CN107541016B - A kind of preparation method of biomass modified epoxy resin - Google Patents
A kind of preparation method of biomass modified epoxy resin Download PDFInfo
- Publication number
- CN107541016B CN107541016B CN201710725990.9A CN201710725990A CN107541016B CN 107541016 B CN107541016 B CN 107541016B CN 201710725990 A CN201710725990 A CN 201710725990A CN 107541016 B CN107541016 B CN 107541016B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- biomass
- modified epoxy
- preparation
- powdered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The present invention is to provide a kind of preparation methods of biomass modified epoxy resin.Biomass material dries pulverizing, sieving, and be further ground to powdered；Powdered biomass is mixed with epoxy resin, stirs 20min at 60 DEG C, then heats to 80 DEG C, 1h is reacted, obtains biomass modified epoxy resin prepolymer；Curing agent is added in modified epoxy performed polymer, solidifies, obtains modified epoxy material.Method of the invention has many advantages, such as that raw material sources are extensive, cheap, and preparation process is simple, easily operated.The modified epoxy obtained using preparation method of the invention is with good stability, and the stretching of material, bending strength highest can promote 46.3%, 36.1% respectively；The promotion of shock resistance reaches as high as 94.2%.Modified epoxy obtained can be used as resin material and use directly as electronic apparatus material, aerospace material and engineering plastics, and the matrix resin that also can be used as composite material uses.
Description
Technical field
The present invention relates to a kind of method of modifying of thermosetting resin, especially a kind of natural biomass modified epoxy tree
The preparation method of rouge.
Background technique
Epoxy resin has excellent performance as a kind of thermoset resin material, has in metal, nonmetallic surface good
Good adhesive strength, to alkali and most of solvent-stable, while have excellent dielectric properties, good heat-moisture resistance energy,
High insulation performance, good dimensional stability and processing performance, it is extensive to can be used as adhesive, lamination material, coating and casting material
Applied to every field such as civilian, national defence.
Epoxy resin is the most widely used matrix of field of polymer-base composite material, it is suitable for a variety of moulding process,
Long with storage time, when solidification, does not discharge small organic molecule, and cure shrinkage is low, and the product after solidification has splendid ruler
Very little stability.Epoxy resin composite material is widely used in aerospace field, as the radome of aircraft, helicopter rotor,
Shell, system unit of solid propellant rocket etc.；In the pressure vessel and pipe that the main application of civil field includes glass reinforced plastic
Road, anticorrosive article etc..
Summary of the invention
The purpose of the present invention is to provide stability, tensile strength, flexural strength, anti-impacts that one kind can improve product
Hit intensity, raw material is cheap and easy to get, simple process, the preparation method of easily operated biomass modified epoxy resin.
The object of the present invention is achieved like this:
(1) biomass material dries pulverizing, sieving, and be further ground to powdered；
(2) powdered biomass is mixed with epoxy resin, stirs 20min at 60 DEG C, then heat to 80 DEG C, reaction
1h obtains biomass modified epoxy resin prepolymer；
(3) curing agent is added in modified epoxy performed polymer, solidifies, obtains modified epoxy material.
The present invention may also include:
1, the biomass is catechu, granatum or Cortex walnut.
2, the drying of biomass material is by biomass in 60 DEG C of vacuum drying 8h, and the average grain diameter of powdered biomass is
0.1~20 μm.Preferably 0.5~2 μm.
3, the mass ratio of powdered biomass and epoxy resin is 0.5/100~10/100.Preferably 1/100~2/100.
4, the epoxy resin includes bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol F type epoxy tree
The mixture of one or more of rouge, bisphenol-s epoxy resin, o-cresol formaldehyde epoxy resin.
5, the curing agent include 4,4- diaminodiphenylmethane, m-phenylene diamine (MPD), alicyclic polyamine, aromatic polyamine,
The mixture of one or more of tertiary amine and imidazole curing agent.
6, described to be cured as intermediate temperature setting, actual conditions are as follows: the precuring of 1~3h and 120 under the conditions of 80~110 DEG C~
The rear solidification of 2~6h under the conditions of 180 DEG C.
