CN106397735A - Biomass oil modified epoxy resin and preparation method thereof - Google Patents
Biomass oil modified epoxy resin and preparation method thereof Download PDFInfo
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- CN106397735A CN106397735A CN201610783511.4A CN201610783511A CN106397735A CN 106397735 A CN106397735 A CN 106397735A CN 201610783511 A CN201610783511 A CN 201610783511A CN 106397735 A CN106397735 A CN 106397735A
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract
The invention discloses biomass oil modified epoxy resin and a preparation method thereof. The biomass oil modified epoxy resin is prepared from the following raw materials in parts by weight: 50 to 100 parts of epoxy resin, 20 to 100 parts of biomass oil, 0.2 to 1.5 parts of basic catalyst, 0.1 to 0.8 part of metallic salt catalyst and 20 to 80 parts of diluting agent. The biomass oil modified epoxy resin provided by the invention has excellent toughness, shock resistance, cracking resistance, weather resistance and the like; the technical difficult problem that epoxy resin is used as anti-corrosive paint is solved. Meanwhile, the preparation method of the biomass oil modified epoxy resin is simple, is stable in process and mild in reaction condition, and is energy-saving and environment-friendly; a biomass material can be sufficiently utilized; the additional utilization value of biomass energy is increased; the production cost is decreased. The biomass oil modified epoxy resin can be also used for preparing a composite material, a binding agent, a material for electronic electric appliances, an engineering plastic material and the like.
Description
Technical field
The invention belongs to resin art is and in particular to a kind of bio-oil modified epoxy and preparation method thereof.
Background technology
Epoxy resin is to refer to the organic compound containing two or more epoxide groups in molecule, has excellent
The adhesive property of physical and mechanical propertiess, electrical insulation capability and various material, and have using the flexible feature of technique.These
Function and feature are not available for other thermosetting plasticses, therefore it can make coating, composite, casting material, adhesive,
Moulding material and injecting forming material, are all widely used in the every field of national economy.Wherein, epoxy resin exists
Application in coating occupies larger ratio, it can make differ from one another, kind that purposes is different.Epoxy resin has following common
Property：1st, chemical-resistant is excellent, especially alkali resistance；2nd, paint film adhesion is strong, particularly to metal；3rd, have preferably heat-resisting
Property and electrical insulating property；4th, paint film colour retention is preferable.But the weatherability of epoxy coating is poor, and fragility is larger, cracking resistance anti-impact
Hit poor performance, easily efflorescence loss of gloss owes plentiful to paint film again out of doors, should not make outdoor coating and high-decoration coating is used.Cause
This, be badly in need of find a kind of modified epoxy, this modified epoxy have excellent toughness, antiseptic property, shock resistance resist open
Fragility energy and weather resistance, it is possible to resolve epoxy resin as the technical barrier of anticorrosive paint, meanwhile, also may be used by this modified epoxy
For preparing composite, binding agent, electronic apparatus material and engineering plastics etc..
Bio-oil is biomass block, mainly contains lignin, cellulose and hemicellulose.Bio-oil be temperature,
In the presence of pressure, reaction medium and catalyst, by controlling response parameter, molecular weight is made to be tens of thousands of to millions of wooden
Element, cellulose and hemicellulose degradation and the molecular weight that obtains is hundreds of thousands of product.Phenols, aldehyde is contained in bio-oil
The materials such as class, alcohols, acids, contain the group such as phenolic hydroxyl group, carboxyl in its strand, these can be used for changing with epoxy reaction
Property epoxy resin.Bio-oil also has other excellent specific properties, such as with low cost, good toughness, weather resistance are good, antiseptic property
Good, raw material is easy to get.
But, Pintsch process bio-oil composition is complicated, substance classes kind up to more than 200, its small molecular its lytic activity
High, it is unsuitable for modified epoxy, macromole product molecule chain is long, steric hindrance is big, so that reaction is difficult to.Therefore, it is necessary to
Preferentially choose crack biomass crude oil, then it carried out extract, distill etc. with separating technology, prepare suitable bio-oil, be used for
Modified epoxy.
