CN109384748A - Biological base epoxy based on natural amino acid and its preparation method and application - Google Patents
Biological base epoxy based on natural amino acid and its preparation method and application Download PDFInfo
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- CN109384748A CN109384748A CN201810972653.4A CN201810972653A CN109384748A CN 109384748 A CN109384748 A CN 109384748A CN 201810972653 A CN201810972653 A CN 201810972653A CN 109384748 A CN109384748 A CN 109384748A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/30—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with carboxyl radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
- C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
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Abstract
It include natural amino acid and aldehyde compound in structural formula the invention discloses a kind of biological base epoxy based on native amino acid compound.The invention also discloses the preparation methods of above-mentioned biological base epoxy, it include: that under heat effect condensation reaction occurs for native amino acid monomers with aldehyde compound under the alcoholic environment of alkalinity, obtained biology base schiff bases polyfunctional monomer is in ethanol solution and reduction reaction occurs for sodium borohydride, epoxidation reaction occurs in obtained biology base polyfunctional monomer and epoxychloropropane solution, biological base epoxy is prepared.Preparation flow provided by the invention is simple, and operating method is easy, and controllability is good, easy to implement, is suitable for large-scale industrial production.Thermosetting epoxy resin prepared by the biological base epoxy provided by the invention based on native amino acid compound and amine or anhydride curing agent has excellent thermal property and mechanical property, has a possibility that substituting existing petroleum-based products.
Description
Technical field
The invention belongs to thermosetting epoxy resin technical fields, in particular to the biology base asphalt mixtures modified by epoxy resin based on natural amino acid
Rouge and its preparation method and application.
Background technique
Epoxy resin refer in molecular structure containing there are two and more epoxy group a quasi polymer general name.It is
The polycondensation product of epoxychloropropane and bisphenol-A or other polyalcohols.Due to the high chemical activity of its structure epoxy group, can with it is more
Compound of the kind containing active hydrogen is reacted, so that solidifying crosslinking generates reticular structure, therefore it is a kind of thermosetting resin.
Epoxy resin is a kind of universal thermosetting resin with very extensive purposes, is answered extensively due to its excellent comprehensive performance
It is a kind of very important high molecular material for fields such as space flight and aviation, coating, bonding agent, circuit packages.However, existing rank
The most of epoxy resin of section all derives from petroleum resources, and petroleum resources are a kind of unsustainable resources, along with it
The increasingly reduction of reserves necessarily will cause the continuous raising of the high molecular material cost from petroleum resources.Recently, it is protecting
Under the dual-pressure of environment and saving petroleum resources, enter people's by the biology base high molecular material of raw material of sustainable resource
The visual field, correlative study and development and utilization are increasingly by the attention of people.
The Chinese patent literature of Publication No. CN107556459A discloses a kind of biology basic ring of structure novel containing pyridazinone
The preparation method of oxygen resin passes through friedel-craft using Lewis acid as catalyst using organism-based raw material guaiacol and succinic anhydride
Reaction obtains intermediate acid；Under the action of hydrazine hydrate, intermediate acid closed loop obtains nitrogen-containing heterocycle compound；Then with a nitro
Benzene sulfonic acid sodium salt is oxidant, and dehydrogenation obtains the class bisphenol compound of the structure containing pyridazinone；Finally using epoxychloropropane as reagent,
The compound both ends of the structure containing pyridazinone introduce epoxy group.The Chinese patent literature of Publication No. CN105273166A discloses one
The preparation method of the biological base epoxy of kind: terminal groups modification is carried out to low molecular weight using maleic anhydride and obtains both ends carboxylic
The polylactic acid of base sealing end；Zinc powder be catalyst, DMSO be solvent under conditions of, by glycidyl methacrylate to poly- cream
Acid is modified, to introduce epoxy group at polylactic acid molecule chain both ends；Cause epoxy finally by curing agent appropriate is added
Base open loop, to be cross-linked into tridimensional network and solidify.Currently, yet there are no the report for preparing epoxy resin with natural amino acid
Road.
Native amino acid compound can be obtained largely from animal and plant, and the amino in structure can be with source
Polycondensation is carried out in the aldehyde compound of plant resources, and multifunctional single group similar with petroleum-based chemicals bisphenol-A is finally prepared
Body it is known that bisphenol-A is under a cloud physiological-toxicity, and has been used by limitation, therefore send out energetically in many countries such as Europe
The exhibition renewable polyfunctional monomer of biology base has extraordinary development prospect and meets the green sustainable of Polymeric Industry
Development strategy.
Summary of the invention
Biological base epoxy that the purpose of the present invention is to provide a kind of based on natural amino acid and preparation method thereof and
Using.Preparing raw material and being obtained from animal and plant for biology base epoxy provided by the invention, it is more environmentally-friendly, in heat
It learns and mechanical property aspect improves relative to traditional bisphenol A epoxide resin；Preparation method provided by the invention is simple
Convenient, operating method is easily understood, and reaction condition is controllable and convenient to carry out, is adapted for large-scale industrial production.
A kind of biological base epoxy based on natural amino acid, has the following structure:
Wherein, the amino acid where R1 be selected from alanine, glutamic acid, asparatate, glycine, histidine, leucine,
One of lysine, phenylalanine, serine, threonine, tyrosine or valine；Aldehyde compound where R2 is selected from perfume
One of Lan Su, syringaldehyde, O-VANILLIN or salicylide.
The preparation method of the present invention also provides a kind of biological base epoxy based on natural amino acid, comprising:
(1) condensation occurs under the alcoholic environment of alkalinity with aldehyde compound under heat effect for native amino acid monomers anti-
It answers, obtains biology base schiff bases polyfunctional monomer, structural formula is
(2) the biology base schiff bases polyfunctional monomer that will be obtained, in ethanol solution and reduction occurs for sodium borohydride instead
It answers, obtains biology base polyfunctional monomer, structural formula is
(3) by obtained biology base polyfunctional monomer under phase transfer catalyst effect, in epoxychloropropane solution
Epoxidation reaction occurs, biological base epoxy is prepared.
In step (1), the native amino acid monomers be selected from alanine, glutamic acid, asparatate, glycine,
One of histidine, leucine, lysine, phenylalanine, serine, threonine, tyrosine or valine；The aldehyde radical
Compound is selected from one of vanillic aldehyde, syringaldehyde, O-VANILLIN or salicylide.
In step (1), the molar ratio of the native amino acid monomers and aldehyde compound is 1:1-2.5.Aldehyde radical phase
To the micro- excess of amino, guarantee that natural amino acid monomer reaction is complete.
In step (1), the reaction temperature of the condensation reaction is 30~80 DEG C, the reaction time is 12~for 24 hours.
Preferably, in step (1), the native amino acid monomers be selected from glutamic acid, tyrosine, asparatate,
Or phenylalanine；The aldehyde compound is selected from vanillic aldehyde or O-VANILLIN；The native amino acid monomers and aldehyde radical
The molar ratio for closing object is 1.1-1.6；The reaction temperature of condensation reaction is 60~80 DEG C, and the reaction time is 12~14h.R1 is more carboxylics
Acid or the structure containing phenyl ring, the glass transition temperature and tensile property of the biology base epoxy resin cured product after solidification are preferable；It rubs
You are according to the decision of the reactivity of above-mentioned native amino acid monomers ratio, reaction temperature and reaction time.
In step (2), the molar ratio of biology base schiff bases polyfunctional monomer and sodium borohydride is 1:2-4.
In step (2), the reaction temperature of the reduction reaction is 10~30 DEG C, and the reaction time is 12~36h.
Preferably, in step (2), the molar ratio of biology base schiff bases polyfunctional monomer and sodium borohydride is 1:2-
3.5；The reaction temperature of reduction reaction be 20~30 DEG C, the reaction time be 12~for 24 hours.Reduction Schiff can be improved in above-mentioned molar ratio
The yield of alkali reduces the generation of side reaction, and reaction temperature and reaction time determine according to reactivity.
In step (3), mole of the biology base polyfunctional monomer and epoxychloropropane and phase transfer catalyst
Than for 1:5-20:0.1-0.5.
The phase transfer catalyst is tetrabutylammonium bromide.
In step (3), the reaction temperature of the epoxidation reaction is 60~100 DEG C, and the reaction time is 1~12h.
The application of the present invention also provides a kind of biological base epoxy based on natural amino acid, the biology base epoxy
Resin and amine curing agent or anhydride curing agent are heating and curing 2-8 hours at 100-180 DEG C of temperature, obtain thermosetting property biology base
Epoxy resin.
Preferably, the biological base epoxy is selected from epoxidation tyrosine-vanillic aldehyde compound, epoxidation benzo ammonia
One of acid-O-VANILLIN compound, glutamic acid-O-VANILLIN or epoxidation asparatate-O-VANILLIN compound, Gu
Thermosetting property biology base epoxy after change has higher hot property and mechanical property.
Compared with prior art, the beneficial effects of the present invention are embodied in:
Forerunner based on the biological base epoxy of native amino acid compound as heat-curable epoxy resin of the invention
Body, as raw material, preparation method is simple and efficient the native amino acid compound and aldehyde compound for directlying adopt bio-based source,
It is easy to operate, controllably make, can be mass produced using existing chemical industry equipment, have yield high, simple process it is excellent
Point is suitable for large-scale industrial production, can also reduce existing petroleum-based epoxy resins to the dependence of fossil resources and its to ring
The pollution in border.
Since origin of amino acid is in biomass material, the exploitation of this biology base epoxy resin product can push away
The development of dynamic bio-based materials, is of great significance to the sustainable development for promoting the fields such as entire high molecular material, is a kind of
Biology base, green, environment-friendly products have the double effects saved petroleum resources and protect environment.
Biological base epoxy provided by the invention based on natural amino acid, the thermoset epoxy obtained after finally solidifying
Resin product crosslink density with higher and have excellent calorifics and mechanical property, relative to traditional bisphenol-A epoxy tree
Rouge, especially glass transition temperature and tensile property are greatly improved, and can be used as the candidate of high-performance bonding agent.
Detailed description of the invention
Fig. 1 is alanine-vanillic aldehyde base epoxy nuclear magnetic resonance spectroscopy prepared by embodiment 11H-NMR；
Fig. 2 is lysine-vanillic aldehyde epoxy resin nuclear magnetic resonance spectroscopy prepared by embodiment 21H-NMR。
Specific embodiment
Below with reference to embodiment, the present invention is further explained.It should be understood that these embodiments be merely to illustrate the present invention without
For limiting the scope of the invention.
The biology base epoxy resin cured product prepared in embodiment passes through nuclear magnetic resonance spectroscopy1H-NMR is public using Brooker
Take charge of III type spectrometer (Spectrometer) of the 400AVANCE measurement of (Bruker), 400MHz, deuterated chloroform (CDCl3)。
The yield of biological base epoxy is calculated by the following formula to obtain:
Yield=biology base epoxy mass number/(molal quantity of amino acid × biology base epoxy molal weight)
× 100%.
Embodiment 1
By 1mol alanine, 1.2mol vanillic aldehyde, 1mol KOH, be dissolved in 250mL ethyl alcohol, react 24 at 30 DEG C
Hour after, be added the sodium borohydride of 3mol and by reaction temperature control at 10 DEG C, the reaction was continued at this temperature 36 hours, finally
Obtain alanine-vanillic aldehyde polyfunctional monomer, yield 89%.
By 1mol alanine-vanillic aldehyde polyfunctional monomer and 5mol epoxychloropropane in 0.1mol tetrabutylammonium bromide
In the presence of, it is reacted 2 hours at 100 DEG C, removes solvent by decompression rotary evaporation, obtain the third ammonia of epoxidation after washing and drying
Acid-vanillic aldehyde compound, yield 93%.Nuclear magnetic resonance spectroscopy1H-NMR is as shown in Figure 1, each peak and epoxidation on figure
Alanine-vanillic aldehyde di-nitrile compound structure hydrogen atom is all one-to-one.
