CN102585532A - Fiber-filled tung-oil-based resin composite material and preparation method thereof - Google Patents
Fiber-filled tung-oil-based resin composite material and preparation method thereof Download PDFInfo
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- CN102585532A CN102585532A CN2012100029513A CN201210002951A CN102585532A CN 102585532 A CN102585532 A CN 102585532A CN 2012100029513 A CN2012100029513 A CN 2012100029513A CN 201210002951 A CN201210002951 A CN 201210002951A CN 102585532 A CN102585532 A CN 102585532A
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Abstract
The invention discloses a fiber-filled tung-oil-based resin composite material and a preparation method thereof, wherein, particularly, petroleum base resin is replaced or partially replaced by natural tung-oil and derivatives thereof serving as a resin material when a fiber filled resin composite material is prepared, aiming at increasing the content of a renewable material in a polymer/fiber composite material. The fiber-filled tung-oil-based resin composite material is combined and prepared from the following raw materials in percentage by weight: 10%-99% of tung-oil-based resin, 0%-99% of industrial resin, 0%-80% of additive, 0.1%-20% of curing agent, 0%-20% of catalyst and 2%-80% of fiber. The fiber-filled tung-oil-based resin composite material provided by the invention is simple and convenient in preparation process, strong in operability and easy to be industrialized, can be used in fields of frames of solar battery assemblies, brackets, environmental-friendly architecture materials, furniture, floors, architectures, directive materials, sports goods and the like, has the characteristics of being environmental-friendly, light, energy-saving, resource saving and the like, and has a wide application prospect.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of biomass-based resin composite material and preparation method thereof, relate in particular to tung oil based resin composite material of a kind of fiber filled and preparation method thereof.
Background technology
In the face of the situation that our the long-term oil and natural gas that relies on can exhaust between following or two hundred years, people are just striving to find the biomass energy and the material that can replace oil and natural gas and are realizing Sustainable development.The widely used plastics of people but rely on petroleum resources for a long time, are difficult to biological degradation, and production process is poisoned big, has brought great pollution to environment.Therefore, be necessary very much to develop the use that bio-based resin new, environmental protection substituted or reduced petroleum-based plastics.
Over more than thousand year, China adopts tung oil making coatings protection furniture, ship and building structure for a long time, because the tung oil coating can oxidized crosslinking curing, viscosity is strong, and is waterproof, and wear-resisting durable, is a kind of biological material with many comprehensive excellent properties.And the suitable tung oil tree growth of China's weather and other physical environments, be always in distant neck other countries aspect the tung oil production with China.But for a long time, the tung oil industry is continued to use traditional technology, and utilizing high-tech is the innovation of tung oil industry ground zero; Multinomial patent has been announced method (the application number 200810031013.X that utilizes tung oil to do coating and resin raw material; 201110093579.7; 201110002171.4; 200410065369.7; 200910185732.1; 200910070756.2; 200910218768.5 etc.); Also having human tung oil to prepare the bio-based plastics in recent years, is that the Chinese patent of 201110076740.X has been introduced the method for utilizing tung oil acid anhydride to prepare full bio-based composition epoxy resin and cured article like application number; Can predict, develop new tung oil technology and application through system's scientific research and innovation, tung oil will become the important source of multiduty biological plastics.And tung oil processed fiber filled bio-based composite material report still seldom.The present invention replaces the petroleum base polymer materials to be used for the preparation of fibre composite the tung oil sill; Have the resin wide material sources, preparation is easy, operability good; Excellent product performance, environmental friendliness; Reduced the consumption of the Composite Preparation PetroChina Company Limited. resource and the energy, green energy conservation has wide application prospect.
Summary of the invention
The technical problem that the present invention will solve provides a kind of tung oil based resin composite material of fiber filled, and the present invention provides a kind of preparation method of tung oil based resin composite material of fiber filled simultaneously.
The tung oil based resin composite material of fiber filled of the present invention, its composition of raw materials is following by weight percentage:
Tung oil base resin 10%～99%;
Resin of industry 0～90%;
Additive 0～80%;
Solidifying agent 0.1%～20%;
Catalyzer 0～20%;
Fiber 2%～80%.
