CN107540820A - A kind of bio-oil base epoxy and its preparation method and application - Google Patents
A kind of bio-oil base epoxy and its preparation method and application Download PDFInfo
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- CN107540820A CN107540820A CN201710629593.1A CN201710629593A CN107540820A CN 107540820 A CN107540820 A CN 107540820A CN 201710629593 A CN201710629593 A CN 201710629593A CN 107540820 A CN107540820 A CN 107540820A
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Abstract
The present invention discloses a kind of bio-oil base epoxy and its preparation method and application.The epoxy resin is obtained from being used as curing agent and epoxy bio oil progress crosslinking curing by natural binary acid, without external catalyst action (or adding catalyst).Epoxy bio oil is used for epoxide resin material by the present invention, for widening natural oil lipid products application and improving its added value, by with positive reference value, and for reducing or serving positive role instead of environmental problem caused by the use of petroleum-type non-renewable resources.And although the introducing of natural binary acid decreases in some aspect of performances, also has in some performances and is significantly lifted, and for the catabolite totally nontoxic of bio-oil base epoxy.Therefore, the epoxy resin is environment-protecting and non-poisonous degradable, has absolute pollution free green environment protection, and has good mechanical property and biocompatibility, is expected to be used widely in fields such as solventless coatings, biomaterial, polymeric membranes.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of bio-oil base epoxy and preparation method thereof and
Using.
Background technology
Epoxy resin (EpoxyResin) refers in molecular structure containing 2 or more than 2 epoxy radicals and consolidated in appropriate
The general name of the lower three-dimensional netted organic high molecular compound formed of agent effect, it is a kind of important thermosetting resin.Because
It has good insulating properties, heat endurance, cohesiveness and mechanical property, and diversified moulding process is cost-effective, extensively should
For the field such as Aeronautics and Astronautics, electronics, electric.Nowadays, about 90% epoxy resin of worldwide production is by bisphenol-A and ring
Oxygen chloropropane reaction generation bisphenol A-type diglycidyl ether (DGEBA), however, bisphenol-A is chaff interference in a kind of environment, it has
There is the characteristic of simulation estrogen, be detrimental to health by this effect, so many countries are strict to limit answering for bisphenol-A
With, and fossil resources are non-renewable resources, long period of development is difficult to ensure that the prospect of its sustainable development.Therefore with renewable
Green resource is that the biological fat-based epoxy resin of raw material research not only conforms with green theory, and can be by asphalt mixtures modified by epoxy resin
The application field of fat expands.Such as Kasaai M R. etc. using and epoxide crosslinking chitosan be prepared for it is a kind of new
Biodegradable shape-memory stents, available in terms of biological medicine.
Vegetable oil is a kind of natural reproducible resource, can be viscous by carrying out the processing such as epoxidation, addition, polymerization to it
It is applied in mixture, coating, slow-release material, biological medicine material Polymer material.Vegetable oil is usually several different
The mixture of fatty acid triglyceride composition, wherein forming long chain fatty acids carbochain by the 14-24 carbon not waited, contain in carbochain
0-3 double bond, the conjugated degree difference of unsaturated bond and degree of unsaturation result in the difference of plant oil structure in molecular structure.It is sweet
Comprising several activation degrees for being easy to participate in chemical reaction in oily three fat, such as double bond, pi-allyl, the alpha active of ester group and ester group
Position, the method for preparing vegetable oil based thermoset applications may be summarized to be three major types, C=C direct polymerizations；C=C epoxidations；Propylene
Acidifying plant oil.There is the strand of one section of saturation between double bond and segment in epoxidized vegetable oil structure, it is participated in vegetable oil