By obtained epoxidation alanine-vanillic aldehyde compound with curing agent DDS according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain third
Propylhomoserin-vanillic aldehyde-DDS epoxy resin-cured product.The glass transition of resulting cured product is 164 DEG C, and tensile strength is
120MPa。
Embodiment 2
By 1mol lysine, 2.5mol vanillic aldehyde, 1.1mol KOH, be dissolved in 200mL ethyl alcohol, reacted at 50 DEG C
After 16 hours, be added the sodium borohydride of 4mol and by reaction temperature control at 20 DEG C, the reaction was continued at this temperature 24 hours, most
Lysine-vanillic aldehyde polyfunctional monomer, yield 81% are obtained eventually.
By 1mol lysine-vanillic aldehyde polyfunctional monomer and 8mol epoxychloropropane in 0.15mol tetrabutylammonium bromide
In the presence of, it is reacted 5 hours at 80 DEG C, removes solvent by decompression rotary evaporation, obtain epoxidation after washing and drying and rely
Propylhomoserin-vanillic aldehyde compound, yield 91%.Nuclear magnetic resonance spectroscopy1H-NMR is as shown in Fig. 2, each peak and epoxy on figure
It is all one-to-one for changing lysine-vanillic aldehyde di-nitrile compound structure hydrogen atom.
By obtained epoxidation lysine-vanillic aldehyde compound with curing agent DDS according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, relied
Propylhomoserin-vanillic aldehyde-DDS epoxy resin-cured product.The glass transition of resulting cured product is 161 DEG C, and tensile strength is
131MPa。
Embodiment 3
By 1mol tyrosine, 1.5mol vanillic aldehyde, 1.5mol KOH, be dissolved in 180mL ethyl alcohol, reacted at 80 DEG C
After 12 hours, be added the sodium borohydride of 2mol and by reaction temperature control at 30 DEG C, the reaction was continued at this temperature 12 hours, most
Tyrosine-vanillic aldehyde polyfunctional monomer, yield 79% are obtained eventually.
By 1mol tyrosine-vanillic aldehyde polyfunctional monomer and 12mol epoxychloropropane in 0.2mol tetrabutylammonium bromide
In the presence of, it is reacted 8 hours at 70 DEG C, removes solvent by decompression rotary evaporation, obtain epoxidation junket after washing and drying
Propylhomoserin-vanillic aldehyde compound, yield 87%.
By obtained epoxidation tyrosine-vanillic aldehyde compound with curing agent DDS according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain junket
Propylhomoserin-vanillic aldehyde-DDS epoxy resin-cured product.The glass transition of resulting cured product is 231 DEG C, and tensile strength is
180MPa。
Embodiment 4
By 1mol threonine, 1.1mol salicylide, 1.0mol KOH, be dissolved in 280mL ethyl alcohol, reacted at 50 DEG C
After 21 hours, the sodium borohydride of 2.5mol is added and controls reaction temperature at 10 DEG C, the reaction was continued at this temperature 20 hours,
Finally obtain threonine-salicylide polyfunctional monomer, yield 89%.
By 1mol threonine-salicylide polyfunctional monomer and 5mol epoxychloropropane in 0.3mol tetrabutylammonium bromide
In the presence of, it is reacted 1 hour at 100 DEG C, removes solvent by decompression rotary evaporation, epoxidation Soviet Union ammonia is obtained after washing and drying
Acid-bigcatkin willow aldehyde compound, yield 93%.
By obtained epoxidation threonine-bigcatkin willow aldehyde compound with curing agent DDM according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, revived
Propylhomoserin-salicylide-DDM epoxy resin-cured product.The glass transition of resulting cured product is 131 DEG C, and tensile strength is
101MPa。
Embodiment 5
By 1mol phenylalanine, 1.6mol O-VANILLIN, 1.7mol KOH, be dissolved in 320mL ethyl alcohol, at 70 DEG C
After reaction 12 hours, the sodium borohydride of 3mol is added and controls reaction temperature at 30 DEG C, it is 12 small that the reaction was continued at this temperature
When, finally obtain phenylalanine-O-VANILLIN polyfunctional monomer, yield 85%.