For the mechanical property for promoting epoxy resin, its application range is extended, the present invention is using from a wealth of sources, cheap
Biomass (such as catechu, granatum, Cortex walnut) is modified epoxy resin, and the stretching for effectively improving epoxy resin is strong
Degree, bending strength and shock resistance.This method has many advantages, such as that preparation process is simple, easily operated, the modified epoxy of acquisition
Resin is with good stability, is with a wide range of applications, can be used as resin material directly as electronic apparatus material,
Aerospace material and engineering plastics use, and the matrix resin that also can be used as composite material uses.
Compared with prior art, the present invention has the feature that
(1) preparation method of biomass modified epoxy resin provided by the invention, use natural biomass (such as catechu,
Granatum, Cortex walnut etc.) advantages such as extensive, cheap, renewable, environmentally protective with raw material sources, and adding on a small quantity
The tensile strength, bending strength and impact strength of epoxy resin can be effectively improved after adding.
(2) preparation method of biomass modified epoxy resin provided by the invention, have mild condition, simple process, easily
In operation, equipment investment is small, is easy the advantages that large-scale production.
(3) there is excellent mechanical property using the biomass modified epoxy resin that preparation method of the invention obtains, it can
It is applied to field of electronics, aerospace field and engineering plastics directly as resin material；And drawing due to biomass
Enter, the compatibility of epoxy resin Yu organic and inorganic reinforcing filler and reinforcing fiber can be effectively improved, therefore as compound
The matrix resin of material uses the performance that can effectively improve composite material.
Specific embodiment
It illustrates below and the present invention is described further.The scope of the present invention is not restricted by the embodiments.
Comparative example 1:
(1) curing agent 4,4-diaminodiphenylmethane (DDM) that mass fraction is 25 is added to mass fraction is 100
In epoxy resin, the heating stirring at 80 DEG C makes curing agent be dissolved completely in epoxy resin；
(2) mixture of above-mentioned epoxy resin and curing agent is placed in vacuum drying oven 15min to remove bubble；
(3) by deaeration, treated that mixture pours into ready mold, is placed in air dry oven, 2h at 80 DEG C,
4h solidifies at 135 DEG C, and the batten after the completion of solidifying is placed in carries out Mechanics Performance Testing afterwards for 24 hours at room temperature.
Test result shows that the tensile strength of epoxy resin, bending strength are respectively 67.6MPa, 108.4MPa, and fracture is stretched
Long rate is 6.3%, impact strength 11.05kJ/m2(being shown in Table 1).
Embodiment 1:
(1) biomass catechu is placed in 60 DEG C of vacuum drying oven drying 8h, is ground into little particle, is screened out with 50 mesh sieve miscellaneous
Matter, by gained powder ball mill grinding at fine powder；
(2) the catechu powder that mass fraction is 1 is mixed with the epoxy resin that mass fraction is 100, is stirred at 60 DEG C
20min is uniformly mixed catechu particle with epoxy resin liquid, then heats to 80 DEG C, reacts 1h, obtains catechu modified epoxy
Resin prepolymer；
(3) the curing agent DDM that mass fraction is 25 is added in above-mentioned catechu modified epoxy performed polymer, temperature is protected
It holds at 80 DEG C, stirring is completely dissolved curing agent；
(4) said mixture is placed in vacuum drying oven 15min to remove bubble；
(5) by deaeration, treated that mixture pours into ready mold, is placed in air dry oven, 2h at 80 DEG C,
4h solidifies at 135 DEG C, and the batten after the completion of solidifying is placed in carries out Mechanics Performance Testing afterwards for 24 hours at room temperature.
Test result shows that the tensile strength of modified epoxy, bending strength are respectively 91.8MPa, 147.4MPa, breaks
Splitting elongation is 6.6%, impact strength 21.5kJ/m2(being shown in Table 1).
Embodiment 2:
In addition to the mass fraction of catechu powder is 1.5, other conditions are same as Example 1.Gained modified epoxy
Mechanical experimental results show that its tensile strength, bending strength are respectively 98.9MPa, 145.3MPa, and elongation at break is
6.4%, impact strength 19.3kJ/m2(being shown in Table 1).
