CN104371275A - Nanocellulose-thermoplastic resin synergically modified epoxy resin composite material and preparation method thereof - Google Patents
Nanocellulose-thermoplastic resin synergically modified epoxy resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nanocellulose-thermoplastic resin synergically modified epoxy resin composite material and a preparation method thereof. The nanocellulose-thermoplastic resin synergically modified epoxy resin composite material is prepared by blending the following components in parts by weight: 100 parts of epoxy resin, 27-33 parts of a curing agent, 7-33.3 parts of thermoplastic resin and 0.1-0.3 part of nanocellulose. The preparation method comprises the following steps: adding nanocellulose into distilled water and carrying out ultrasonic dispersion to form turbid liquid; adding absolute ethyl alcohol and carrying out centrifugal replacement to remove water; adding epoxy resin, carrying out magnetic stirring and dispersion, and heating to volatilize and remove ethanol; adding thermoplastic resin, carrying out oil path and mechanical stirring, cooling, adding the curing agent, and further stirring to obtain a blend; removing bubbles in a vacuum oven, pouring the blend into a mold, and heating for curing so as to prepare the nanocellulose-thermoplastic resin synergically modified epoxy resin composite material. According to the preparation method, the epoxy resin is commonly modified by virtue of environmental-friendly nanocellulose and thermoplastic resin, so that the interface bonding force is increased, and the cooperative reinforcement and toughening of the epoxy resin are achieved.
Description
Technical field
A kind of matrix material that the invention belongs to polymer matrix composites technical field and preparation method thereof, the specifically epoxy resin composite material and preparation method thereof of a kind of nano-cellulose-thermoplastic resin modified synergic.
Background technology
The advantages such as cure shrinkage is low owing to having for epoxy resin, cohesive force strong, the rear product mechanical property of solidification is high, chemical resistant properties is good, electrical insulation capability is good, in fibre-reinforced polymer matrix composites, there is irreplaceable status, be widely used in the fields such as space flight, aviation, automobile, building.But, because epoxy resin can produce highly cross-linked in the curing process, cause cured article to have the defects such as matter is crisp, impact resistance is poor, limit its application in engineering.This just requires to carry out modification to epoxy resin.
By introducing second-phase material in epoxy resin, form certain microscopical structure, increasing waste of energy, is important toughness reinforcing approach.Wherein, thermoplastic resin (as polysulfones, polyethersulfone, polyimide etc.) receives much concern to the modification of epoxy resin.But, often demonstrate phase structure interface more clearly after modified system curing reaction prepared by the method, show that phase interface bonding strength is not strong, thus toughening effect is inherently by impact to a certain extent.Along with the development of nanotechnology, it is found that adopt two kinds of properties-correcting agent to carry out modification to epoxy resin is the effective ways improving epoxy resin over-all properties further simultaneously.The Nano filling (as carbon nanotube, titanium dioxide etc.) of different shape is incorporated in thermoplastic resin modified epoxy-resin systems, reaches the effect of collaborative activeness and quietness.
In recent years, nano-cellulose, owing to having the advantages such as high strength, high-modulus, high-specific surface area, biodegradable and raw materials be abundant, receives the concern of more and more investigator, is widely used in the field such as reinforced composite, biological medicine material.Utilize nano-cellulose to replace carbon nanotube etc. to carry out reinforced epoxy, comply with the requirement of environmental protection to a certain extent, reduce environmental pollution, meanwhile, also avoid the safety and health problem that application inorganic nano-filler may bring out.At present, though utilize the research of nano-cellulose to simple epoxy-resin systems modification to carry out but still be in the starting stage, there is nano-cellulose and be difficult to dispersion and the unconspicuous problem of modified effect.But, have not been reported with the research of nano-cellulose and the common modified epoxy of thermoplastic resin.
Summary of the invention
In order to solve Problems existing in background technology, the invention provides epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic and preparation method thereof, object carries out collaborative activeness and quietness with the high length-diameter ratio nano-cellulose of excellent in mechanical performance and thermoplastic resin to epoxy resin.