By 1mol phenylalanine-O-VANILLIN polyfunctional monomer and 14mol epoxychloropropane in 0.5mol tetrabutyl bromine
It in the presence of changing ammonium, is reacted 2 hours at 100 DEG C, removes solvent by decompression rotary evaporation, obtain epoxy after washing and drying
Change phenylalanine-O-VANILLIN compound, yield 96%.
By obtained epoxidation phenylalanine-O-VANILLIN compound and curing agent DDM according to epoxy and NH mono- to one
Molar ratio in acetone in carry out heating precuring in convection oven after mixing, finally 180 DEG C carry out after solidify 2h, obtain
To phenylalanine-O-VANILLIN-DDM epoxy resin-cured product.The glass transition of resulting cured product is 217 DEG C, is drawn
Stretching intensity is 160MPa.
Embodiment 6
By 1mol leucine, 1.2mol syringaldehyde, 1.1mol KOH, be dissolved in 220mL ethyl alcohol, reacted at 40 DEG C
After 22 hours, be added the sodium borohydride of 3mol and by reaction temperature control at 30 DEG C, the reaction was continued at this temperature 14 hours, most
Leucine-syringaldehyde polyfunctional monomer, yield 79% are obtained eventually.
By 1mol leucine-syringaldehyde polyfunctional monomer and 9mol epoxychloropropane in 0.2mol tetrabutylammonium bromide
In the presence of, it is reacted 5.5 hours at 80 DEG C, removes solvent by decompression rotary evaporation, it is bright to obtain epoxidation after washing and drying
Propylhomoserin-cloves aldehyde compound, yield 93%.
By obtained epoxidation leucine-cloves aldehyde compound with curing agent DDM according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain bright
Propylhomoserin-syringaldehyde-DDM epoxy resin-cured product.The glass transition of resulting cured product is 119 DEG C, and tensile strength is
127MPa。
Embodiment 7
By 1mol glutamic acid, 1.5mol O-VANILLIN, 2mol KOH, be dissolved in 220mL ethyl alcohol, reacted at 60 DEG C
After 14 hours, the sodium borohydride of 3.5mol is added and controls reaction temperature at 20 DEG C, the reaction was continued at this temperature 18 hours,
Finally obtain glutamic acid-O-VANILLIN polyfunctional monomer, yield 83%.
By 1mol glutamic acid-O-VANILLIN polyfunctional monomer and 20mol epoxychloropropane in 0.3mol tetrabutyl phosphonium bromide
It in the presence of ammonium, is reacted 12 hours at 70 DEG C, removes solvent by decompression rotary evaporation, obtain epoxidation after washing and drying
Glutamic acid-O-VANILLIN compound, yield 88%.
By obtained epoxidation glutamic acid-O-VANILLIN compound and curing agent DDM rubbing according to epoxy and NH mono- to one
You, which compare in acetone, carries out heating precuring in convection oven after mixing, solidifies 2h after finally carrying out at 180 DEG C, obtains
Glutamic acid-O-VANILLIN-DDM epoxy resin-cured product.The glass transition of resulting cured product is 230 DEG C, is stretched strong
Degree is 171MPa.
Embodiment 8
By 1mol asparatate, 1.1mol O-VANILLIN, 2mol KOH, be dissolved in 200mL ethyl alcohol, at 70 DEG C
After reaction 12 hours, the sodium borohydride of 3mol is added and controls reaction temperature at 20 DEG C, it is 24 small that the reaction was continued at this temperature
When, finally obtain asparatate-O-VANILLIN polyfunctional monomer, yield 81%.
By 1mol asparatate-O-VANILLIN polyfunctional monomer and 20mol epoxychloropropane in the 0.3mol tetrabutyl
It in the presence of ammonium bromide, is reacted 12 hours at 60 DEG C, removes solvent by decompression rotary evaporation, obtain ring after washing and drying
Aoxidize asparatate-O-VANILLIN compound, yield 90%.