Embodiment 3:
In addition to used biomass is granatum, other conditions are same as Example 1.Gained modified epoxy
Mechanical experimental results show that its tensile strength, bending strength are respectively 95.4MPa, 120.1MPa, and elongation at break is
6.8%, impact strength 18.3kJ/m2(being shown in Table 1).
Comparative example 2:
(1) the curing agent m-phenylene diamine (MPD) (PDA) that mass fraction is 13 is added to the epoxy resin that mass fraction is 100
In, the heating stirring at 80 DEG C makes curing agent be dissolved completely in epoxy resin；
(2) mixture of above-mentioned epoxy resin and curing agent is placed in vacuum drying oven 15min to remove bubble；
(3) by deaeration, treated that mixture pours into ready mold, is placed in air dry oven, 1h at 80 DEG C,
1h at 105 DEG C, 2h solidifies at 150 DEG C, and the batten after the completion of solidifying is placed in carries out Mechanics Performance Testing afterwards for 24 hours at room temperature.
Test result shows that the tensile strength of epoxy resin, bending strength are respectively 63.9MPa, 105.8MPa, and fracture is stretched
Long rate is 3.6% (being shown in Table 1).
Embodiment 4:
(1) biomass catechu is placed in 60 DEG C of vacuum drying oven drying 8h, is ground into little particle, is screened out with 50 mesh sieve miscellaneous
Matter, by gained powder ball mill grinding at fine powder；
(2) the catechu powder that mass fraction is 1 is mixed with the epoxy resin that mass fraction is 100, is stirred at 60 DEG C
20min is uniformly mixed catechu particle with epoxy resin liquid, then heats to 80 DEG C, reacts 1h, obtains catechu modified epoxy
Resin prepolymer；
(3) the curing agent PDA that mass fraction is 13 is added in above-mentioned catechu modified epoxy performed polymer, temperature is protected
It holds at 80 DEG C, stirring is completely dissolved curing agent；
(4) said mixture is placed in vacuum drying oven 15min to remove bubble；
(5) by deaeration, treated that mixture pours into ready mold, is placed in air dry oven, 1h at 80 DEG C,
1h at 105 DEG C, 2h solidifies at 150 DEG C, and the batten after the completion of solidifying is placed in carries out Mechanics Performance Testing afterwards for 24 hours at room temperature.
Test result shows that the tensile strength of modified epoxy, bending strength are respectively 77.6MPa, 159.3MPa, breaks
Splitting elongation is 5.2% (being shown in Table 1).
Embodiment 5:
In addition to used biomass is granatum, other conditions are same as Example 4.Gained modified epoxy
Mechanical experimental results show that its tensile strength, bending strength are respectively 73.7MPa, 136.4MPa, and elongation at break is
6.0% (being shown in Table 1).
The mechanical property of table 1 epoxy resin and biomass modified epoxy resin
Claims (7)
1. a kind of preparation method of biomass modified epoxy resin, it is characterized in that:
(1) biomass material dries pulverizing, sieving, and be further ground to powdered；
(2) powdered biomass is mixed with epoxy resin, stirs 20min at 60 DEG C, then heat to 80 DEG C, reacted 1h, obtain
To biomass modified epoxy resin prepolymer, the mass ratio of powdered biomass and epoxy resin is 1/100~2/100；
(3) curing agent is added in modified epoxy performed polymer, solidifies, obtains modified epoxy material.
2. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that: the biomass is youngster
Tea, granatum or Cortex walnut.
3. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that: the baking of biomass material
Dry is by biomass in 60 DEG C of vacuum drying 8h, and the average grain diameter of powdered biomass is 0.1~20 μm.
4. the preparation method of biomass modified epoxy resin according to claim 3, it is characterized in that: powdered biomass is flat
Equal partial size is 0.5~2 μm.
5. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that: the epoxy resin
Including bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, adjacent first
The mixture of one or more of novolac epoxy resin.
6. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that: the curing agent packet
Include one in 4,4- diaminodiphenylmethane, m-phenylene diamine (MPD), alicyclic polyamine, aromatic polyamine, tertiary amine and imidazole curing agent
Kind or several mixtures.
7. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that: described be cured as medium temperature
Solidification, actual conditions are as follows: under the conditions of 80~110 DEG C under the conditions of the precuring of 1~3h and 120~180 DEG C 2~6h rear solidification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710725990.9A CN107541016B (en) | 2017-08-22 | 2017-08-22 | A kind of preparation method of biomass modified epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710725990.9A CN107541016B (en) | 2017-08-22 | 2017-08-22 | A kind of preparation method of biomass modified epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107541016A CN107541016A (en) | 2018-01-05 |
| CN107541016B true CN107541016B (en) | 2019-11-01 |
Family
ID=60958708
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710725990.9A Active CN107541016B (en) | 2017-08-22 | 2017-08-22 | A kind of preparation method of biomass modified epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107541016B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591494B (en) * | 2022-02-18 | 2023-10-03 | 泰州市天润合成化工有限公司 | Biomass-based modified epoxy resin and production process thereof |
| CN115433470B (en) * | 2022-10-09 | 2023-12-22 | 王祥宇 | Epoxy resin walnut sand material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19909270A1 (en) * | 1999-03-03 | 2000-09-07 | Henkel Teroson Gmbh | Thermosetting, thermally expandable molded body |
| CN101265364B (en) * | 2007-07-27 | 2010-08-11 | 张国栋 | Thermoset plastics infiltration strengthened powdery plant fiber material and preparation method thereof |
| CN102838860A (en) * | 2011-06-23 | 2012-12-26 | 广东晨宝复合材料有限公司 | Formula and preparation method of wood-plastic composite material |
| CN105670180B (en) * | 2016-04-12 | 2017-09-19 | 桂林舒康建材有限公司 | A kind of wood moulding clothes hanger and its preparation technology |
-
2017
- 2017-08-22 CN CN201710725990.9A patent/CN107541016B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107541016A (en) | 2018-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102337007B (en) | High-performance epoxy resin composition for sheet molding compound (SMC) | |
| CN101747882B (en) | Tectorial membrane sand solidifying system suitable for low-temperature reservoir sand prevention | |
| CN102746622A (en) | Prepreg with moderate-temperature cured epoxy resin as substrate material and preparation method thereof | |
| CN105400133A (en) | Method for enhancing carbon fiber resin based composite material through organic modified nano-particles | |
| CN104277418A (en) | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof | |
| CN103437158B (en) | A kind of carbon-fibre composite and its preparation method | |
| CN102286138A (en) | Heat-resistant epoxide resin composition for rapid pultrusion | |
| CN105255425A (en) | Bi-component epoxy adhesive for temporary adhesion as well as preparation method and application of bi-component epoxy adhesive | |
| CN102344647B (en) | Environmentally-friendly high-seepage epoxy grouting material and preparation method and application thereof | |
| CN107541016B (en) | A kind of preparation method of biomass modified epoxy resin | |
| CN105368046B (en) | Cyanate ester resin/heat conduction filler composition, prepreg and its application | |
| CN101914267A (en) | High-performance epoxy resin composition for pulling and extrusion and preparation method thereof | |
| CN103865235A (en) | Solid buoyancy material with high impact strength and preparation method thereof | |
| CN112680072A (en) | Low-viscosity high-toughness quick-drying finish paint containing hyperbranched modified epoxy resin and preparation method thereof | |
| CN109777040A (en) | A kind of biomass-based recoverable version epoxy resin and its preparation method and application | |
| CN103421140A (en) | Epoxy resin curing agent and preparation method thereof | |
| CN117143317A (en) | Degradable epoxy resin and preparation method and application thereof | |
| CN109608889B (en) | POSS (polyhedral oligomeric silsesquioxane) modified high-toughness solid buoyancy material and preparation method thereof | |
| CN105968715A (en) | Toughened and modified epoxy resin system for carbon fiber prepreg, preparation method of epoxy resin system, and prepreg prepared from epoxy resin system | |
| CN113999490A (en) | Tough epoxy resin system and preparation method and application thereof | |
| CN104725777A (en) | Low density high heat stability epoxy resin matrix preparation | |
| CN106751819A (en) | A kind of RTM techniques cyanate resin composition and preparation method | |
| RU2543871C2 (en) | Method of obtaining chemically stable press-moulds and instruments | |
| CN108162567A (en) | A kind of preparation method of packaging material | |
| CN103980464B (en) | A kind of macromole epoxy curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |