CN111286008B - Bio-based epoxy resin curing agent and preparation method thereof - Google Patents
Bio-based epoxy resin curing agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bio-based epoxy resin curing agent and a preparation method thereof, wherein the preparation method comprises the steps of carrying out condensation reaction on degraded lignin and amino acid to obtain an amino acid lignin solution, and carrying out nanofiltration drying to obtain amino acid lignin; and carrying out curing reaction on the obtained amino acid lignin and epoxy resin to obtain the biological epoxy resin curing agent. The main advantages of the invention are: (1) the invention firstly provides and prepares amino acid lignin, and applies the amino acid lignin to an epoxy resin curing agent according to the structural characteristics of the amino acid lignin to replace the traditional aromatic amine curing agent 590#, 701#, 702 #. (2) After the technology provided by the invention is pretreated, the molecular weight is reduced, the content of active hydroxyl is increased, active sites can be reacted with amino acid to increase, and the activity of a corresponding curing agent is increased; meanwhile, the epoxy resin prepared by the method has stronger ultraviolet aging resistance due to good ultraviolet resistance of lignin.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a bio-based epoxy resin curing agent and a preparation method thereof.
Background
The epoxy resin is a common thermosetting resin, has good heat resistance, adhesiveness, chemical stability and dimensional stability, excellent mechanical property and easy processing and forming, and is widely applied to the fields of coatings, adhesives, electronic packaging materials, composite materials and the like. In order to obtain the desired properties of the epoxy resin, the curing agent acts as a catalyst or undergoes polyaddition or copolymerization with epoxide groups to give a thermoset network structure. The three-dimensional network structure of such thermosets depends on the epoxy resin and the curing agent.
In the epoxy resin curing process, the curing agent of addition polymerization type includes polyamine type, acid anhydride type, phenol type, polythiol type. The commonly used aromatic amine curing agent brand and the structure name thereof comprise 590# (m-phenylenediamine and epoxy phenylalkyl phenyl ether condensate); 701#, 702# (phenol formaldehyde aliphatic diamine condensate); 704#, 705# (methyl imidazole and epoxypropyl isooctyl ether).
However, the traditional epoxy resin curing agent is derived from non-renewable petrochemical resources, so that the problems of resource waste, environmental pollution and the like are caused. The biomass raw material has wide source, environment friendliness and low cost, and the biomass is adopted to prepare the epoxy resin curing agent, so that epoxy resins with different properties can be obtained. Meanwhile, the biomass curing agent can improve the degradability of the epoxy resin, reduce the pollution to the environment caused by the thermosetting epoxy resin after use and reduce the dependence of people on petrochemical products. Lignin and cellulose products can be obtained by separating the biomass, wherein the amino acid compounds can be obtained by further fermenting the cellulose. Therefore, development of a full bio-based epoxy resin curing agent is required.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a bio-based epoxy resin curing agent aiming at the defects of the prior art.
The technical problem to be solved by the invention is to provide a preparation method of the curing agent.
In order to solve the technical problem, the invention discloses a preparation method of a bio-based epoxy resin curing agent, which is characterized in that a biomass downstream product lignin and amino acid are subjected to a composite reaction to prepare the aromatic amine bio-based epoxy resin curing agent.
Preferably, the preparation method comprises the steps of degrading lignin to increase active structural units such as phenolic hydroxyl, alcoholic hydroxyl and the like, carrying out condensation reaction on the degraded lignin and amino acid to obtain an amino acid lignin solution, and carrying out nanofiltration drying to obtain the amino acid lignin; and carrying out curing reaction on the obtained amino acid lignin and epoxy resin to obtain the biological epoxy resin curing agent.
Wherein the degradation is to carry out acidolysis reaction on lignin and an acidolysis catalyst in a solvent; wherein, the acidolysis catalyst is an organic solvent with good solubility to lignin, and preferably any one or the combination of two of hydrobromic acid and hydroiodic acid; the solvent is any one or the combination of two of N, N-dimethylformamide and tetrahydrofuran; the mass volume ratio of the lignin to the solvent is 0.2-0.5 g/mL; the mass ratio of the acidolysis catalyst to the lignin is (0.05-2): 1; the reaction temperature is 70-110 ℃, and the reaction time is 1-3 h. After the reaction is finished, cooling the reactant to room temperature, dropwise adding the reactant into a hydrochloric acid solution with the mass fraction of 2%, stirring, centrifuging, taking the precipitate, washing the precipitate with distilled water, washing the supernatant to be neutral, and freeze-drying to obtain the degraded lignin.