Content of the invention
It is an object of the invention to：For above-mentioned epoxy resin toughness, shock resistance anti-cracking performance and weather resistance difference
Problem, the present invention provides a kind of bio-oil modified epoxy and preparation method thereof.
The technical solution used in the present invention is as follows：
A kind of bio-oil modified epoxy, described bio-oil modified epoxy includes the former of following weight portion
Material：50～100 parts of epoxy resin, 20～100 parts of bio-oil, 0.2～1.5 part of base catalyst, metallic salt catalyst 0.1
～0.8 part, 20～80 parts of diluent.The chemical constituent of this bio-oil modified epoxy includes bio-oil, bio-oil
Strand in contain the group such as phenolic hydroxyl group, carboxyl, these groups can be introduced in the molecular structure of epoxy resin.And it is biological
Matter oil has that good toughness, weather resistance be good, shock resistance anti-cracking performance and the excellent specific property such as antiseptic property is good, is conducive to improving ring
The toughness of oxygen tree fat, weather resistance, antiseptic property and shock resistance anti-cracking performance etc..
But Pintsch process bio-oil composition is complicated, substance classes kind up to more than 200, its small molecular its lytic activity pole
Height, inapplicable modified epoxy, and macromole product molecule chain is long, steric hindrance is big, so that reaction is difficult to.Therefore, it is necessary to
Prepare suitable bio-oil for epoxy resin modification.The preparation of bio-oil preferentially can choose biomass crude oil by first,
Biomass crude oil carried out extracting again, distill etc. with separating technology to complete, the preparation method of described bio-oil is as follows：
(1) get the raw materials ready：Take the thermal cracking biomass crude oil of knockout tower stage casing part, its average molecular mass Mn be 100～
500；
(2) extract：By weight, 20～100 parts of described biomass crude oils are added in container, add distilled water 20
～80 parts of stirrings, and it is warming up to 40～50 DEG C, it is incubated 20～60min, stratification simultaneously removes the supernatant, add distilled water 10
～50 parts of stirrings, and it is warming up to 60～80 DEG C, it is incubated 20～60min, stratification simultaneously removes the supernatant；
(3) distill：By weight, the bio-oil after extraction is heated to 80～105 DEG C, vacuum distillation, remove water
Point, add 10～50 parts of diluent to obtain bio-oil.
The average molecular mass Mn of described bio-oil is 400～3000, and the bio-oil of this scope has moderate activity,
Be conducive to modified epoxy.
Further, the average molecular mass Mn of described bio-oil is 500～1000.
Described epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic aldehyde
One of type epoxy resin and resorcinol type epoxy.
Further, described epoxy resin is bisphenol A type epoxy resin or phenol aldehyde type epoxy resin.
Described diluent is selected from ethanol, n-butyl alcohol, butyl acetate, ethyl acetate, oxolane, ethylene glycol and glycerol
One or more.
Described base catalyst is one of potassium hydroxide, sodium hydroxide, calcium acetate, barium hydroxide and magnesium carboxylates.Alkali
Property catalyst is used for promoting epoxy ring-opening, and with bio-oil in phenolic hydroxyl group, carboxyl reaction.
Described metallic salt catalyst is one of ferric chloride, boron chloride and aluminium isopropoxide.Metallic salt
Catalyst is conducive to reaction to generate side chain, improves the degree of cross linking and the degree of compaction of solidfied material molecular network.
A kind of preparation method of bio-oil modified epoxy, step is：Prepare described bio-oil modified epoxy tree
The method of fat, step is：Epoxy resin, diluent and bio-oil are sequentially added to reactor, start reactor stirring,
It is warming up to 50～65 DEG C, adds base catalyst, be heated to 60～75 DEG C and be incubated 0.5～2.0h, add metallic salt catalysis
Agent, flows back and is incubated 0.5～2.0h after being heated to 75～85 DEG C, cooling obtains bio-oil modified epoxy.