The technical solution used in the present invention is:
One, the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic:
Form by epoxy resin, solidifying agent, thermoplastic resin and nano-cellulose are blended, the weight proportion of epoxy resin, solidifying agent, thermoplastic resin and nano-cellulose is 100:27 ~ 33:7 ~ 33.3:0.1 ~ 0.3.
A preparation method for the epoxy resin composite material of two, nano-cellulose-thermoplastic resin modified synergic, comprises the following steps:
1) preparation of nano-cellulose/epoxy-resin systems:
1.1) nano-cellulose of 0.1 ~ 0.3 weight part is joined the distilled water of 100 ~ 300 weight parts, sonic oscillation is until the stable suspension liquid of the dispersed formation of nano-cellulose;
1.2) to step 1.1) add and step 1.1 in the nano-cellulose aqueous solution prepared) in the dehydrated alcohol of distilled water identical weight part carry out centrifugal displacement, through displacement by water removing wherein, obtain the ethanolic soln of nano-cellulose; Again carry out sonic oscillation process 20 minutes, until nano-cellulose evenly spreads in ethanol;
1.3) to step 1.2) add the epoxy resin of 100 weight parts in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing;
2) preparation of nano-cellulose/thermoplastic resin/epoxy resin composite system:
2.1) in step 1.3) in the homodisperse epoxy resin of nano-cellulose that obtains, add the thermoplastic resin of 7 ~ 33.3 weight parts in 120 ~ 150 DEG C of oil baths, carry out mechanical stirring after 2 ~ 4 hours, the solidifying agent of 27 ~ 33 weight parts is added while stirring after being cooled to 60 ~ 110 DEG C, continue stirring 10 ~ 30 minutes, obtain nano-cellulose, thermoplastic resin and epoxy resin blend;
2.2) step 2.1) in the blend of gained in vacuum drying oven, vacuumize 20 ~ 40 minutes remove bubble, be cast in afterwards in Teflon mould, be heating and curing at being 60 ~ 200 DEG C in normal pressure, temperature, the epoxy resin composite material of obtained nano-cellulose and thermoplastic resin modified synergic.
Described step 1.3) in heat treated after 4 hours, then be placed in 80 DEG C of vacuum drying ovens and carry out vacuumizing process 4 hours, to be removed completely by ethanol.
Described epoxy resin is liquid bisphenol A type epoxy resin E51, and epoxy equivalent (weight) is 185 ~ 200g/eq.
Described solidifying agent is amine curing agent, be specially 4,4 '-diaminodiphenylsulfone(DDS) (DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane (DDM) or polyetheramine (D230), prioritizing selection 4,4 '-diaminodiphenylsulfone(DDS) (DDS).
Described thermoplastic resin is polyimide (PI), polyetherimide (PEI), polysulfones (PSF) or polycaprolactone (PCL), prioritizing selection polysulfones.
Described nano-cellulose adopts the high aspect fibers element nanofiber being easy to run through and tangle, and its mean fibre length is 300-600um, and mean diameter is 50-100nm.
The present invention be intended to by nano-cellulose in regulation and control phase separation between different phase region mutually run through and with the mutual entanglement effect of thermoplastic resin, improve interfacial adhesion, and then improve Material reinforcement toughening effect.
The present invention selects excellent in mechanical performance, environmental protection and the high length-diameter ratio nano-cellulose of abundance, the method combined by exchange of solvent and melt blending is dispersed in epoxy resin-base, and in phase separation, high length-diameter ratio nano-cellulose, thermoplastic resin macromolecular chain easily tangle.By nano-cellulose between different phase region run through and and thermoplastic resin macromolecular chain between entanglement, improve interfacial adhesion.Meanwhile, nano-cellulose can regulate and control the size of domain size.The raising of phase interface bonding strength and the regulation and control of domain size, be all conducive to the raising of material mechanical performance.
The epoxy-resin systems that the epoxy resin composite material mechanical property of the modified synergic of gained of the present invention is purer or simple nano-cellulose or thermoplastic resin modified epoxy resin composite system all increase.
The present invention has following beneficial effect:
1. the present invention utilizes nano-cellulose to replace carbon nanotube etc. to carry out reinforced epoxy, complies with environmental requirement, reduces environmental pollution, meanwhile, has also avoided the safety and health problem that application inorganic nano-filler may bring out.
2. its nano-cellulose does not carry out any chemical modification, thus prevents the reduction of nano-cellulose mechanical property.
3. nanofiber cellulose content controls in lower scope, and makes it dispersed as far as possible by the method for exchange of solvent, and avoiding reunites because nanofiber cellulose content is high causes composite materials property to reduce.
4. adopt high length-diameter ratio nano-cellulose fiber and thermoplastic resin modified synergic, by nano-cellulose different mutually interval run through and with the mutual entanglement of thermoplastic resin macromolecular chain, improve interfacial adhesion, and then improve material property.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the matrix material section that the embodiment of the present invention 1 prepares.
Fig. 2 schemes with the SEM of the epoxy resin composite material section of the embodiment of the present invention 1 polysulfones modification in proportion.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
Embodiments of the invention are as follows:
The present inventor through repeatedly studying, and by the checking of lot of experiments, obtains the optimised process preparing nano-cellulose/thermoplastic resin/epoxy resin composite material.Illustrate performance of the present invention below in conjunction with several representational embodiment, but subordinate's embodiment is not construed as limiting the invention.
Embodiment 1
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.1g in the beaker that 100ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 100g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens again and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 14.1g polysulfones and carry out mechanical stirring after 3 hours in 140 DEG C of oil baths, the DDS of 27g is added while stirring after being cooled to 110 DEG C, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 30 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 6h at the curing process first stage 160 DEG C, at subordinate phase 180 DEG C 2h and at the phase III 200 DEG C the program of 2h heat-treat, obtain mechanical test batten after being cooled to the room temperature demoulding.
Matrix material tensile strength prepared by the present embodiment is 83MPa, and modulus in tension is 2.8GPa, and shock strength is 24KJ/m
2; The tensile strength of pure liquid bisphenol A type epoxy resin E51 matrix is 81MPa, and modulus in tension is 2.6GPa, and shock strength is 18KJ/m
2; The tensile strength of the epoxy resin composite material of polysulfones modification is in proportion 74MPa, and modulus in tension is 2.7GPa, and shock strength is 20KJ/m
2.As can be seen here, nano-cellulose and the common modified epoxy of thermoplastic resin polysulfones can play the effect of collaborative activeness and quietness.
Contrast is schemed from the SEM of Fig. 1 and Fig. 2, the matrix material prepared in the embodiment of the present invention all defines the appearance structure of polysulfones even particulate dispersion in epoxy resin-base with the epoxy-resin systems of polysulfones modification in proportion, there is not obvious agglomeration in nano-cellulose, and adding of nano-cellulose obviously makes interfacial adhesion improve, therefore the composite materials property prepared significantly improves, and has significant technique effect.
Embodiment 2
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.2g in the beaker that 200ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 200g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 14.1g polysulfones and carry out mechanical stirring after 3 hours in 140 DEG C of oil baths, the DDS of 27g is added while stirring after being cooled to 110 DEG C, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 30 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 6h at the curing process first stage 160 DEG C, at subordinate phase 180 DEG C 2h and at the phase III 200 DEG C the program of 2h heat-treat, obtain mechanical test batten after being cooled to the room temperature demoulding.
Matrix material tensile strength prepared by the present embodiment is 85MPa, and modulus in tension is 2.8GPa, and shock strength is 31KJ/m
2, show that composite materials property increases with nanofiber cellulose content and continue to increase.Nano-cellulose and the common modified epoxy of thermoplastic resin polysulfones can play the effect of collaborative activeness and quietness.
Embodiment 3
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.3g in the beaker that 300ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 300g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 14.1g polysulfones and carry out mechanical stirring after 3 hours in 140 DEG C of oil baths, the DDS of 27g is added while stirring after being cooled to 110 DEG C, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 30 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 6h at the curing process first stage 160 DEG C, at subordinate phase 180 DEG C 2h and at the phase III 200 DEG C the program of 2h heat-treat, obtain mechanical test batten after being cooled to the room temperature demoulding.
