CN107541016A - A kind of preparation method of biomass modified epoxy resin - Google Patents
A kind of preparation method of biomass modified epoxy resin Download PDFInfo
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- CN107541016A CN107541016A CN201710725990.9A CN201710725990A CN107541016A CN 107541016 A CN107541016 A CN 107541016A CN 201710725990 A CN201710725990 A CN 201710725990A CN 107541016 A CN107541016 A CN 107541016A
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- epoxy resin
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Abstract
The present invention is to provide a kind of preparation method of biomass modified epoxy resin.Biomass material dries pulverizing, sieving, and be further ground to powdered；Powdered biomass is mixed with epoxy resin, 20min is stirred 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.The method of the present invention has the advantages that raw material sources are extensive, cheap, and preparation technology is simple, easily operated.The modified epoxy obtained using the preparation method of the present invention has good stability, and the stretching of material, bending strength highest can lift 46.3%, 36.1% respectively；The lifting of shock resistance reaches as high as 94.2%.The modified epoxy obtained can be used as resin material and be used directly as electronic apparatus material, aerospace material and engineering plastics, can also be used as the matrix resin of composite.
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 fat.
Background technology
Epoxy resin has excellent performance, had in metal, nonmetallic surface good as a kind of thermoset resin material
Good adhesive strength, to alkali and most of solvent-stable, while have excellent dielectric properties, good heat-moisture resistance energy,
High insulating properties, good dimensional stability and processing characteristics, adhesive, lamination material, coating and casting material can be used as extensive
Applied to every field such as civilian, national defence.
Epoxy resin is the most widely used matrix of field of polymer-base composite material, and it is applied to a variety of moulding process,
Grown with storage time, do not discharge small organic molecule during solidification, cure shrinkage is low, and the product after solidification has splendid chi
Very little stability.Epoxy resin composite material is widely used in aerospace field, the rotor of radome, helicopter such as aircraft,
The housing of solid propellant rocket, system unit etc.；Include the pressure vessel and pipe of fiberglass in the main application of civil area
Road, anticorrosive article etc..
The content of the invention
It is an object of the invention to provide a kind of stability that can improve product, tensile strength, flexural strength, anti-impact
Hit intensity, raw material is cheap and easy to get, technique is simple, 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, 20min is stirred at 60 DEG C, then heat to 80 DEG C, reaction
1h, obtain biomass modified epoxy resin prepolymer；
(3) curing agent is added in modified epoxy performed polymer, solidifies, obtain modified epoxy material.
The present invention can also include：
1st, the biomass is catechu, granatum or Cortex walnut.
2nd, the drying of biomass material is to be in 60 DEG C of vacuum drying 8h, the average grain diameter of powdered biomass by biomass
0.1~20 μm.Preferably 0.5~2 μm.
3rd, the mass ratio of powdered biomass and epoxy resin is 0.5/100~10/100.Preferably 1/100~2/100.
4th, described epoxy resin includes bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol F type epoxy tree
One or more of mixtures in fat, bisphenol-s epoxy resin, o-cresol formaldehyde epoxy resin.
5th, described curing agent include 4,4- MDAs, m-phenylene diamine (MPD), alicyclic polyamine, aromatic polyamine,
One or more of mixtures in tertiary amine and imidazole curing agent.
6th, described to be cured as intermediate temperature setting, actual conditions is：1~3h precuring and 120 under the conditions of 80~110 DEG C~
2~6h solidify afterwards under the conditions of 180 DEG C.
To lift the mechanical property of epoxy resin, its application is extended, the present invention is using wide material sources, cheap
Biomass (such as catechu, granatum, Cortex walnut) is modified to epoxy resin, and the stretching for being effectively improved epoxy resin is strong
Degree, bending strength and shock resistance.This method has the advantages that preparation technology is simple, easily operated, the modified epoxy of acquisition
Resin has good stability, is with a wide range of applications, you can as resin material directly as electronic apparatus material,
Aerospace material and engineering plastics use, and can also be used as the matrix resin of composite.
Compared with prior art, the present invention has following feature：
(1) preparation method of biomass modified epoxy resin provided by the invention, use natural biomass (such as catechu,
Granatum, Cortex walnut etc.) have that raw material sources are extensive, the advantage such as cheap, renewable, green, 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, technique simple, easy
In operation, equipment investment is small, easily mass produce the advantages that.
(3) the biomass modified epoxy resin obtained using the preparation method of the present invention has excellent mechanical property, can
It is applied to field of electronics, aerospace field and engineering plastics directly as resin material；And drawing due to biomass
Enter, epoxy resin and organic and inorganic reinforcer and the compatibility of reinforcing fiber can be effectively improved, therefore as compound
The matrix resin of material uses the performance that can effectively improve composite.
Embodiment
Illustrate below and the present invention is described further.The scope of the present invention is not restricted by the embodiments.
Comparative example 1：
(1) it is 100 curing agent 4,4-MDA (DDM) that mass fraction is 25 to be added into mass fraction
In epoxy resin, the heating stirring at 80 DEG C, curing agent is set to 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) mixture after deaeration is handled is poured into ready mould, is placed in air dry oven, 2h at 80 DEG C,
4h solidifies at 135 DEG C, and the batten after the completion of solidification carries out Mechanics Performance Testing after being placed in 24h at room temperature.