In sum, due to employing technique scheme, the invention has the beneficial effects as follows：
1. provide a kind of bio-oil modified epoxy, this bio-oil modified epoxy has excellent tough
Property, antiseptic property, shock resistance anti-cracking performance and weather resistance, solve epoxy resin as the technical barrier of anticorrosive paint,
Meanwhile, this bio-oil modified epoxy can be additionally used in preparing composite, binding agent, electronic apparatus material and engineering plastics
Deng；
2. provide a kind of preparation method of bio-oil modified epoxy, the method is simple, process stabilizing, react bar
Part is gentle, can make full use of biological material, energy-conserving and environment-protective, improve the additional value of biomass energy；
3. the raw material adopting is easy to get, and cheap, it is possible to decrease production cost.
Specific embodiment
All features disclosed in this specification, in addition to mutually exclusive feature and/or step, all can be with any
Mode combines.
A kind of bio-oil modified epoxy, described bio-oil modified epoxy includes the former of following weight portion
Material：50～100 parts of epoxy resin, 20～100 parts of bio-oil, 0.2～1.5 part of base catalyst, metallic salt catalyst 0.1
～0.8 part, 20～80 parts of diluent.
Preferably, the preparation method of bio-oil is as follows：
(1) get the raw materials ready：Take the thermal cracking biomass crude oil of knockout tower stage casing part, its average molecular mass Mn be 100～
500；
(2) extract：By weight, 20～100 parts of described biomass crude oils are added in container, add distilled water 20
～80 parts of stirrings, and it is warming up to 40～50 DEG C, it is incubated 20～60min, stratification simultaneously removes the supernatant, add distilled water 10
～50 parts of stirrings, and it is warming up to 60～80 DEG C, it is incubated 20～60min, stratification simultaneously removes the supernatant；
(3) distill：By weight, the bio-oil after extraction is heated to 80～105 DEG C, vacuum distillation, remove water
Point, add 10～50 parts of diluent to obtain bio-oil.
Preferably, the average molecular mass Mn of bio-oil is 400～3000, and the bio-oil of this scope has moderate work
Property, be conducive to modified epoxy.Further, the average molecular mass Mn of bio-oil is 500～1000.
Preferably, epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol
One of aldehyde type epoxy resin and resorcinol type epoxy.Further, described epoxy resin is bisphenol A type epoxy resin
Or phenol aldehyde type epoxy resin.
Preferably, diluent is selected from ethanol, n-butyl alcohol, isobutanol, butyl acetate, ethyl acetate, oxolane, ethylene glycol
One or more of with glycerol.
Preferably, base catalyst is one of potassium hydroxide, sodium hydroxide, calcium acetate, barium hydroxide and magnesium carboxylates,
Metallic salt catalyst is one of ferric chloride, boron chloride and aluminium isopropoxide.
A kind of preparation method of bio-oil modified epoxy, step is：Prepare described bio-oil modified epoxy tree
The method of fat, step is：Epoxy resin, diluent and bio-oil are sequentially added to reactor, start reactor stirring,
It is warming up to 50～65 DEG C, adds base catalyst, be heated to 60～75 DEG C and be incubated 0.5～2.0h, add metallic salt catalysis
Agent, flows back and is incubated 0.5～2.0h after being heated to 75～85 DEG C, cooling obtains bio-oil modified epoxy.
Embodiment 1
The determination step of epoxy resin gel time is：By epoxy resin ethanol dilution, make solids content 60wt%
Mixture, add tetrabydrophthalic anhydride the 15% of epoxy resin quality (consumption of tetrabydrophthalic anhydride be) and mix
Close uniformly, obtain test sample.Weigh 0.5g test sample, be placed in the circular hot plate of diameter 2cm (hot plate holding constant temperature
150 ± 1 DEG C), and be stirred continuously up to gel using the draw point of diameter 1mm.The time that test sample is changed into gel is as solidifying
The glue time.
Embodiment 2
The first step, the preparation method of bio-oil is as follows：
(1) get the raw materials ready：Take the thermal cracking biomass crude oil of knockout tower stage casing part, its average molecular mass Mn is 162；
(2) extract：Above-mentioned biomass crude oil 1000g is added in there-necked flask, adds distilled water 800g stirring, and rise
Temperature, to 50 DEG C, is incubated 30min, and stratification 30min simultaneously removes the supernatant, adds distilled water 500g stirring, and is warming up to 80
DEG C, it is incubated 35min, stratification 30min simultaneously removes the supernatant；
(3) distill：By extraction after bio-oil be heated to 105 DEG C, vacuum distillation, control vacuum be -0.095～-
0.09MPa, removes moisture, obtains the liquid bio matter oil of toughness, adds ethanol 500g to obtain bio-oil.Gained biomass
In oil, the mass percent of solid content is 61.2%, and the average molecular mass Mn of bio-oil is 516.
Second step, the preparation method of bio-oil modified epoxy is as follows：
By bisphenol A type epoxy resin E51 (epoxide number 0.516, average molecular mass Mn is 392, gel time 148s)
1000g, ethanol 480g and described bio-oil 600g sequentially add to reactor, start reactor stirring 30min, slow liter
Temperature, to 55 DEG C, adds potassium hydroxide 9g, is heated to 65 DEG C and is incubated 1.5h, add ferric chloride 4.8g, returns after being heated to 85 DEG C
Flow and be incubated, start to measure epoxide number, the stopped reaction when epoxide number is 0.25～0.30 after insulation 20min, lower the temperature at once
Obtain bio-oil modified epoxy to 35 DEG C.The technical specification of gained bio-oil modified epoxy is as follows：Epoxide number
0.287, average molecular mass Mn is 559, gel time 94s, solids content 63.4wt%.
Embodiment 3
The first step, the preparation method of bio-oil is as follows：
(1) get the raw materials ready：Take the thermal cracking biomass crude oil of knockout tower stage casing part, its average molecular mass Mn is 215；
(2) extract：Above-mentioned biomass crude oil 800g is added in there-necked flask, adds distilled water 400g stirring, and rise
Temperature, to 45 DEG C, is incubated 40min, and stratification 25min simultaneously removes the supernatant, adds distilled water 300g stirring, and is warming up to 75
DEG C, it is incubated 30min, stratification 20min simultaneously removes the supernatant；
(3) distill：By extraction after bio-oil be heated to 98 DEG C, vacuum distillation, control vacuum be -0.095～-
0.09MPa, removes moisture, obtains the liquid bio matter oil of toughness, adds ethyl acetate 300g to obtain bio-oil.Gained is given birth to
In material oil, the mass percent of solid content is 68.4%, and the average molecular mass Mn of bio-oil is 607.
Second step：The preparation method of bio-oil modified epoxy is as follows：
By phenol aldehyde type epoxy resin F44 (epoxide number 0.457, average molecular mass Mn be 445, gel time 137s) 800g,
Ethyl acetate 400g and described bio-oil 600g sequentially add to reactor, start reactor stirring 20min, slow intensification
To 60 DEG C, add calcium acetate 5g, be heated to 65 DEG C and be incubated 1.5h, add boron chloride 6g, flow back after being heated to 80 DEG C and protect
Temperature, starts to measure epoxide number, the stopped reaction when epoxide number reaches 0.2～0.25 after insulation 20min, is cooled to 35 DEG C at once
Obtain bio-oil modified epoxy.The technical specification of gained bio-oil modified epoxy is as follows：Epoxide number 0.220,
Average molecular mass Mn is 697, gel time 85s, solids content 66.8wt%.
Embodiment 4
The first step, the preparation method of bio-oil is as follows：
(1) get the raw materials ready：Take the thermal cracking biomass crude oil of knockout tower stage casing part, its average molecular mass Mn is 294；
(2) extract：Above-mentioned biomass crude oil 600g is added in there-necked flask, adds distilled water 450g stirring, and rise
Temperature, to 40 DEG C, is incubated 50min, and stratification 20min simultaneously removes the supernatant, adds distilled water 250g stirring, and is warming up to 70
DEG C, it is incubated 55min, stratification 15min simultaneously removes the supernatant；
(3) distill：By extraction after bio-oil be heated to 102 DEG C, vacuum distillation, control vacuum be -0.095～-
0.09MPa, removes moisture, obtains the liquid bio matter oil of toughness, adds oxolane 300g to obtain bio-oil.Gained is given birth to
In material oil, the mass percent of solid content is 62.5%, and the average molecular mass Mn of bio-oil is 689.