Said tung oil base resin is one or more in natural tung oil, polymerized tung oil, epoxy tung oil, acroleic acid esterification epoxy tung oil, the resol tung oil.
Described resin of industry is meant one or more in the epoxy resin that derives from petroleum path, Vinylite, unsaturated polyester resin, resol, urethane resin, propenoate, the vinyl monomer.
Described additive is meant that carbon black, WHITE CARBON BLACK, lime carbonate, polynite, clay, one or many reclaim one or more in plastic cement, thinner, oxidation inhibitor, UV light absorber, softening agent, static inhibitor, fire retardant, thermo-stabilizer, anti-impact modifier, photostabilizer, the pigment.
Described fiber is one or both in organic fibre, the inorganic fibre.
Described organic fibre is vegetable fibre, synthetic plastic fiber; Inorganic fibre is mineral fibre, spun glass, thomel.
The preparation method of the tung oil based resin composite material of fiber filled of the present invention comprises following steps:
1.. tung oil sill, solidifying agent, additive and mixing diluents evenly are made into glue;
2.. glue and fiber thorough mixing are even, make the glue infiltrated fiber, form mixture;
3.. above-mentioned mixture is put into mould, under certain pressure, temperature condition, utilize the molding mode of light or hot irradiation to cause the tung oil based resin composite material that above-mentioned crosslinking complexes curing obtains fiber filled.
The pressure of step described in 3. is 0～15 MPa, and temperature is 25 ℃～250 ℃.
The molding mode of step described in 3. comprises compression molding, extrusion moulding, injection moulding.
The preparation method of the tung oil based resin composite material of fiber filled of the present invention; Be that tung oil base resin, solidifying agent and other associated materials are uniformly mixed to form glue; With the glue infiltrated fiber; Compatible well with fiber, under certain temperature, pressure condition, utilize the mode of light or hot irradiation to cause the crosslinking complexes curing molding this mixture.
The present invention adopts green reproducible tung oil base resin to substitute the raw material that petroleum base resin is made polymer fiber composites, have equipment simple, easy and simple to handle, help environment protection, reduce carbon footprint and the characteristics of cost of polymer fiber composites in producing.
Embodiment
The tung oil based resin composite material of a kind of fiber filled of the present invention; Its solidifying agent can be a polycondensation add-on type solidifying agent; Like acid anhydride type curing agent, polyamines class solidifying agent, phenolic solidifying agent, thio-alcohol solidifying agent; Also can be initiated polymerization type solidifying agent, like radical or ionic light or thermic initiator; Described curing is meant with visible light source, ultraviolet source, radioactive source or adds the thermal initiation mode goes to cause organic molecule functional group chemistry to be cross-linked into polymkeric substance, and light source can be various manual works and lamps such as luminescent lamp, argon and xenon glow lamp, the tungsten lamp of carbon arc, mercury (steam arc) lamp, emitted in ultraviolet light, electrodeless lamp, radioactive source, sunshine.
Said recovery plastic cement can be the mixture of various rubber-plastics materials, wherein can contain materials such as plastics additive, stick, paper, pigment.
Described fiber is meant organic fibre, inorganic fibre, and organic and inorganic fibre mixture contain the organic fibre of particulate state additive, contain the inorganic fibre of particulate state additive, or contain the organic of particulate state additive and inorganic fibre mixture.These fibers can be modification or unmodified herbage or xylophyta, and wooden chaff or other wooden reclaimed materials, paper product reclaimed materials, cloth matter reclaimed materials are received spun glass, mineral fibre, plastic optical fibre, nanofiber etc.; Particle can be an organic granular, inorganic particle, organic and inorganic particle mixture; Fiber and particle can be nano-scales or greater than nano-scale.The mechanical property that these material select targets are reinforced composite finished products and other chemistry and physicals, or from the needs of energy-conserving and environment-protective, green recycling economy.
Can further be expressly understood the present invention through specific embodiment of the present invention given below, but following embodiment is not to qualification of the present invention.
Embodiment 1
100 parts of epoxy tung oil (oxirane value is 0.6), 30 parts of maleic anhydrides, 1.5 parts of DMP-30 (2,4,6-three (dimethylaminomethyl) phenol) are made into glue; Under vacuum condition,, then, mixture is poured in the mould with 130 parts of xylon mixing deaerations; Under 145 ℃ of temperature; Pressurize 4h under the 3MPa, the cooling demoulding naturally obtains tung oil/Wood Fiber Composites.
Embodiment 2
100 parts of epoxy tung oil (oxirane value is 0.6), 10 parts of E-51 (bisphenol A type epoxy resin, oxirane value are 0.51), 24 parts of T31 (phenolic aldehyde amine), 0.5 part of UV light absorber UV-531 are mixed, be made into glue; Under vacuum condition with 5 parts of lime carbonate, 10 parts of bamboo fibres, 120 parts of xylon mixing deaerations; Then mixture is poured in the mould, under 100 ℃ of temperature, pressurize 2h under 3 MPa; Naturally the cooling demoulding obtains tung oil/Wood Fiber Composites.
Embodiment 3
100 parts of epoxy tung oil (oxirane value is 0.6), 20 parts of TDI-80/ Polypropylene Glycol Glycerin Ether performed polymers (nco value is 4%), 22 parts of solidifying agent MOCA (3,3'-two chloro-4,4'-diaminodiphenyl-methane), 0.4 part of stannous octoate are mixed; Be made into glue, under vacuum condition,, then mixture poured in the mould with 5 powder lime carbonate, 140 parts of xylon mixing deaerations; Under 120 ℃ of temperature; Pressurize 3h under 3 MPa, the cooling demoulding naturally obtains tung oil/Wood Fiber Composites.
Embodiment 4
100 parts of natural tung oil, 15 parts of vinylbenzene, 30 parts of Vinylstyrenes, 5 parts of BPOs are mixed; Be made into glue, under vacuum condition,, then mixture poured in the mould with 150 parts of xylon mixing deaerations; Under 80 ℃ of temperature; Pressurize 3h under 3 MPa, the cooling demoulding naturally obtains tung oil/Wood Fiber Composites.
Embodiment 5
100 parts of epoxy tung oil (oxirane value is 0.8), 15 parts of E-44 (bisphenol A type epoxy resin, oxirane value are 0.45), 5 parts of ICAM-8409 (the cationic thermal initiator of hexafluoro antimonate) are mixed, be made into glue; Under vacuum condition with 10 parts of Chinese silvergrasses, 10 parts of bamboo fibres, 100 parts of xylon mixing deaerations; Then mixture is poured in the mould, under 100 ℃ of temperature, pressurize 20min under 3 MPa; Naturally the cooling demoulding obtains tung oil/Wood Fiber Composites.
Embodiment 6
With 100 parts of epoxy tung oil (oxirane value is 0.8), 25 parts of E-44 (bisphenol A type epoxy resins; Oxirane value is 0.45), 6 parts of cation light initiator triaryl phosphofluoric acid sulfosalts, 0.5 part of oxidation inhibitor butylated hydroxytoluene mix, and are made into glue, under vacuum condition with 130 parts of grindings after xylon (particle diameter is less than 100 μ m) mix deaeration; Then mixture is poured in the mould; Being pressed into the thick thin slice of 100 μ m, is the medium pressure mercury lamp irradiation 3min of 800W then with power, and the lamp distance is 20cm; Glue-line is a fast setting, obtains tung oil/Wood Fiber Composites.
Embodiment 7
Mix with 100 parts of epoxy resin E-44s (oxirane value is 0.43), with 150 parts of tung oil acid anhydrides, 4 parts of DBU (1,8-diazabicylo [5.4.0] 11 carbon-7-alkene), be made into glue; Under vacuum condition with 300 parts of spun glass mixing deaerations; Then mixture is poured in the mould, under 145 ℃ of temperature, pressurize 4h under 3 MPa; Naturally the cooling demoulding obtains tung oil/glass fiber composite material.
