hydrophobic is changed from 0°, 60° to 156°.

[0037] In this embodiment, the use of aminophenol-furfural-silicone ketone composite biological plastic, the homogenization extrusion, granulation and pressing of the biological polyester and the modified biogas residue aminophenol are carried out at a ratio of 0.5:1-0.5:3 to form a degradable tray, which has higher rigidity and bearing capacity than wood and full plastic, is resistant to sunlight aging, and after degradation can be used as a soil conditioner or recycled.

[0038] The biological polyester is the product of steps S1, S2 and S3; the modified biogas residue aminophenol is the product of step S1.

[0039] Under the action of Bacillus aryabhattai and its metabolic aldehyde condensing enzyme, the biogas residue after cassava saccharification for ethanol production, furfural-sugar aldehyde and silane ketone are combined at a ratio of 1:1:1 and 2:1:1 to form a packaging foam cushion material, which has a relative density of 20% of PE plastic, similar mechanical properties to wood, an elastic modulus of 6300-11500Mpa, and a bending strength of 41-80Mpa, and can be recycled. Example One

[0040] In this embodiment, 100 parts of biogas residue after cassava saccharification for ethanol production is used, and the concentration of Bacillus aryabhattai and its metabolic cellulase is U1.0 / kg biogas residue, the decomposition of Mg 2+ , Ca 2+ is carried out at a temperature of 40℃, pH 7.0, and a time of 20min, and the Si-O-P-O-Si silanization reaction of silicon, oxygen and phosphorus is combined with furfural (furfural) and furan ketone, aminophenol, and amidoalkyl ketone ester to carry out polyesterization reaction under the action of aldehyde condensing enzyme, the time is 2h, the temperature is 50℃, and the homogenization extrusion, granulation and pressing are carried out at a ratio of 0.5:1 to form a degradable egg tray, which has higher rigidity and bearing capacity than wood and full plastic, and after use, the light degradation can be carried out by the presence of nitrogen, phosphorus, potassium and other photosensitive groups according to the national standard "GB / t1040.2-2016" for biodegradation, and the degraded soil conditioner has resistance to pests, diseases and nematodes, and can be recycled in ecological agriculture. Example two

[0041] This example is cassava sugar ethanol after the sludge 100 parts, bacillus aryabhatta and its metabolic cellulase concentration according to U1.0 / kg sludge, at temperature 50℃, pH8.5, time 30min, decomposition of Mg 2+ , Ca 2+ , Si-O-P-O-Si silane reaction with furfural and (furfural) and furan ketone, aminophenol, amido alkyl ketone ester, copolymerization and foaming under the action of acetalase, according to the ratio of 2:1:1, foaming into the plant growth with three-dimensional green foam wall material, relative density is 20% of PE plastic, mechanical properties similar to wood, elastic modulus is 10200Mpa, bending strength is 80Mpa, tensile strength 62.5 MPa, water absorption 3.0%, thermal stability 110℃. Example three

[0042] This example is cassava sugar ethanol after the sludge 100 parts, bacillus aryabhatta and its metabolic cellulase concentration according to U1.0 / kg sludge, at temperature 40℃, pH7.5, time 25min, decomposition of Na + , Fe 3+ , impurities, Si-O-P-O-Si silane reaction with furfural (furfural) and furan ketone, aminophenol, amido alkyl ketone ester, copolymerization and esterification reaction with recycled old plastic PET ( ) under the action of acetalase, time 3h, temperature 50℃, and according to 0.5:1 homogenization extrusion, granulation and compression into degradable industrial product packaging tray, rigidity and carrying capacity higher than wood and all plastic, after use, can be photodegraded by the presence of nitrogen, phosphorus, potassium and other photosensitive groups according to the national standard "GB / t1040.2-2016" and biodegradation. Example four

[0043] This example is cassava sugar ethanol after the sludge 100 parts, bacillus aryabhatta and its metabolic cellulase concentration according to U1.0 / kg sludge, at temperature 50℃, pH8.5, time 30min, decomposition of Na + , Fe 3,Chimeric silicon, oxygen, phosphorus Si-O-P-O-Si silanization reaction, with furfural and (furfural) and furan ketone, amino polyphenol, amido alkyl ketone ester, in the presence of acetalase with recycled old plastic PET (polyethylene terephthalate) copolymerization foaming, according to the ratio of 2:1:1, foaming into packaging foam cushion material, relative density of PE plastic is 30%, the mechanical properties are similar to wood, elastic modulus is 12500Mpa, bending strength is 90Mpa, tensile strength is 67.0 MPa, water absorption is 2.0%, thermal stability is 150℃, the amount is large, and the recycling rate is high.