Wherein the degradation is to pyrolyze the lignin at 140-200 ℃ for 1-3 h.
The degradation is to place lignin in a solvent, add a catalyst, and carry out high-pressure hydrogenolysis reaction; wherein, the solvent is any one or the combination of two of methanol and ethanol; the catalyst is a solid acid catalyst loaded by hydrogenation metal, and the metal is preferably Pd, Ru or Ni; the mass-volume ratio of the lignin to the solvent is 20-80 mg/mL; the mass ratio of the lignin to the catalyst is 1 (0.02-0.05), and the high-pressure reaction is carried out for 6-12 hours at the hydrogen pressure of 2-6 MPa and the temperature of 160-250 ℃.
Wherein the amino acid is any one of histidine, arginine, tryptophan and lysine.
The condensation reaction is a Mannich reaction, and amino acid is connected with lignin in a carbon-carbon connection mode; and (3) degrading the lignin: formaldehyde: amino acids: sodium hydroxide: water is mixed according to the weight ratio of 100-200 g: 30-150 g: 0.5-2 mol: 120-200 g: the reaction is carried out for 3-6 h at the temperature of 50-90 ℃ in the dosage of 1000 mL.
Wherein the condensation reaction is an epoxy amination reaction, an ether bond is adopted to connect the amino acid and the lignin, and the epoxy amination reaction comprises the following steps: (1) preparing solution containing chlorohydrin intermediate from amino acid and chloropropane oxide; (2) adding degraded lignin and sodium hydroxide into the chlorohydrin intermediate solution obtained in the step (1) for reaction; in the step (1), amino acid and chloropropane are dissolved in water according to a molar ratio of 1:1, and react for 3-7 h at 50-80 ℃; the concentration of the amino acid is 0.2-2 mol/L; in the step (2), the molar mass ratio of the chlorohydrin intermediate to the degraded lignin is (0.2-2): (100-200) mol/g; the mass ratio of the sodium hydroxide to the lignin is 1-2: 1.2-2; the reaction is carried out for 3-6 h at the temperature of 25-60 ℃.
Wherein the condensation reaction is an esterification reaction, and the amino acid is connected with lignin through an ester bond, specifically, the degraded lignin: amino acids: catalyst: dehydrating agent: the solvent is mixed according to the weight ratio of 100-200 g: 0.5-2 mol: 1-4 mol: 1.5-3 mol: reacting for 2-6 h at 70-100 ℃ by using 1000mL of the catalyst; the catalyst is concentrated sulfuric acid or an acylation reagent, and the concentrated sulfuric acid is concentrated sulfuric acid with the mass fraction of 98%; the acylating agent is preferably 4-dimethylaminopyridine; the solvent is anhydrous N, N-dimethylformamide or anhydrous tetrahydrofuran.
Wherein the nanofiltration is performed by adopting a nanofiltration membrane with the interception amount of 300-600 Da to obtain a concentrated solution which does not permeate the filtration membrane; and the pH value of the nanofiltration end point concentrated solution is 4-8.
Wherein the drying is spray drying or freeze drying, and the spray drying temperature is 100-140 ℃.
The structure of the amino-acidified lignin after drying is shown in fig. 1.
The curing reaction is to mix amino acid lignin and epoxy resin according to the mass ratio of 0.1-0.5: 1, pre-cure the mixture for 2-4 h (preferably 3h) at 20-40 ℃ (preferably 30 ℃), cure the mixture for 2-3 h (preferably 3h) at 100-120 ℃, and finally cure the mixture for 0.5-2 h (preferably 1h) at 160-200 ℃ (preferably 180 ℃).
The bio-based epoxy resin curing agent prepared by the method is also within the protection scope of the invention.
Has the advantages that: compared with the prior art, the invention has the main advantages that:
(1) the invention firstly provides and prepares amino acid lignin, and applies the amino acid lignin to an epoxy resin curing agent according to the structural characteristics of the amino acid lignin to replace the traditional aromatic amine curing agent 590#, 701#, 702 #.
(2) After the technology provided by the invention is pretreated, the molecular weight is reduced, the content of active hydroxyl is increased, active sites can be reacted with amino acid to increase, and the activity of a corresponding curing agent is increased; meanwhile, the epoxy resin prepared by the method has stronger ultraviolet aging resistance due to good ultraviolet resistance of lignin.