Side chain is formed after polymerization has the function that plasticising, and Long carbon chain polarity is low to cause the very strong hydrophobicity of vegetable oil and hydrolysis-stable
Property.Animal fat is broadly divided into terricole grease and ocean class animal fat, wherein terricole grease mainly by stearic acid,
Palmitic acid and the aliphatic acid of triglyceride saturation composition；Ocean class animal fat composition is except containing palmitic acid, stearic acid, oil
Beyond acid, the unsaturated acids also containing 22-24 carbon and 4-6 double bond and the unsaturated acids containing 10-14 carbon.For terrestrial
Animal fat, under conditions of strong, the aliphatic acid of saturation also can epoxidation；For marine animal grease as vegetable fat
It is easy to epoxidation.Due to having oxygen-containing tricyclic structure in epoxy bio-oil structure, there is larger tension force, can be former with active hydrogen
Hydroxyl, amido, acid anhydrides and the radical polymerisation containing unsaturated bond of son.Such as Sibi etc. has developed from epoxidation sucrose soybean fat
Complete reproducible epoxy thermoset material is solidified in the presence of DBU is as catalyst with the bio-based dicarboxylic acids of end-blocking；Matharu
Et al. develop a kind of new completely renewable thermosetting by ELO and two biologically-derived acid crosslinking agents in the presence of amine catalyst
Property resin；Robertson et al. have studied epoxidised soybean oil and business BPA bases component and 4,4'- diaminodiphenyl-methanes
As the hydrolytic degradation of the mixture epoxy resin of curing agent and hot property etc.；But all these plant oil epoxy resin systems
The curing agent used during standby, ring opening agent or catalyst both are from fossil resource, do not meet the hair of current environmental protection and energy saving
Exhibition trend.
It is many to be related to the patent of epoxy resin at present, but is seldom related to the patent of bio-oil base epoxy, and is related to
Although the patent of bio-oil base epoxy also has been reported that, such as Publication No. CN104448365A Chinese invention patent hair
Understand a kind of epoxidized vegetable oil it is epoxy resin toughened/method of cellulose composite membrane, Publication No. CN104693418A China
Patent of invention has invented a kind of epoxy resin cure film of high fat content and preparation method and application, Publication No.
CN104892858A Chinese invention patent invented a kind of high Bio-based content composition epoxy resin and its curing and
Using, although several patents of invention of the above are not curing agent as raw material using natural binary acid all using vegetable oil as raw material,
And curing accelerator beyond curing agent or organic solvent are all added for auxiliary.This patent is using bio oil as raw material, natural binary
Acid is curing agent, addition do not add water either as solvent, it is necessary to or be not required to external catalyst preparation neo-epoxy resin, behaviour
Make simple, material environment friendly poisonless biological degradable.
The content of the invention
The shortcomings that in order to overcome prior art, is to provide a kind of bio-oil basic ring with deficiency, primary and foremost purpose of the invention
The preparation method of oxygen tree fat.For this method using epoxy bio oil as raw material, natural binary acid is curing agent, adds or does not add water
As adjuvant, it is necessary to or be not required to external catalyst preparation epoxy resin, it is simple to operate, material environment friendly it is nontoxic can biology drops
Solution.
Another object of the present invention is to provide a kind of bio-oil base epoxy.The bio-oil base epoxy is
A kind of new thermosetting resin, it is to carry out crosslinking curing as curing agent and epoxy bio oil to obtain by natural binary acid
Arrive, without external catalyst action (or adding catalyst).Non-toxic degradable can be reached, and there is good mechanics
Performance and biocompatibility, it is expected to be used widely in fields such as solventless coatings, biomaterial, polymeric membranes.
It is yet a further object of the present invention to provide above-mentioned bio-oil base epoxy in biomaterial (such as human body skin
Wound repair vector), the aspect application of solventless coatings, polymeric membrane etc..