Matrix material tensile strength prepared by the present embodiment is 86MPa, and modulus in tension is 2.8GPa, and shock strength is 26KJ/m
2, show that nano-cellulose and the common modified epoxy of thermoplastic resin polysulfones can play the effect of collaborative activeness and quietness.
Embodiment 4
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.1g in the beaker that 100ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 100g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 17.3g polysulfones and carry out mechanical stirring after 3 hours in 140 DEG C of oil baths, the DDS of 27g is added while stirring after being cooled to 110 DEG C, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 30 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 6h at the curing process first stage 160 DEG C, at subordinate phase 180 DEG C 2h and at the phase III 200 DEG C the program of 2h heat-treat, obtain mechanical test batten after being cooled to the room temperature demoulding.
Matrix material tensile strength prepared by the present embodiment is 76MPa, and modulus in tension is 2.8GPa, and shock strength is 25KJ/m
2; The epoxy resin composite material tensile strength of polysulfones modification is in proportion 66MPa, and modulus in tension is 2.8GPa, and shock strength is 17KJ/m2.As can be seen here, nano-cellulose and the common modified epoxy of thermoplastic resin polysulfones can play the effect of collaborative activeness and quietness.
Embodiment 5
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.3g in the beaker that 300ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 300g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 33.3g polycaprolactone and carry out mechanical stirring after 2 hours in 120 DEG C of oil baths, the DDS of 33g is added while stirring after being cooled to 110 DEG C, continue stirring 30 minutes, obtain nano-cellulose fiber, polycaprolactone (PCL) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 40 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 6h at the curing process first stage 160 DEG C, at subordinate phase 180 DEG C, the program of 2h is heat-treated, and obtains mechanical test batten after being cooled to the room temperature demoulding.
Matrix material tensile strength prepared by the present embodiment is 34MPa, and modulus in tension is 1.7GPa, and shock strength is 26KJ/m
2; Epoxy resin composite material tensile strength Polycaprolactone modified is in proportion 33MPa, and modulus in tension is 1.7GPa, and shock strength is 14KJ/m2.As can be seen here, nano-cellulose and the common modified epoxy of thermoplastic resin polycaprolactone can play the effect of coordination plasticizing.
Embodiment 6
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.1g in the beaker that 100ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 100g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 14.1g polysulfones and carry out mechanical stirring after 3 hours in 140 DEG C of oil baths, the DDM of 27g is added while stirring after being cooled to 80 DEG C, continue stirring 10 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 20 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 2h at the curing process first stage 100 DEG C, at subordinate phase 160 DEG C 6h and at the phase III 180 DEG C the program of 2h heat-treat, obtain mechanical test batten after being cooled to the room temperature demoulding.
The present embodiment is compared with embodiment 1 noted earlier, and preparation method is identical, and difference is that solidifying agent kind is different.The composites prepared by this embodiment can reach the object of modified synergic.
Embodiment 7
Raw material and consumption are:
The mean length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, and mean diameter is 50-100nm.
A) joined by the nano-cellulose fiber of 0.1g in the beaker that 100ml distilled water is housed, sonic oscillation 20 minutes is until the stable suspension liquid of the dispersed formation of nano-cellulose fiber;
B) add 100g dehydrated alcohol in nano-cellulose fiber aqueous solution a) prepared to step and carry out centrifugal displacement, through 5 displacements by water removing wherein, obtain the ethanolic soln of nano-cellulose fiber; Again carry out sonic oscillation process 20 minutes, until nano-cellulose fiber evenly spreads in ethanol;
C) to step b) add the liquid bisphenol A type epoxy resin E51 of 100g in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing; Be placed in 80 DEG C of vacuum drying ovens and vacuumize process again 4 hours, remove ethanol further;
D) in step c) the homodisperse bisphenol A type epoxy resin E51 of nano-cellulose fiber that obtains transfers in flask, wherein add 7g polyetherimide and carry out mechanical stirring after 3 hours in 150 DEG C of oil baths, the D230 of 31g is added while stirring after being cooled to 60 DEG C, continue stirring 20 minutes, obtain nano-cellulose fiber, polyetherimide (PEI) and bisphenol A type epoxy resin E51 blend;
E) steps d) in the blend of gained in vacuum drying oven, vacuumize 20 minutes remove bubble, be cast in afterwards in Teflon mould, afterwards at ambient pressure successively according to 2h at the curing process first stage 80 DEG C, at subordinate phase 120 DEG C 4h and at the phase III 160 DEG C the program of 2h heat-treat, obtain mechanical test batten after being cooled to the room temperature demoulding.