Second step, the preparation method of bio-oil modified epoxy is as follows：
By bisphenol A type epoxy resin E55 (epoxide number 0.554, average molecular mass Mn be 367, gel time 162s) 600g,
Oxolane 350g and described bio-oil 600g sequentially adds to reactor, starts reactor stirring 40min, slow intensification
To 65 DEG C, add magnesium carboxylates 12g, be heated to 65 DEG C and be incubated 1.0h, add aluminium isopropoxide 3.0g, return after being heated to 78 DEG C
Flow and be incubated, start to measure epoxide number, the stopped reaction when epoxide number reaches 0.2～0.25 after insulation 20min, lower the temperature at once
Obtain bio-oil modified epoxy to 35 DEG C.The technical specification of gained bio-oil modified epoxy is as follows：Epoxide number
0.239, average molecular mass Mn is 711, gel time 79s, solids content 60.4wt%.
Embodiment 5
Based on above-described embodiment 2, by mass percentage, by bio-oil modified epoxy described in 43% and 8% positive fourth
Alcohol mixes, and adds 0.5% titanium dioxide, 37% Pulvis Talci, 4% zinc powder, 2.5% Kaolin, 0.4% wetting dispersing agent and 0.6%
Organic silicon defoamer, disperses 30min at a high speed with the rotating speed of 1500 turns/min at 45 DEG C, adds 4% acetone, stir,
Ripening obtained coating composition after 1 day；By mass percentage, by 90% phenol aldehyde modified amine T31,1% triethanolamine and 9% acetic acid fourth
Ester mixes, and stirs at normal temperatures, obtains curing component；By mass percentage, 50% dimethylbenzene and 50% isobutanol are stirred
Mix uniformly, obtain the diluent for preparing anticorrosive paint, then by coating composition and curing component in mass ratio for 10:1 mixes
Close, add described diluent in right amount and stir, after ripening 15min, obtain bio-oil modified epoxy anticorrosive paint.
Comparative example
This comparative example be the difference is that only with embodiment 5：Epoxy resin used is unmodified bisphenol A-type ring
Oxygen tree fat E51, and with ethanol dilution bisphenol A type epoxy resin E51 so as to bio-oil described in solids content and embodiment 5
The solids content of modified epoxy is identical.
Coating by the bio-oil modified epoxy anticorrosive paint of above-described embodiment 5 gained and comparative example's gained
It is applied on smooth aluminium sheet, the performance of test paint film, this test is passed through bio-oil modified epoxy and modified epoxy
Resin is prepared into anticorrosive paint respectively, indirectly characterizes the items of bio-oil modified epoxy and unmodified epoxy resin
Can, test report is as shown in table 1.
Table 1 paint film property test report
As can be seen from the table, the toughness of bio-oil modified epoxy and shock resistance anti-cracking performance are better than unmodified
Epoxy resin, be mainly manifested in the 8th and the 9th two index.8th impact property, its value shows more greatly the anti-impact of paint film
Hit anti-cracking performance better, the 9th bending property, its value is less to represent that the crooking ability of paint film is better, and toughness is also better.Its
Secondary, the weatherability of bio-oil modified epoxy is significantly improved more before modified, and this is from the ultra-violet resistance of the 16th
Can be it can be seen that coming.In addition, the adhesive force pull-out strength of bio-oil modified epoxy also more unmodified front big, hydrophobicity
Also it is improved, accelerate drying time it is seen then that the combination property of bio-oil modified epoxy has obtained significantly carrying
High.Can be seen that bio-oil modified epoxy from above-mentioned test report and there is excellent toughness, antiseptic property, shock resistance
Anti-cracking performance and weather resistance, solve epoxy resin as the technical barrier of anticorrosive paint, meanwhile, this bio-oil is modified
Epoxy resin can be additionally used in preparing composite, binding agent, electronic apparatus material and engineering plastics etc..