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of bio-oil base epoxy, comprises the following steps：
(1) the natural binary acid measured and deionized water are sequentially added in a kettle, stirs and heats up, and are added for the first time
Enter the epoxy bio oil of part, stir and be warming up to 70~160 DEG C, 10~90min of reaction；Then once or repeatedly add
The epoxy bio oil of remainder, 70~160 DEG C of reaction temperature, 2~90min of reaction (once or repeatedly add epoxy biology
The total time of oil reaction)；If adding dry catalyst (or being not added with) before reaction terminates, intermediate product is obtained；
Or
The natural binary acid measured and deionized water are sequentially added in a kettle, stirs and heats up, and add epoxy life
Thing oil, stir and be warming up to 70~160 DEG C, 10~90min of reaction；If dry catalyst is added before reaction terminates (or not
Add), obtain intermediate product；
(2) intermediate product made from step (1) is placed in into temperature is in 80~180 DEG C of baking oven, is vacuumizing or not
Under conditions of vacuumizing, 1~24h is reacted, obtains bio-oil base epoxy.
Natural binary acid carboxyl (- COOH) group and deionized water (H described in step (1)2O) mol ratio is 1:0~
1:7；Described deionized water is adjuvant.
The total amount of addition epoxy bio oil described in step (1) is according to epoxy radicals (- EPO) and the carboxyl of natural binary acid
The mol ratio of (- COOH) group calculates, mol ratio 1.5:1~0.7:1.
Natural binary acid described in step (1) refers to naturally occurring dicarboxylic acids, preferably malonic acid, fourth two
At least one of acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or decanedioic acid；
Epoxy bio oil described in step (1) includes epoxidized vegetable oil and epoxy animal oil, wherein epoxidized vegetable oil bag
Epoxy herbaceous plant oil or epoxy xylophyta oil are included, epoxy animal oil includes epoxy terricole oil or epoxy marine animal
Oil；
Described epoxy herbaceous plant oil is preferably epoxy linseed oil, epoxy grape-kernel oil, epoxy perilla herb oil, epoxy core
Peach oil, epoxy apricot kernel oil, epoxy Seabuckthorn Oil, epoxy evening primrose oil, expoxy glass lettuce oil, epoxidized soybean oil, epoxy corn oil, ring
Oxygen peanut oil, epoxy rapeseed oil, epoxy sesame oil, epoxy sunflower oil, epoxy cottonseed oil, epoxy small oil, epoxy fire sesame oil
Or at least one of epoxy siritch etc.；
Described epoxy xylophyta oil is preferably epoxy camellia seed oil, epoxy peony seed oil, epoxy palm oil, epoxy paulownia
At least one of oil, epoxy coconut oil or epoxy olive oil etc.；
Described epoxy terricole oil is preferably epoxy pork fat, epoxy butter, epoxy sheep oil, epoxy chicken fat or epoxy duck
At least one of oil etc.；
Described epoxy marine animal oil is preferably at least one of epoxy whale oil or epoxy deep sea fish oil etc.；
Further, the epoxy bio oil described in step (1) is preferably in epoxidized soybean oil or epoxy linseed oil
It is at least one；
Catalyst described in step (1) includes tertiary amine (such as triethylamine (TEA)), 1- methylimidazoles, 2-methylimidazole, 1,
In the carbon -7- alkene (DBU) of 8- diazacyclos [5,4,0] 11, DMAP (DMAP) or boron trifluoride complex etc.
It is at least one；Preferably at least one of DBU or DMAP.
A kind of bio-oil base epoxy, is prepared by above-mentioned preparation method.
Described bio-oil base epoxy is in biomaterial (such as human body skin wound repair vector), solvent-free painting
Application in the fields such as material, polymeric membrane.
The present invention is had the following advantages and effect relative to prior art：
(1) epoxy bio oil is used for epoxide resin material by the present invention, for widening natural oil lipid products application and carrying
Its high added value, by the use with positive reference value, and for reducing or instead of petroleum-type non-renewable resources
Caused by environmental problem serve positive effect.And although the introducing of natural binary acid has been dropped in some aspect of performances
It is low, but also have greatly improved in some performances, and for bio-oil base epoxy catabolite entirely without
Poison.