By obtained epoxidation asparatate-O-VANILLIN compound and curing agent DDM according to epoxy and NH mono- to one
Molar ratio in acetone in carry out heating precuring in convection oven after mixing, finally 180 DEG C carry out after solidify 2h,
Obtain asparatate-O-VANILLIN-DDM epoxy resin-cured product.The glass transition of resulting cured product is 222
DEG C, tensile strength 165MPa.
Embodiment 9
By 1mol glycine, 1.3mol salicylide, 1.2mol KOH, be dissolved in 200mL ethyl alcohol, reacted at 40 DEG C
After 18 hours, be added the sodium borohydride of 2mol and by reaction temperature control at 10 DEG C, the reaction was continued at this temperature 24 hours, most
Glycine-salicylide polyfunctional monomer, yield 89% are obtained eventually.
By 1mol glycine-salicylide polyfunctional monomer and 8mol epoxychloropropane in 0.2mol tetrabutylammonium bromide
In the presence of, it is reacted 8 hours at 80 DEG C, removes solvent by decompression rotary evaporation, obtain the sweet ammonia of epoxidation after washing and drying
Acid-bigcatkin willow aldehyde compound, yield 90%.
By obtained epoxidation glycine-bigcatkin willow aldehyde compound with curing agent DDM according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain sweet
Propylhomoserin-salicylide-DDM epoxy resin-cured product.The glass transition of resulting cured product is 158 DEG C, and tensile strength is
119MPa。
Embodiment 10
By 1mol histidine, 1.3mol syringaldehyde, 1.2mol KOH, be dissolved in 180mL ethyl alcohol, reacted at 30 DEG C
After 20 hours, the sodium borohydride of 2.5mol is added and controls reaction temperature at 30 DEG C, the reaction was continued at this temperature 12 hours,
Finally obtain histidine-syringaldehyde polyfunctional monomer, yield 79%.
By 1mol histidine-syringaldehyde polyfunctional monomer and 10mol epoxychloropropane in 0.15mol tetrabutylammonium bromide
In the presence of, it is reacted 2 hours at 100 DEG C, removes solvent by decompression rotary evaporation, obtain epoxidation group after washing and drying
Propylhomoserin-cloves aldehyde compound, yield 92%.
By obtained epoxidation histidine-cloves aldehyde compound with curing agent DDM according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain group
Propylhomoserin-syringaldehyde-DDM epoxy resin-cured product.The glass transition of resulting cured product is 170 DEG C, and tensile strength is
135MPa。
Embodiment 11
By 1mol serine, 1.1mol salicylide, 1.1mol KOH, be dissolved in 220mL ethyl alcohol, reacted at 40 DEG C
After 20 hours, be added the sodium borohydride of 3mol and by reaction temperature control at 25 DEG C, the reaction was continued at this temperature 28 hours, most
Serine-salicylide polyfunctional monomer, yield 85% are obtained eventually.
By 1mol serine-salicylide polyfunctional monomer and 18mol epoxychloropropane in 0.2mol tetrabutylammonium bromide
In the presence of, it is reacted 10 hours at 70 DEG C, removes solvent by decompression rotary evaporation, obtain epoxidation silk after washing and drying
Propylhomoserin-bigcatkin willow aldehyde compound, yield 89%.
By obtained epoxidation serine-bigcatkin willow aldehyde compound with curing agent DDM according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain silk
Propylhomoserin-salicylide-DDM epoxy resin-cured product.The glass transition of resulting cured product is 128 DEG C, and tensile strength is
128MPa。
Embodiment 12
By 1mol valine, 1.1mol vanillic aldehyde, 1.1mol KOH, be dissolved in 200mL ethyl alcohol, reacted at 50 DEG C
After 18 hours, the sodium borohydride of 2.5mol is added and controls reaction temperature at 25 DEG C, the reaction was continued at this temperature 16 hours,
Finally obtain valine-vanillic aldehyde polyfunctional monomer, yield 85%.
By 1mol valine-vanillic aldehyde polyfunctional monomer and 16mol epoxychloropropane in 0.4mol tetrabutylammonium bromide
In the presence of, it is reacted 10 hours at 90 DEG C, removes solvent by decompression rotary evaporation, obtain epoxidation figured silk fabrics after washing and drying
Propylhomoserin-vanillic aldehyde compound, yield 91%.