Test result shows that tensile strength, the bending strength of epoxy resin 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 into fine powder；
(2) the catechu powder that mass fraction is 1 is mixed with the epoxy resin that mass fraction is 100, stirred at 60 DEG C
20min makes catechu particulate be well mixed 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
Hold at 80 DEG C, stirring is completely dissolved curing agent；
(4) said mixture is placed in vacuum drying oven 15min to remove bubble；
(5) mixture after deaeration is handled is poured into ready mould, is placed in air dry oven, 2h at 80 DEG C,
4h solidifies at 135 DEG C, and the batten after the completion of solidification carries out Mechanics Performance Testing after being placed in 24h at room temperature.
Test result shows that tensile strength, the bending strength of modified epoxy are respectively 91.8MPa, 147.4MPa, are broken
It is 6.6% to split elongation, 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, curing agent is 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) mixture after deaeration is handled is poured into ready mould, 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 solidification carries out Mechanics Performance Testing after being placed in 24h at room temperature.
Test result shows that tensile strength, the bending strength of epoxy resin 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 into fine powder；
(2) the catechu powder that mass fraction is 1 is mixed with the epoxy resin that mass fraction is 100, stirred at 60 DEG C
20min makes catechu particulate be well mixed 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
Hold at 80 DEG C, stirring is completely dissolved curing agent；
(4) said mixture is placed in vacuum drying oven 15min to remove bubble；
(5) mixture after deaeration is handled is poured into ready mould, 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 solidification carries out Mechanics Performance Testing after being placed in 24h at room temperature.
Test result shows that tensile strength, the bending strength of modified epoxy are respectively 77.6MPa, 159.3MPa, are broken
It is 5.2% (being shown in Table 1) to split elongation.
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 the epoxy resin of table 1 and biomass modified epoxy resin
Claims (9)
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, 20min is stirred at 60 DEG C, then heat to 80 DEG C, reacted 1h, obtain
To biomass modified epoxy resin prepolymer；
(3) curing agent is added in modified epoxy performed polymer, solidifies, obtain 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 that the average grain diameter of powdered biomass is 0.1~20 μm in 60 DEG C of vacuum drying 8h by biomass.
4. the preparation method of biomass modified epoxy resin according to claim 3, it is characterized in that：Powdered biomass is put down
Equal particle diameter is 0.5~2 μm.
5. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that：Powdered biomass and ring
The mass ratio of oxygen tree fat is 0.5/100~10/100.
6. the preparation method of biomass modified epoxy resin according to claim 5, it is characterized in that：Powdered biomass and ring
The mass ratio of oxygen tree fat is 1/100~2/100.
7. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that：Described epoxy resin
Including bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, adjacent first
One or more of mixtures in novolac epoxy resin.
8. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that：Described curing agent bag
Include one in 4,4- MDAs, m-phenylene diamine (MPD), alicyclic polyamine, aromatic polyamine, tertiary amine and imidazole curing agent
Kind or several mixtures.
9. the preparation method of biomass modified epoxy resin according to claim 1, it is characterized in that：It is described to be cured as medium temperature
Solidification, actual conditions are：Under the conditions of 80~110 DEG C under the conditions of 1~3h precuring and 120~180 DEG C 2~6h solidify afterwards.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591494A (en) * | 2022-02-18 | 2022-06-07 | 泰州市天润合成化工有限公司 | Biomass-based modified epoxy resin and production process thereof |
| CN115433470A (en) * | 2022-10-09 | 2022-12-06 | 王祥宇 | Epoxy resin walnut sand material and preparation method thereof |
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| US6573309B1 (en) * | 1999-03-03 | 2003-06-03 | Henkel Teroson Gmbh | Heat-curable, thermally expandable moulded park |
| CN101265364A (en) * | 2007-07-27 | 2008-09-17 | 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 |
| CN105670180A (en) * | 2016-04-12 | 2016-06-15 | 桂林舒康建材有限公司 | Wood plastic clothes rack and preparation technology thereof |
-
2017
- 2017-08-22 CN CN201710725990.9A patent/CN107541016B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6573309B1 (en) * | 1999-03-03 | 2003-06-03 | Henkel Teroson Gmbh | Heat-curable, thermally expandable moulded park |
| CN101265364A (en) * | 2007-07-27 | 2008-09-17 | 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 |
| CN105670180A (en) * | 2016-04-12 | 2016-06-15 | 桂林舒康建材有限公司 | Wood plastic clothes rack and preparation technology thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114591494A (en) * | 2022-02-18 | 2022-06-07 | 泰州市天润合成化工有限公司 | Biomass-based modified epoxy resin and production process thereof |
| 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 |
| CN115433470A (en) * | 2022-10-09 | 2022-12-06 | 王祥宇 | Epoxy resin walnut sand material and preparation method thereof |
| CN115433470B (en) * | 2022-10-09 | 2023-12-22 | 王祥宇 | Epoxy resin walnut sand material and preparation method thereof |
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| CN107541016B (en) | 2019-11-01 |
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