(2) present invention uses or does not use deionized water not utilize (or using) external catalyst as solvent, prepare new
Type bio-oil base epoxy, compared to other epoxy resin, it can not only reduce the consumption of fossil energy but also can obtain
Totally nontoxic and the material that can be degraded, the new bio grease base epoxy have absolute pollution free green environment protection.
Brief description of the drawings
Fig. 1 is FTIR (Fourier transform infrared spectrum analysis) spectrogram of the epoxidized soybean oil of embodiment 1.
Fig. 2 is ATR-FTIR (the Fourier transformation decay ATR-FTIRs of the epoxidized soybean oil base epoxy of embodiment 1
Spectrum) spectrogram.
Fig. 3 is the biocompatibility test result of the epoxidized soybean oil base epoxy of embodiment 6.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) malonic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
0.9), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir
And 120 DEG C are warming up to, react 40min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=
0.5:1), 120 DEG C of reaction temperature, 50min is reacted；To pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates,
Obtain intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
8h is dried in baking oven, obtains epoxidized soybean oil base epoxy.
Examination of infrared spectrum, it will treat that test sample (epoxidized soybean oil) coated on KBr pieces, is subsequently placed at German Brooker company
Tested on the type infrared spectrometers of VERTEX 70.Scanning wave-number range is 4000~400cm-1, resolution ratio 4cm-1, scanning 128
Average to obtain the infrared spectrogram of sample after secondary, as shown in Figure 1.
Change the In situ ATR-FTIR figure that decay total emission annex surveys epoxidized soybean oil base epoxy film；Such as Fig. 2 institutes
Show.
Fig. 1 be epoxidized soybean oil (ESO) infrared spectrogram, 750~890cm-1Epoxide group absworption peak, in Fig. 1
The peak position 818cm of mark-1For the absworption peak of epoxide group；As shown in Figure 2, with the progress of reaction, 750~890cm-1's
The absworption peak of epoxide group is wholly absent, and tert-hydroxyl is formed during epoxide group open loop, radiates peak position
1459cm-1, this shows that reaction generates new epoxy resin.
Embodiment 2
(1) malonic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
7), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir simultaneously
160 DEG C are warming up to, reacts 90min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=
0.2:1), 160 DEG C of reaction temperature, 90min is reacted；To pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates,
Obtain intermediate product.
(2) intermediate product made from step (1) is put into 180 DEG C of vacuum drying oven, vacuum dries 24h, and it is big to obtain epoxy
Soya-bean oil base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 3
(1) malonic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
1), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir simultaneously
120 DEG C are warming up to, reacts 40min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=0.5:
1), 120 DEG C of reaction temperature, react 50min, after pour into 7.5cm*7.5cm silica gel mould, the first step reaction terminates, obtain
Intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
8h is dried in baking oven, obtains epoxidized soybean oil base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 4
(1) glutaric acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
1), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir simultaneously
120 DEG C are warming up to, reacts 40min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=0.6:
1), 120 DEG C of reaction temperature, 50min is reacted；Pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates, and obtains
Intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
5h is dried in baking oven, obtains epoxidized soybean oil base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 5
(1) glutaric acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
0), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured：- COOH=1.5:1), stir and be warming up to
70 DEG C, react 10min；Pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates, and obtains intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of baking oven and dries 1h, obtain epoxidized soybean oil basic ring oxygen
Resin.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 6
(1) pimelic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
1), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir simultaneously
120 DEG C are warming up to, reacts 40min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=0.6:
1), 120 DEG C of reaction temperature, 50min is reacted；Pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates, and obtains
Intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
8h is dried in baking oven, obtains epoxidized soybean oil base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 7
The pimelic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:1), stir
Mix and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir and be warming up to
120 DEG C, react 40min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=0.5:1), instead
120 DEG C of temperature is answered, reacts 50min；Before reaction terminates 2min add 2-3 drop catalyst DBU, after pour into 7.5cm*7.5cm's
In silica gel mould, first step reaction terminates, and obtains intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
5h is dried in baking oven, obtains epoxidized soybean oil base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 8
(1) azelaic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
1), stir and heat up, add the epoxidized soybean oil (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir simultaneously
120 DEG C are warming up to, reacts 40min；Then epoxidized soybean oil (molar ratio-the EPO measured is added again：- COOH=0.5:
1), 120 DEG C of reaction temperature, 50min is reacted；Pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates, and obtains
Intermediate product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
6h is dried in baking oven, obtains epoxidized soybean oil base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Embodiment 9
(1) azelaic acid measured and deionized water (molar ratio-COOH are sequentially added in a kettle：H2O=1:
1), stir and heat up, add the epoxy pork fat (molar ratio-EPO measured for the first time：- COOH=0.5:1), stir and rise
Temperature reacts 40min to 120 DEG C；Then epoxy pork fat (molar ratio-the EPO measured is added again：- COOH=0.6:1),
120 DEG C of reaction temperature, react 50min；Pour into afterwards in 7.5cm*7.5cm silica gel mould, first step reaction terminates, and obtains centre
Product.