Drawings
FIG. 1 is a diagram of the structure of the amino-acidified lignin.
FIG. 2 is the nuclear magnetic hydrogen spectrum of lignin after acidolysis pretreatment.
FIG. 3 is a nuclear magnetic hydrogen spectrum of amino acid complex lignin.
FIG. 4 is an infrared spectrum of amino acid-lignin complex.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
Example 1: degradation-acidolysis of lignin
In a 50mL reaction flask, 5g of lignin was dissolved in 20mL of DMF, and the mixture was reacted in a microwave reactor at 90 ℃ for 30min with 5g of HBr (10% by mass). After the reaction, the reaction product was cooled to room temperature, added dropwise to 200mL of a 2% hydrochloric acid solution, stirred for 30min, centrifuged, and the precipitate was washed with distilled water, washed to neutrality with supernatant, lyophilized, and the changes in molecular weight and phenolic hydroxyl groups before and after acidolysis were detected by nuclear magnetic resonance (fig. 2) and GPC, the results of which are shown in table 1.
In the figure 2, p-nitrobenzaldehyde is taken as an internal standard substance, and the-ArOH peak in the figure is integrated, so that the phenolic hydroxyl content in the acidolysis lignin is calculated to be 4.52 percent, and the phenolic hydroxyl content in the original lignin is 3.15 percent[1]。
Example 2: pyrolytic lignin
1.5g of lignin is pyrolyzed at 200 ℃ for 3h to obtain pyrolyzed lignin. Changes in molecular weight and phenolic hydroxyl group content before and after pyrolysis were measured by nuclear magnetism (fig. 1) and GPC, and the results are shown in table 1.
Example 3: hydrogenolysis of
1.5g of lignin was dissolved in 20mL of methanol in a 50mL reaction flask, 0.1g of (Pd) catalyst was added, and the mixed solution was charged into a 100mL autoclave, and 2MPa of hydrogen was introduced to the autoclave to react at 160 ℃ for 6 hours. After the reaction is finished, cooling the reactant to room temperature, filtering, and then carrying out rotary evaporation drying on the filtrate to obtain a sample. Changes in molecular weight and phenolic hydroxyl group content before and after hydrogenolysis were measured by nuclear magnetic resonance and GPC, and the results are shown in table 1 below.
TABLE 1 changes in molecular weight and phenolic hydroxyl groups before and after acid hydrolysis of lignin
| Sample (I) | Phenolic hydroxyl group content (wt%) | Alcohol hydroxyl group content (wt%) | Molecular weight (Da) |
| Original lignin | 3.15 | 2.81 | 3387 |
| Lignin after acidolysis | 4.52 | 3.52 | 2010 |
| Hydrogenolysis of lignin | 4.24 | 3.73 | 2127 |
| Pyrolyzed lignin | 4.23 | 3.84 | 2239 |
Examples 4 to 7: mannich reaction for preparing amino-acid lignin by condensation of acidolyzed lignin and amino acid
100g of the lignin after acid hydrolysis prepared in example 1 was added to a glass reaction vessel, and 120g of sodium hydroxide was added thereto and dissolved in 1000mL of water to completely dissolve the lignin. Then, 174g (1mol) of arginine (example 4), 204g (1mol) of tryptophan (example 5), 146 g (1mol) of lysine (example 6), 155g (1mol) of histidine (example 7) and 120g of a 37% formaldehyde solution were added to the round-bottomed flask, respectively. After the addition of the reactants was completed, the glass reaction kettle was fixed in a water bath at 70 ℃ for reaction for 3 hours. And (3) after the reaction is finished, carrying out nanofiltration on the reaction liquid by adopting a nanofiltration membrane with the molecular weight cutoff of 200-500 Da, wherein the pH of the nanofiltration end point is 4-8, and freeze-drying the nanofiltration concentrated solution to obtain the amino acid lignin. Using nuclear magnetism1H NMR (fig. 3), FTIR (fig. 4) and elemental analysis, which showed N contents of 9.02%, 5.45%, 7.24%, 7.96%, respectively.