By obtained epoxidation valine-vanillic aldehyde compound with curing agent DDM according to mole of epoxy and NH mono- to one
Than carrying out heating precuring in convection oven after mixing in acetone, solidifies 2h after finally carrying out at 180 DEG C, obtain figured silk fabrics
Propylhomoserin-vanillic aldehyde-DDM epoxy resin-cured product.The glass transition of resulting cured product is 105 DEG C, and tensile strength is
107MPa。
From above-described embodiment as can be seen that the solidification of the biological base epoxy provided by the invention based on natural amino acid
Object, that is, thermosetting epoxy resin calorifics with higher and mechanical property, glass transition temperature are 105-231 DEG C, are stretched strong
Degree is 101-180Mpa.Particularly, the glass transition of the solidfied material for the biological base epoxy that embodiment 3,5,7 and 8 provides
Temperature is at least 217 DEG C, and tensile strength is at least 165Mpa, has better calorifics and mechanical property.
Claims (8)
1. a kind of biological base epoxy based on natural amino acid, has the following structure:
Wherein, the amino acid where R1 is selected from alanine, glutamic acid, asparatate, glycine, histidine, leucine, relies ammonia
One of acid, phenylalanine, serine, threonine, tyrosine or valine；Aldehyde compound where R2 is selected from chinese cymbidium
One of element, syringaldehyde, O-VANILLIN or salicylide.
2. a kind of method for preparing the biological base epoxy described in claim 1 based on natural amino acid, comprising:
(1) under heat effect condensation reaction occurs for native amino acid monomers with aldehyde compound under the alcoholic environment of alkalinity,
Biology base schiff bases polyfunctional monomer is obtained, structural formula is
(2) the biology base schiff bases polyfunctional monomer that will be obtained, in ethanol solution and reduction reaction occurs for sodium borohydride, obtains
To biology base polyfunctional monomer, structural formula is
(3) obtained biology base polyfunctional monomer and is occurred under phase transfer catalyst effect in epoxychloropropane solution
Biological base epoxy is prepared in epoxidation reaction.
3. the preparation method of the biological base epoxy according to claim 1 based on natural amino acid, which is characterized in that
In step (1), the native amino acid monomers are selected from alanine, glutamic acid, asparatate, glycine, histidine, bright
One of propylhomoserin, lysine, phenylalanine, serine, threonine, tyrosine or valine；The aldehyde compound choosing
From one of vanillic aldehyde, syringaldehyde, O-VANILLIN or salicylide.
4. the preparation method of the biological base epoxy according to claim 2 based on natural amino acid, which is characterized in that
In step (1), the molar ratio of the native amino acid monomers and aldehyde compound is 1:1-2.5, the condensation reaction
Reaction temperature be 30~80 DEG C, the reaction time be 12~for 24 hours.
5. the preparation method of the biological base epoxy according to claim 4 based on natural amino acid, which is characterized in that
In step (1), the native amino acid monomers in glutamic acid, asparatate, tyrosine or phenylalanine one
Kind.
6. the preparation method of the biological base epoxy according to claim 2 based on natural amino acid, which is characterized in that
In step (2), the molar ratio of biology base schiff bases polyfunctional monomer and sodium borohydride is 1:2-4, the reduction reaction
Reaction temperature be 10~30 DEG C, the reaction time be 12~36h.
7. the preparation method of the biological base epoxy according to claim 1 based on natural amino acid, which is characterized in that
In step (3), the biology base polyfunctional monomer is 1:5- with the molar ratio of epoxychloropropane and phase transfer catalyst
20:0.1-0.5.
8. a kind of application of the biological base epoxy described in claim 1 based on natural amino acid, which is characterized in that described
Biological base epoxy and amine curing agent or anhydride curing agent be heating and curing at 100-180 DEG C of temperature 2-8 hours, obtain
Thermosetting property biology base epoxy.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111187190A (en) * | 2020-01-10 | 2020-05-22 | 华南理工大学 | Epoxy resin based on vanillin and amino acid and preparation method and application thereof |
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