Embodiment 8
With 100 parts of epoxy tung oil (oxirane value is 0.8), 24 parts of Vicbase EH3535 (Shenzhen Kai Ji Applied Materials Inc trade names, imidazoles addition epoxy resin modification thing), mix; Be made into glue, under vacuum condition,, then mixture poured in the mould with 5 powder lime carbonate, 10 parts of bamboo fibres, 120 parts of xylon mixing deaerations; Under 100 ℃ of temperature; Pressurize 2h under 3 MPa, the cooling demoulding naturally obtains tung oil/Wood Fiber Composites.
Embodiment 9
With 100 parts of epoxy tung oil (oxirane value is 0.8), 15 parts of Dyhard RU 100s, 1 part of Vicbase EH3535 (Shenzhen Kai Ji Applied Materials Inc trade names, imidazoles addition epoxy resin modification thing), mix; Be made into glue, under vacuum condition,, then mixture poured in the mould with 5 powder lime carbonate, 10 parts of bamboo fibres, 100 parts of xylon mixing deaerations; Under 130 ℃ of temperature; Pressurize 2h under 3 MPa, the cooling demoulding naturally obtains tung oil/Wood Fiber Composites.
Embodiment 10
It is for use that 100 parts of epoxy tung oil are stirred and heated to 90 ° of C; 1.5 parts of triphenylphosphines, 0.5 part of p methoxy phenol are dissolved in 60 parts of vinylformic acid; Stir, the vinylformic acid mixed solution is added in the epoxy tung oil react, when reaction system acid number during less than 3mgKOH/g; Finish reaction, obtain the epoxy tung oil of acroleic acid esterification;
Epoxy tung oil and 20 parts of vinylbenzene, 20 parts of bisphenol-A epoxy vinylester resins, 2 parts of cobalt octoates, 1 part of Diethyl Aniline, 2 parts of methylethyl ketone peroxides of 60 parts of aforesaid propylene acid estersization are mixed, be made into glue, with 5 powder lime carbonate, 10 parts of bamboo fibres, 120 parts of xylon mixing deaerations; Then mixture is poured in the mould; Under 50 ℃ of temperature, pressurize 1h under 3 MPa, pressurize 1h is continued in the back under 100 ° of C temperature; Naturally the cooling demoulding obtains tung oil/Wood Fiber Composites.
Embodiment 11
Epoxy tung oil and 20 parts of TEB 3Ks, 20 parts of dihydroxyphenyl propane unsaturated polyester resins, 2 parts of cobalt octoates, 1 part of Diethyl Aniline, 2 parts of methylethyl ketone peroxides of 60 parts of acroleic acid esterifications are mixed, be made into glue, with 5 whitewash carbon blacks, 10 parts of bamboo fibres, 120 parts of xylon mixing deaerations; Then mixture is poured in the mould; Under 50 ℃ of temperature, pressurize 1h under 3 MPa, pressurize 1h is continued in the back under 100 ° of C temperature; Naturally the cooling demoulding obtains tung oil/Wood Fiber Composites.
Embodiment 12
40 parts of natural tung oil, 100 parts of phenol, 0.5 part of p-methyl benzenesulfonic acid, 100 ° of C back flow reaction 2 hours are cooled to 50 ° of C, with the alkali neutralization, regulate PH to 8; Add 100 parts of formaldehyde, 0.5 part of sodium hydroxide, stir and to be warming up to 100 ° of C, react 1.5 hours, be cooled to 50 ° of C, with in the acid and PH to 7, decompression dehydration obtains tung oil modified phenolic resin;
100 parts of tung oil modified phenolic resins, 50 parts of recovery PS, 50 parts of xylons are mixed and vacuum defoamation; Pour mixture into mould then, under 200 ℃ of temperature, pressurize 2h under 3 MPa; Naturally the cooling demoulding obtains tung oil modified phenolic resin/plastics, Wood Fiber Composites.
Claims (8)
1. the tung oil based resin composite material of a fiber filled is characterized in that, said matrix material its composition of raw materials by mass percentage is following:
Tung oil base resin 10%～99%;
Resin of industry 0～90%;
Additive 0～80%;
Solidifying agent 0.1%～20%;
Catalyzer 0～20%;
Fiber 2%～80%.
2. the tung oil based resin composite material of fiber filled according to claim 1, it is characterized in that: said tung oil base resin is one or more in natural tung oil, polymerized tung oil, epoxy tung oil, acroleic acid esterification epoxy tung oil, the resol tung oil.