Claims (10)
1. a kind of bio-oil modified epoxy it is characterised in that described bio-oil modified epoxy include following heavy
The raw material of amount part：50～100 parts of epoxy resin, 20～100 parts of bio-oil, 0.2～1.5 part of base catalyst, metallic salt
0.1～0.8 part of catalyst, 20～80 parts of diluent.
2. a kind of bio-oil modified epoxy according to claim 1 is it is characterised in that the system of described bio-oil
Preparation Method is as follows：
(1) get the raw materials ready：Take the thermal cracking biomass crude oil of knockout tower stage casing part, its average molecular mass Mn is 100～500；
(2) extract：Count by weight, 20～100 parts of described biomass crude oils be added in container, add distilled water 20～
80 parts of stirrings, and are warming up to 40～50 DEG C, are incubated 20～60min, and stratification simultaneously removes the supernatant, add distilled water 10～
50 parts of stirrings, and it is warming up to 60～80 DEG C, it is incubated 20～60min, stratification simultaneously removes the supernatant；
(3) distill：Count by weight, the bio-oil that (2) are extracted is heated to 80～105 DEG C, vacuum distillation, remove water
Point, add 10～50 parts of diluent to obtain bio-oil.
3. a kind of bio-oil modified epoxy according to claim 1 and 2 is it is characterised in that described bio-oil
Average molecular mass Mn be 400～3000.
4. a kind of bio-oil modified epoxy according to claim 3 it is characterised in that described bio-oil flat
Average molecular weight Mn is 500～1000.
5. a kind of bio-oil modified epoxy according to claim 1 is it is characterised in that described epoxy resin includes
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type epoxy resin and resorcinol epoxy
One of resin.
6. according to claim 1 or 5 a kind of bio-oil modified epoxy it is characterised in that described epoxy resin
For bisphenol A type epoxy resin or phenol aldehyde type epoxy resin.
7. a kind of bio-oil modified epoxy according to claim 1 and 2 is it is characterised in that described diluent selects
From one or more of ethanol, n-butyl alcohol, isobutanol, butyl acetate, ethyl acetate, oxolane, ethylene glycol and glycerol.
8. a kind of bio-oil modified epoxy according to claim 1 is it is characterised in that described base catalyst is
One of potassium hydroxide, sodium hydroxide, calcium acetate, barium hydroxide and magnesium carboxylates.
9. a kind of bio-oil modified epoxy according to claim 1 is it is characterised in that described metallic salt is catalyzed
Agent is one of ferric chloride, boron chloride and aluminium isopropoxide.
10. a kind of preparation method of bio-oil modified epoxy is it is characterised in that described bio-oil modified epoxy
Preparation process be：Epoxy resin, diluent and bio-oil are sequentially added to reactor, starts reactor stirring, rise
Temperature, to 50～65 DEG C, adds base catalyst, is heated to 60～75 DEG C and is incubated 0.5～2.0h, adds metallic salt catalyst,
Flow back and be incubated 0.5～2.0h after being heated to 75～85 DEG C, cooling obtains bio-oil modified epoxy.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN118420844A (en) * | 2023-09-28 | 2024-08-02 | 重庆工业职业技术学院 | Flexible acrylic resin modified epoxy resin and preparation method thereof |
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| CN105860428A (en) * | 2016-05-30 | 2016-08-17 | 四川国能高科生物树脂有限公司 | Biomass oil suitable for modifying thermosetting resin and preparation method thereof |
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| CN110041506B (en) * | 2019-05-10 | 2021-08-24 | 河南省高新技术实业有限公司 | Wood tar-based epoxy resin, anticorrosive paint and preparation method thereof |
| CN118420844A (en) * | 2023-09-28 | 2024-08-02 | 重庆工业职业技术学院 | Flexible acrylic resin modified epoxy resin and preparation method thereof |
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| CN106397735B (en) | 2018-07-03 |
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