The present embodiment is using polyetheramine as solidifying agent, and polyetherimide prepares matrix material as thermoplastic resin, and the method that describes in preparation method and previous embodiment is basically identical.The composites prepared by this embodiment can reach the object of modified synergic.
Claims (7)
1. the epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic, it is characterized in that: form by epoxy resin, solidifying agent, thermoplastic resin and nano-cellulose are blended, the weight proportion of epoxy resin, solidifying agent, thermoplastic resin and nano-cellulose is 100:27 ~ 33:7 ~ 33.3:0.1 ~ 0.3.
2. a preparation method for the epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic, is characterized in that comprising the following steps:
1) preparation of nano-cellulose/epoxy-resin systems:
1.1) nano-cellulose of 0.1 ~ 0.3 weight part is joined the distilled water of 100 ~ 300 weight parts, sonic oscillation is until the stable suspension liquid of the dispersed formation of nano-cellulose;
1.2) add and step 1.1) in the dehydrated alcohol of distilled water identical weight part carry out centrifugal displacement, through displacement by water removing wherein, obtain the ethanolic soln of nano-cellulose; Again carry out sonic oscillation process 20 minutes, until nano-cellulose evenly spreads in ethanol;
1.3) to step 1.2) add the epoxy resin of 100 weight parts in the solution prepared, carry out magnetic agitation and disperse 6 hours, afterwards temperature adjusting is carried out heat treated 4 hours to 80 DEG C, by ethanol volatilization removing;
2) preparation of nano-cellulose/thermoplastic resin/epoxy resin composite system:
2.1) in step 1.3) in the homodisperse epoxy resin of nano-cellulose that obtains, add the thermoplastic resin of 7 ~ 33.3 weight parts in 120 ~ 150 DEG C of oil baths, carry out mechanical stirring after 2 ~ 4 hours, the solidifying agent of 27 ~ 33 weight parts is added while stirring after being cooled to 60 ~ 110 DEG C, continue stirring 10 ~ 30 minutes, obtain nano-cellulose, thermoplastic resin and epoxy resin blend;
2.2) step 2.1) in the blend of gained in vacuum drying oven, vacuumize 20 ~ 40 minutes remove bubble, be cast in afterwards in Teflon mould, be heating and curing at being 60 ~ 200 DEG C in normal pressure, temperature, the epoxy resin composite material of obtained nano-cellulose and thermoplastic resin modified synergic.
3. the preparation method of the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 2, it is characterized in that: described step 1.3) in heat treated after 4 hours, be placed in 80 DEG C of vacuum drying ovens again to carry out vacuumizing process 4 hours, so that ethanol is removed completely.
4. the preparation method of the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 1 or the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 2, is characterized in that: described epoxy resin is liquid bisphenol A type epoxy resin E51.
5. the preparation method of the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 1 or the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 2, it is characterized in that: described solidifying agent is amine curing agent, be specially 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylmethane or polyetheramine.
6. the preparation method of the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 1 or the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 2, is characterized in that: described thermoplastic resin is polyimide, polyetherimide, polysulfones or polycaprolactone.
7. the preparation method of the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 1 or the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic according to claim 2, it is characterized in that: the mean fibre length of described nano-cellulose is 300-600um, and mean diameter is 50-100nm.