Examples 8 to 9: condensation of acidolyzed lignin and organic amine or amino acid to prepare aminated lignin-epoxy amination reaction
Adding 174g (1mol) of arginine (example 8), 74g (1mol) of 1, 3-propanediamine (example 9) and 93g (1mol) of epichlorohydrin into a glass reaction kettle, dissolving the arginine, the 1, 3-propanediamine and the epichlorohydrin in 1000mL of water, reacting at 70 ℃ for 7h to prepare a chlorohydrin intermediate solution after the reaction is finished, wherein the chlorohydrin intermediate is taken; 100g of the acid-hydrolyzed lignin prepared in example 1 was added thereto, 120g of sodium hydroxide was added thereto, and the reaction mixture was reacted in a water bath at 40 ℃ for 6 hours. And (3) after the reaction is finished, nanofiltration is carried out on the reaction liquid by adopting a nanofiltration membrane with the molecular weight cutoff of 200-500 Da, the pH of the nanofiltration end point is 4-8, and the concentrated solution after nanofiltration is freeze-dried to obtain amino acid lignin and 1, 3-propane diamine aminated lignin. The N content was found to be 8.96%, 11.25%.
Example 10: condensation of acid hydrolyzed lignin and amino acid to prepare amino acid lignin-esterification reaction
Adding 100g of the acid hydrolyzed lignin prepared in the example 1 into a glass reaction kettle, adding 174g (1mol) of arginine into the glass reaction kettle, dissolving the arginine into 1000mL of anhydrous DMF, adding 244g (2mol) of dimethylaminopyridine serving as a catalyst and 412g (1.99mol) of dicyclohexylcarbodiimide serving as a dehydrating agent into the glass reaction kettle, adding 120g of sodium hydroxide into the glass reaction kettle, reacting for 20 hours at 40 ℃, filtering after the reaction is finished, adding 4000mL of water for washing, performing nanofiltration on the reaction liquid by adopting a nanofiltration membrane with the molecular weight cutoff of 200-500 Da, wherein the pH of the nanofiltration end point is 4-8, and freeze-drying the nanofiltration concentrated solution to obtain the amino acid hydrolyzed lignin. The N content was tested to be 9.63%.
Example 11: preparation of amino acid lignin by condensation of pyrolysis lignin and amino acid
In the same manner as in example 8, the acid-hydrolyzed lignin was further changed to a pyrolyzed lignin, and finally, the N content was found to be 9.07%.
Example 12: preparation of amino acid lignin by condensation of hydrogenolysis lignin and amino acid
In the same manner as in example 8, the acid-hydrolyzed lignin was further changed to hydrogenolysis lignin, and the N content thereof was finally measured to be 9.32%.
Comparative example 1: preparation of amino acid lignin by condensation of undegraded lignin and amino acid
10g of lignin as it is was added to a round-bottomed flask, and 12g of sodium hydroxide was added thereto and dissolved in 100mL of water to completely dissolve the lignin. Then, 17.4g (0.1mol) of arginine and 12g of a 37% formaldehyde solution were sequentially added to the round-bottomed flask. After the addition of the reactants was complete, the round bottom flask was fixed in a water bath at 70 ℃ for 3 h. And after the reaction is finished, placing the round-bottom flask in ice water for rapid cooling, then putting the reacted mixed solution into a dialysis bag of 1000Da for dialysis and purification, and freeze-drying the dialysis product to obtain the amino acid lignin. The N content was tested to be 7.91%.
Example 13
The amino acid lignin prepared in the embodiments 4 to 12 is respectively applied to curing epoxy resin and compared with the traditional epoxy resin curing agent 704, 10g of amino acid lignin or 704 curing agent is weighed, 20g of epoxy resin is put in a beaker, the mixture is evenly mixed and poured into a mould, the curing conditions are 30 ℃, the precuring is carried out for 3h, the curing is carried out at 100 ℃ and 120 ℃ for 3h, and the curing is carried out at 180 ℃ for 1h, so as to obtain the cured epoxy resin. The cured epoxy resin properties were measured as shown in table 2.
TABLE 2 Properties of the cured epoxy resins
And (3) testing mechanical properties: the test was carried out according to GB/T1447-2005 using a H10K-S universal material testing machine from Tiniius Olsen, USA, with a tensile speed of 20 mm/min.
Water absorption test: accurately weighing the dried sample mass M1Immersing in distilled water for a certain period of time, taking out, wiping off surface water, and precisely weighing mass M2Then, the water absorption W% of the cured epoxy resin can be calculated by the following formula: w% ((M))2-M1)/M1。
The invention provides a bio-based epoxy resin curing agent and a preparation method thereof, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the invention, and it should be noted that, for those skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and these improvements and decorations should also 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.