Claims

1. A complex bioplastic of amino polyphenol chimeric furfural-sugar- acran-silane ketone, characterized by: The preparation method comprises the following steps: S1, lignin amino polyphenol and derivatives in biogas residue are modified by reaction under the action of Bacillus aryabhattai; S2, furfural and sugar aldehyde and derivatives are formed under the action of Bacillus aryabhattai metabolic enzymes; S3, amino polyphenol is chimeric with furfural, sugar aldehyde, methyl silane and silane ketone to perform biological plasticization reaction; The classification name of the Bacillus aryabhattai is Bacillus aryabhattai, the preservation address is China Center for Type Culture Collection, the preservation number is CCTCC NO: M20232038, and the preservation time is November 1, 2023.

2. The aminophenolic chimeric furfural-sugar aldehyde-silane ketone complex bio-plastic of claim 1, characterized by: In the step S1, the biogas residue is selected from the biogas residue after cassava saccharification for ethanol production.

3. The aminophenolic chimeric furfural-sugar aldehyde-silane ketone complex bio-plastic of claim 1, wherein: The specific method of the step S1 is as follows: under the action of Bacillus aryabhattai and metabolic enzymes, the hydrophilic hydroxyl (-OH) of the biogas residue is changed into Si (OC2H5) 4+H2O at a temperature of 40-50 DEG C, a pH of 7.0-8.5 and a time of 20-35 min; R-N-O chimeric aromatic ring reaction is performed; Si-O-P-O-Si silanization reaction modification of silicon, oxygen and phosphorus is performed.

4. The aminophenolic chimeric furfural-sugar aldehyde-silane ketone complex bio-plastic of claim 1, wherein: In the step S1, the culture medium of the Bacillus aryabhattai and metabolic enzymes comprises trace amounts of phosphorus salt, potassium salt, HOC2H5, peptone 0.3% and sodium chloride, and the mass percentages are as follows: phosphorus salt 0.03%, potassium salt 0.02%, HOC2H5 0.1%, peptone 0.03% and sodium chloride 1.00%.

5. The aminophenolic chimeric furfural-sugar aldehyde-silane ketone complex bio-plastic of claim 1, wherein: The O - , COO - , P ions on the surface of the lignin in the cassava ethanol production after saccharification of the biogas residue will be adsorbed, ringed and enzymatically hydrolyzed into furfural and sugar aldehyde .

6. The aminophenolic chimeric furfural-sugar aldehyde-silane ketone complex bio-plastic of claim 1, wherein: In the step S3, under the action of aldehyde aldolase of the Bacillus aryabhattai and metabolism, lignin polyphenol and amino polyphenol are chimeric with furfural, and superhydrophobic polyesterization reaction of furfural is performed; sol-gel is reacted at room temperature for 2-3 h, vacuum dried at 50 DEG C, and the contact angle of the superhydrophobicity is changed from 0 DEG to 60 DEG to 156 DEG by using a scanning electron microscope.

7. The use of the amino polyphenol-furfural-glucuronide-silane ketone composite bioplastic according to claim 1, characterized in that: The biopolyester and the modified biogas residue amino polyphenol are homogenized, extruded, granulated and pressed into degradable trays at a ratio of 0.5:1-0.5:3, and the rigidity and bearing capacity are higher than those of wood and full plastic, the trays are resistant to sunlight aging, and after degradation, the trays can be used as soil conditioners or recycled.

8. The use of the amino polyphenol-furfural-glucuronide-silane ketone composite bioplastic according to claim 1, characterized in that: The biopolyester is the product of the steps S1, S2 and S3; and the modified biogas residue amino polyphenol is the product of the step S1.

9. The use of the amino polyphenol-furfural-glucuronide-silane ketone composite bioplastic according to claim 1, characterized in that: Under the action of aldehyde aldolase of the Bacillus aryabhattai and metabolism, the biogas residue after cassava saccharification for ethanol production is chimeric with furfural-sugar aldehyde and silane ketone at a ratio of 1:1:1 and 2:1:1, and foamed to form a foamed pad material for packaging, the relative density of the foamed pad material is 20% of that of PE plastic, the mechanical properties are similar to those of wood, the elastic modulus is 6300-11500 Mpa, the bending strength is 41-80 Mpa, and the foamed pad material can be recycled.

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