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| CN106009248A (en) * | 2016-05-18 | 2016-10-12 | 浙江农林大学 | Method for manufacturing high-toughness traditional Chinese medicine residue / plastic composite material |
| CN109206850A (en) * | 2018-07-17 | 2019-01-15 | 蚌埠中梁机械科技有限公司 | A kind of preparation method of the resin glasses frame of polyether sulfone-nitrile rubber-fibre reinforced toughening |
| CN110396280A (en) * | 2019-08-29 | 2019-11-01 | 国网河南省电力公司内乡县供电公司 | Fiber reinforced epoxy resin based composites and preparation method thereof |
| CN113603397A (en) * | 2021-08-16 | 2021-11-05 | 长沙新立硅材料科技有限公司 | Modified asphalt mixture and preparation method thereof |
| CN113621246A (en) * | 2021-09-01 | 2021-11-09 | 长沙新立硅材料科技有限公司 | Nano-cellulose, thermoplastic and thermosetting synergistically modified asphalt material and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013052A (en) * | 2012-12-17 | 2013-04-03 | 吉林大学 | Degradable underground blocking material |
| CN103396656A (en) * | 2013-08-27 | 2013-11-20 | 连云港神鹰碳纤维自行车有限责任公司 | Preparation method of epoxy resin system for nanometer modified carbon fiber prepreg |
| CN103467920A (en) * | 2013-09-12 | 2013-12-25 | 北京理工大学 | Method for improving mechanical property and heat resistance property of epoxy resin |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
-
2014
- 2014-11-19 CN CN201410663406.8A patent/CN104371275B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013052A (en) * | 2012-12-17 | 2013-04-03 | 吉林大学 | Degradable underground blocking material |
| CN103396656A (en) * | 2013-08-27 | 2013-11-20 | 连云港神鹰碳纤维自行车有限责任公司 | Preparation method of epoxy resin system for nanometer modified carbon fiber prepreg |
| CN103467920A (en) * | 2013-09-12 | 2013-12-25 | 北京理工大学 | Method for improving mechanical property and heat resistance property of epoxy resin |
| CN103694644A (en) * | 2013-12-30 | 2014-04-02 | 景旺电子科技(龙川)有限公司 | Epoxy resin composition, metal-based copper-clad plate and manufacturing method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106009248A (en) * | 2016-05-18 | 2016-10-12 | 浙江农林大学 | Method for manufacturing high-toughness traditional Chinese medicine residue / plastic composite material |
| CN106009248B (en) * | 2016-05-18 | 2018-05-29 | 浙江农林大学 | A kind of preparation method of Chinese medicine dreg/plastic composite of high tenacity |
| CN109206850A (en) * | 2018-07-17 | 2019-01-15 | 蚌埠中梁机械科技有限公司 | A kind of preparation method of the resin glasses frame of polyether sulfone-nitrile rubber-fibre reinforced toughening |
| CN109206850B (en) * | 2018-07-17 | 2020-11-03 | 蚌埠中梁机械科技有限公司 | Preparation method of polyether sulfone-nitrile rubber-carbon fiber reinforced and toughened resin spectacle frame |
| CN110396280A (en) * | 2019-08-29 | 2019-11-01 | 国网河南省电力公司内乡县供电公司 | Fiber reinforced epoxy resin based composites and preparation method thereof |
| CN110396280B (en) * | 2019-08-29 | 2022-04-05 | 国网河南省电力公司内乡县供电公司 | Fiber-reinforced epoxy resin-based composite material and preparation method thereof |
| CN113603397A (en) * | 2021-08-16 | 2021-11-05 | 长沙新立硅材料科技有限公司 | Modified asphalt mixture and preparation method thereof |
| CN113621246A (en) * | 2021-09-01 | 2021-11-09 | 长沙新立硅材料科技有限公司 | Nano-cellulose, thermoplastic and thermosetting synergistically modified asphalt material and preparation method thereof |
| CN115584186A (en) * | 2022-11-11 | 2023-01-10 | 广州飞思合成材料有限公司 | Water-based epoxy silicon steel sheet self-bonding coating and preparation method thereof |
| CN115584186B (en) * | 2022-11-11 | 2023-09-12 | 广州飞思合成材料有限公司 | Water-based epoxy silicon steel sheet self-adhesive coating and preparation method thereof |
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