Reference documents:
[1] preparation and application of zhangwei, biological refining lignin-based phenolic resin [ D ]. beijing: china forestry science research institute, 2013: 1-167.
Claims (3)
1. A preparation method of a bio-based epoxy resin curing agent is characterized in that degraded lignin and amino acid are subjected to condensation reaction to obtain an amino acid lignin solution, and the amino acid lignin solution is subjected to nanofiltration drying to obtain amino acid lignin; carrying out curing reaction on the obtained amino acid lignin and epoxy resin to obtain a biological epoxy resin curing agent;
wherein, the degradation is any one of acidolysis, pyrolysis and hydrogenolysis;
wherein, the acidolysis is to carry out acidolysis reaction on lignin and an acidolysis catalyst in a solvent; wherein, the acidolysis catalyst is any one or the combination of two of hydrobromic acid and hydroiodic acid; the solvent is any one or the combination of two of N, N-dimethylformamide and tetrahydrofuran; the mass volume ratio of the lignin to the solvent is 0.2-0.5 g/mL; the mass ratio of the acidolysis catalyst to the lignin is (0.05-2): 1; the reaction temperature is 70-110 ℃, and the reaction time is 1-3 h;
wherein the pyrolysis is to pyrolyze the lignin at 140-200 ℃ for 1-3 h;
wherein, the hydrogenolysis is to place the lignin in a solvent, add a catalyst and carry out high-pressure hydrogenolysis reaction; wherein, the solvent is any one or the combination of two of methanol and ethanol; the catalyst is a hydrogenation metal loaded solid acid catalyst; the mass-volume ratio of the lignin to the solvent is 20-80 mg/mL; the mass ratio of the lignin to the catalyst is 1 (0.02-0.05), and the high-pressure reaction is carried out for 6-12 h at the hydrogen pressure of 2-6 MPa and the temperature of 160-250 ℃;
wherein the condensation reaction is any one of the following three methods:
the method comprises the following steps: degraded lignin: formaldehyde: amino acids: sodium hydroxide: water is mixed according to the weight ratio of 100-200 g: 30-150 g: 0.5-2 mol: 120-200 g: reacting for 3-6 h at the temperature of 50-90 ℃ by using 1000mL of the catalyst;
the second method comprises the following steps: (1) dissolving amino acid and chloropropane in water according to a molar ratio of 1:1, and reacting at 50-80 ℃ for 3-7 h to obtain a chlorohydrin intermediate solution; (2) adding degraded lignin and sodium hydroxide into the chlorohydrin intermediate solution obtained in the step (1) to react for 3-6 h at 25-60 ℃;
in the step (1), the concentration of the amino acid is 0.2-2 mol/L;
in the step (2), the molar mass ratio of the chlorohydrin intermediate to the degraded lignin is (0.2-2): (100-200) mol/g; the mass ratio of the sodium hydroxide to the lignin is 1-2: 1.2-2;
the third method comprises the following steps: degraded lignin: amino acids: catalyst: dehydrating agent: the solvent is mixed according to the weight ratio of 100-200 g: 0.5-2 mol: 1-4 mol: 1.5-3 mol: reacting for 2-6 h at 70-100 ℃ by using 1000mL of the catalyst; wherein, the catalyst is concentrated sulfuric acid or an acylation reagent; the solvent is anhydrous N, N-dimethylformamide or anhydrous tetrahydrofuran.
2. The preparation method of the bio-based epoxy resin curing agent according to claim 1, wherein the curing reaction is to mix the amino acid lignin and the epoxy resin according to a mass ratio of 0.1-0.5: 1, pre-cure the mixture for 2-4 hours at 20-40 ℃, cure the mixture for 2-3 hours at 100-120 ℃, and finally cure the mixture for 0.5-2 hours at 160-200 ℃.
3. A bio-based epoxy resin curing agent prepared by the method of any one of claims 1 to 2.
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| CN113402731B (en) * | 2021-07-09 | 2022-06-21 | 山西生物质新材料产业研究院有限公司 | Curing accelerator based on enzymatic hydrolysis lignin, preparation method and application thereof |
| CN113667099B (en) * | 2021-07-19 | 2024-04-26 | 中国科学院宁波材料技术与工程研究所 | Single-component epoxy resin based on amino acid type curing agent |
| CN113667081B (en) * | 2021-07-21 | 2022-05-20 | 南京工业大学 | Lignin-based polyurethane chain extender and preparation method and application thereof |
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