3. the tung oil based resin composite material of fiber filled according to claim 1 is characterized in that: described resin of industry is meant one or more in the epoxy resin that derives from petroleum path, Vinylite, unsaturated polyester resin, resol, urethane resin, propenoate, the vinyl monomer.
4. the tung oil based resin composite material of fiber filled according to claim 1, it is characterized in that: described fiber is one or both in organic fibre, the inorganic fibre.
5. according to the tung oil based resin composite material of claim 1 or 4 described fiber filled, it is characterized in that: organic fibre is vegetable fibre, synthetic plastic fiber; Inorganic fibre is mineral fibre, spun glass, thomel.
6. be used for the preparation method of tung oil based resin composite material of the fiber filled of claim 1, it is characterized in that comprising following steps:
1.. tung oil base resin material, resin of industry solidifying agent, additive and catalyst mix evenly are made into glue;
2.. glue and fiber thorough mixing are even, make the glue infiltrated fiber, form mixture;
3.. above-mentioned mixture is put into mould, under certain pressure and temperature condition, utilize the molding mode of light or hot irradiation to cause the tung oil based resin composite material that above-mentioned crosslinking complexes curing obtains fiber filled.
7. the preparation method of the tung oil based resin composite material of fiber filled according to claim 6 is characterized in that: the pressure of step described in 3. is 0～15 MPa, and temperature is 25 ℃～250 ℃.
8. the preparation method of the tung oil based resin composite material of fiber filled according to claim 6 is characterized in that: the molding mode of step described in 3. comprises compression molding, extrusion moulding, injection moulding.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102732200A (en) * | 2012-07-13 | 2012-10-17 | 中物院成都科学技术发展中心 | Vegetable oil-based adhesive, composite plywood and method for manufacturing composite plywood |
| CN105461899A (en) * | 2015-12-08 | 2016-04-06 | 王景泉 | Natural-based modified light-cured resin and preparation method thereof |
| CN105968544A (en) * | 2016-07-29 | 2016-09-28 | 安徽科邦树脂科技有限公司 | Wear-resisting synthetic resin and preparation method thereof |
| CN106243544A (en) * | 2016-07-29 | 2016-12-21 | 安徽科邦树脂科技有限公司 | A kind of high flame retardant synthetic resin and preparation method thereof |
| TWI563037B (en) * | 2015-10-27 | 2016-12-21 | Sungo Green Science And Technology Inc | A bio-composite substrate simulating metal |
| CN107474574A (en) * | 2017-09-07 | 2017-12-15 | 绵阳旺通科技有限公司 | A kind of environment-friendly type tung-oil-based resin composite material and preparation method thereof |
| CN116515313A (en) * | 2023-05-16 | 2023-08-01 | 佳贺科技无锡有限公司 | Environment-friendly buffer logistics packaging material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732200A (en) * | 2012-07-13 | 2012-10-17 | 中物院成都科学技术发展中心 | Vegetable oil-based adhesive, composite plywood and method for manufacturing composite plywood |
| TWI563037B (en) * | 2015-10-27 | 2016-12-21 | Sungo Green Science And Technology Inc | A bio-composite substrate simulating metal |
| CN105461899A (en) * | 2015-12-08 | 2016-04-06 | 王景泉 | Natural-based modified light-cured resin and preparation method thereof |
| CN105968544A (en) * | 2016-07-29 | 2016-09-28 | 安徽科邦树脂科技有限公司 | Wear-resisting synthetic resin and preparation method thereof |
| CN106243544A (en) * | 2016-07-29 | 2016-12-21 | 安徽科邦树脂科技有限公司 | A kind of high flame retardant synthetic resin and preparation method thereof |
| CN107474574A (en) * | 2017-09-07 | 2017-12-15 | 绵阳旺通科技有限公司 | A kind of environment-friendly type tung-oil-based resin composite material and preparation method thereof |
| CN116515313A (en) * | 2023-05-16 | 2023-08-01 | 佳贺科技无锡有限公司 | Environment-friendly buffer logistics packaging material and preparation method thereof |
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Application publication date: 20120718 |