(2) intermediate product made from step (1) is put into 150 DEG C of vacuum drying oven, vacuum dry 15min, after at 120 DEG C
5h is dried in baking oven, obtains epoxy pork fat base epoxy.
Composed with the FTIR of the building-up process of the German type infrared spectrometer neo-epoxy resins of Brooker company VERTEX 70
Figure, acquired results characteristic peak are same as Example 1.
Test example 1：Each embodiment product all-round property testing
Film body Analysis of tensile strength, UTM4204 type universal electricals testing machine measure asphalt mixtures modified by epoxy resin is used according to GB13022-91
The mechanical property of adipose membrane.Each embodiment test result is shown in Table 1.
Each embodiment product all-round property testing result of table 1
| Embodiment | Tensile strength/Mpa | Elongation at break/% |
| Embodiment 1 | 0.0714±0.0041 | 119.39±14.01 |
| Embodiment 2 | 0.4023±0.0183 | 60.23±1.06 |
| Embodiment 3 | 0.0913±0.0022 | 104.98±1.09 |
| Embodiment 4 | 0.0870±0.0085 | 213.07±20.06 |
| Embodiment 5 | 0.0905±0.0138 | 256.19±17.60 |
| Embodiment 6 | 0.0896±0.0005 | 166.71±2.997 |
| Embodiment 7 | 0.2304±0.0038 | 92.92±0.6295 |
| Embodiment 8 | 0.1142±0.0029 | 126.13±1.108 |
| Embodiment 9 | 0.0701±0.0019 | 97.64±3.871 |
From table 1 above it can be seen that neo-epoxy resin film, has good tensile strength and excellent extension at break
Rate；Tensile strength is all in more than 0.07MPa, and elongation at break is more than 60%, for being used in operation suture thread and human body
Skin wounds healing carrier reaches the requirement of mechanical property, and the mechanical property of film fully meets the demand of practice.
Test example 2
Differential scans thermometric analysis, and neo-epoxy resin is surveyed using U.S.'s PE companies DSC8000 type differential scannings
Take temperature sign, heating rate：10℃/min；Temperature scanning scope：-90℃-120℃；Atmosphere：Nitrogen；Crucible material：Aluminium crucible.
Record the glass transition temperature of each embodiment.
Membrane degradation is tested, and film is respectively put into 1mol/L NaOH solution, 1mol/L HCl solution and deionized water
In, separated in time surveys the change of the quality of film, records the time used in film quality degraded 90% respectively (if non-degradable use
"-" symbol is indicated)
Each embodiment product all-round property testing result of table 2
Neo-epoxy resin glass transition temperature is relatively low as can be seen from Table 2, and rubber is in normal temperature and body temperature material
State, there is good mechanical property.New epoxy resin film is in acid condition and substantially non-degradable in deionized water,
Time under alkalescence condition used in degraded 90% is all not above 720h (one month), and the normal PH=7-7.4 of tissue,
In alkalescent, this film is used in skin wounds healing carrier and takes out and directly can be degraded in human body without second operation.
Test example 3
Biocompatibility is tested：Cultured cell (people's renal epithelial cell) is inoculated in 96 orifice plates, in CO2Incubator is trained
Support 24h；Testing sample is made into concentration gradient, adds in corresponding orifice plate, separately sets blank group, be put into CO2Incubator culture 48h
Afterwards, orifice plate nutrient solution is discarded, then adds 90 μ L nutrient solutions (serum-free) and 10 μ L MTT into each orifice plate successively, in CO2Training
Support after acting on 4h in case, discard nutrient solution in orifice plate, 100 μ L DMSO are added after 20min is vibrated on oscillator, in ELIASA
Interior detection 490nm absorbance.According to the relation between absorbance derived sample concentration and cell survival ratio.
As seen from Figure 3, under different concentration, the survival ratio of people's renal epithelial cell has been above 80%, and concentration is
During 45 μ L/mL, the survival ratio of cell is far longer than 50% for 85%, therefore the biocompatibility of neo-epoxy resin film is very
Good, this also meets the requirement in the application of skin wound healing pharmaceutical carrier.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of bio-oil base epoxy, it is characterised in that comprise the following steps：
(1) the natural binary acid measured and deionized water are sequentially added in a kettle, are stirred and are heated up, first time addition portion
The epoxy bio oil divided, stir and be warming up to 70~160 DEG C, 10~90min of reaction；Then residue once or is repeatedly added
Partial epoxy bio oil, 70~160 DEG C of reaction temperature, the total time 2 that once or repeatedly addition epoxy bio oil is reacted~
90min；If adding dry catalyst before reaction terminates or being not added with, intermediate product is obtained；
Or
The natural binary acid measured and deionized water are sequentially added in a kettle, stirs and heats up, and add epoxy bio oil,
Stir and be warming up to 70~160 DEG C, 10~90min of reaction；If dry catalyst is added before reaction terminates or is not added with, in obtaining
Between product；
(2) intermediate product made from step (1) is placed in temperature as 80~180 DEG C, in the condition for vacuumizing or not vacuumizing
Under, 1~24h is reacted, obtains bio-oil base epoxy.
2. the preparation method of bio-oil base epoxy according to claim 1, it is characterised in that：
The total amount of addition epoxy bio oil described in step (1) is according to epoxy radicals and mole of the carboxylic group of natural binary acid
Than calculating, mol ratio 1.5:1~0.7:1.
3. the preparation method of bio-oil base epoxy according to claim 1, it is characterised in that：
Natural binary acid carboxylic group and deionized water mol ratio described in step (1) are 1:0~1:7；
Described deionized water is adjuvant.
4. the preparation method of bio-oil base epoxy according to claim 1, it is characterised in that：
Natural binary acid described in step (1) refers to naturally occurring dicarboxylic acids；
Epoxy bio oil described in step (1) includes epoxidized vegetable oil and epoxy animal oil.
5. the preparation method of the bio-oil base epoxy according to claim 1 or 4, it is characterised in that：
Described natural binary acid is malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or the last of the ten Heavenly stems two
At least one of acid.
6. the preparation method of bio-oil base epoxy according to claim 4, it is characterised in that：
Described epoxidized vegetable oil includes epoxy herbaceous plant oil or epoxy xylophyta oil；
Described epoxy animal oil includes epoxy terricole oil or epoxy marine animal oil.
7. the preparation method of bio-oil base epoxy according to claim 6, it is characterised in that：
Described epoxy herbaceous plant oil is epoxy linseed oil, epoxy grape-kernel oil, epoxy perilla herb oil, epoxy walnut oil, ring
Oxygen apricot kernel oil, epoxy Seabuckthorn Oil, epoxy evening primrose oil, expoxy glass lettuce oil, epoxidized soybean oil, epoxy corn oil, epoxy peanut
Oil, epoxy rapeseed oil, epoxy sesame oil, epoxy sunflower oil, epoxy cottonseed oil, epoxy small oil, epoxy fire sesame oil or epoxy
At least one of siritch；
Described epoxy xylophyta oil is epoxy camellia seed oil, epoxy peony seed oil, epoxy palm oil, epoxy castor oil, epoxy
At least one of coconut oil or epoxy olive oil；
Described epoxy terricole oil be in epoxy pork fat, epoxy butter, epoxy sheep oil, epoxy chicken fat or epoxy duck oil extremely
Few one kind；
Described epoxy marine animal oil is at least one of epoxy whale oil or epoxy deep sea fish oil.
8. the preparation method of bio-oil base epoxy according to claim 1, it is characterised in that：
Catalyst described in step (1) includes tertiary amine, 1- methylimidazoles, 2-methylimidazole, 1,8- diazacyclos [5,4,0] ten
At least one of one carbon -7- alkene, DMAP or boron trifluoride complex.
9. a kind of bio-oil base epoxy, it is characterised in that pass through the preparation method system described in any one of claim 1~8
It is standby to obtain.
10. the bio-oil base epoxy described in claim 9 is in biomaterial, solventless coatings, polymeric membrane field
Application.
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| CN108558523A (en) * | 2018-06-07 | 2018-09-21 | 中国林业科学研究院林产化学工业研究所 | One vegetable oil based polyalcohol coated fertilizer and coat fertilizer and preparation method thereof |
| CN108586710A (en) * | 2018-05-17 | 2018-09-28 | 中国林业科学研究院林产化学工业研究所 | Polynary daiamid epoxy curing agent of xylophyta fat-based and preparation method thereof |
| CN108727552A (en) * | 2018-05-07 | 2018-11-02 | 华南农业大学 | A kind of full biology base emulsifier and its preparation method and application |
| CN110041506A (en) * | 2019-05-10 | 2019-07-23 | 河南省高新技术实业有限公司 | A kind of wood tar base epoxy, anticorrosive paint and preparation method thereof |
| CN110229531A (en) * | 2019-07-11 | 2019-09-13 | 江南大学 | A kind of complete bio-based source epoxy resin composite material and preparation method thereof |
| CN111019091A (en) * | 2019-12-10 | 2020-04-17 | 广东科德环保科技股份有限公司 | Bio-based modified epoxy resin, bio-based electrophoretic coating and preparation method thereof |
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| CN113045955A (en) * | 2021-03-25 | 2021-06-29 | 河北涂铠新材料科技有限公司 | Low-surface-treatment heavy-duty anticorrosive paint and preparation method and application thereof |
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| CN108727552A (en) * | 2018-05-07 | 2018-11-02 | 华南农业大学 | A kind of full biology base emulsifier and its preparation method and application |
| CN108586710A (en) * | 2018-05-17 | 2018-09-28 | 中国林业科学研究院林产化学工业研究所 | Polynary daiamid epoxy curing agent of xylophyta fat-based and preparation method thereof |
| CN108558523A (en) * | 2018-06-07 | 2018-09-21 | 中国林业科学研究院林产化学工业研究所 | One vegetable oil based polyalcohol coated fertilizer and coat fertilizer and preparation method thereof |
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| CN110229531A (en) * | 2019-07-11 | 2019-09-13 | 江南大学 | A kind of complete bio-based source epoxy resin composite material and preparation method thereof |
| CN110229531B (en) * | 2019-07-11 | 2021-03-23 | 江南大学 | Completely bio-based epoxy resin composite material and preparation method thereof |
| CN111019091A (en) * | 2019-12-10 | 2020-04-17 | 广东科德环保科技股份有限公司 | Bio-based modified epoxy resin, bio-based electrophoretic coating and preparation method thereof |
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| CN112409583A (en) * | 2020-11-11 | 2021-02-26 | 大连理工大学 | Preparation method of animal/vegetable oil bio-based polymer based on mechanochemical method |
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