CN104371275B - Epoxy resin composite material of nano-cellulose thermoplastic resin modified synergic and preparation method thereof - Google Patents
Epoxy resin composite material of nano-cellulose thermoplastic resin modified synergic and preparation method thereof Download PDFInfo
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- CN104371275B CN104371275B CN201410663406.8A CN201410663406A CN104371275B CN 104371275 B CN104371275 B CN 104371275B CN 201410663406 A CN201410663406 A CN 201410663406A CN 104371275 B CN104371275 B CN 104371275B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 78
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 229920002678 cellulose Polymers 0.000 title claims abstract description 58
- 239000001913 cellulose Substances 0.000 title claims abstract description 56
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 114
- 235000019441 ethanol Nutrition 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000013019 agitation Methods 0.000 claims abstract description 20
- 238000006073 displacement reaction Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000001291 vacuum drying Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000005119 centrifugation Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229920003043 Cellulose fiber Polymers 0.000 claims description 60
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 46
- 229920002492 poly(sulfone) Polymers 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 230000010355 oscillation Effects 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 229920001601 polyetherimide Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 7
- 239000002121 nanofiber Substances 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000007385 chemical modification Methods 0.000 claims description 3
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000012461 cellulose resin Substances 0.000 claims description 2
- 239000000088 plastic resin Substances 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 4
- 150000002148 esters Chemical class 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000005802 health problem Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- -1 Benzene sulfone Chemical class 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of epoxy resin composite material of nano-cellulose thermoplastic resin modified synergic and preparation method thereof.By epoxy resin, curing agent, thermoplastic resin and nano-cellulose with weight proportion 100:27~33:7~33.3:0.1~0.3 blending forms；Nano-cellulose is added into distilled water, ultrasonic disperse is into suspension；Addition absolute ethyl alcohol carries out centrifugation displacement and removes water；Epoxy resin is added, heats after magnetic agitation is scattered and removes ethanol volatilization；Thermoplastic resin oil bath and mechanical agitation are added, cooling adds curing agent, continues stirring and obtain blend；Bubble is removed in vacuum drying oven, is cast in mould, is then heating and curing, the epoxy resin composite material of nano-cellulose and thermoplastic resin modified synergic is made.The nano-cellulose and the common modified epoxy of thermoplastic resin of present invention selection environment-friendly and green, improve interfacial adhesion, realize the collaboration activeness and quietness to epoxy resin.
Description
Technical field
The invention belongs to a kind of composite of polymer matrix composites technical field and preparation method thereof, is specifically one kind
Epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic and preparation method thereof.
Background technology
Epoxy resin is due to cure shrinkage is low, cohesive force is strong, product mechanical property height, chemical resistance after solidification
Good, the advantages that electrical insulation capability is good, there is irreplaceable status, extensive use in fibre-reinforced polymer matrix composites
In fields such as space flight, aviation, automobile, buildings.However, because epoxy resin can produce highly cross-linked in the curing process, cause
Solidfied material has the defects of matter is crisp, impact resistance is poor, limits its application in engineering.This is required must be to asphalt mixtures modified by epoxy resin
Fat is modified.
By introducing the second phase material into epoxy resin, certain microscopical structure is formed, increases energy dissipation, is important
Toughness reinforcing approach.Wherein, the modification of thermoplastic resin (such as polysulfones, polyether sulfone, polyimides) to epoxy resin receives much concern.So
And often shown after modified system curing reaction prepared by this method and compare clearly phase structure interface, show boundary knot
It is not strong with joint efforts, so as to which toughening effect is inherently by a certain degree of influence.With the development of nanometer technology, it has been found that simultaneously
It is the further effective ways for improving epoxy resin combination property that epoxy resin, which is modified, using two kinds of modifying agent.By difference
The Nano filling (such as CNT, titanium dioxide) of form is incorporated into thermoplastic resin modified epoxy-resin systems, is reached
Cooperate with the effect of activeness and quietness.
In recent years, nano-cellulose is due to former with high intensity, high-modulus, high-specific surface area, biodegradable and preparation
The advantages that material is abundant, is paid close attention to by more and more researchers, is widely used in strengthening composite, biological medicine material etc.
Field.CNT etc. is replaced to comply with the requirement of environmental protection to a certain extent, reduce come reinforced epoxy using nano-cellulose
Environmental pollution, meanwhile, also avoid the safety and health problem that may be induced using inorganic nano-filler.At present, nanometer is utilized
Though the research that cellulose is modified to simple epoxy-resin systems has been carried out but still at an early stage, nano-cellulose hardly possible be present
With the scattered and unconspicuous problem of modified effect.However, with nano-cellulose and the common modified epoxy of thermoplastic resin
Research has not been reported.
The content of the invention
In order to solve problem present in background technology, the invention provides a kind of nano-cellulose-thermoplastic resin association
With modified epoxy resin composite material and preparation method thereof, it is therefore an objective to the high length-diameter ratio nano-cellulose of excellent in mechanical performance
Collaboration activeness and quietness is carried out to epoxy resin with thermoplastic resin.
The technical solution adopted by the present invention is：
First, the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic：
It is made up of the blending of epoxy resin, curing agent, thermoplastic resin and nano-cellulose, epoxy resin, curing agent, thermoplastic
Property resin and nano-cellulose weight proportion be 100:27~33:7~33.3:0.1~0.3.
2nd, the preparation method of the epoxy resin composite material of a kind of nano-cellulose-thermoplastic resin modified synergic, including
Following steps：
1) preparation of nano-cellulose/epoxy-resin systems：
1.1) nano-cellulose of 0.1~0.3 parts by weight is added to the distilled water of 100~300 parts by weight, sonic oscillation
Stable suspension is formed until nano-cellulose is dispersed；
1.2) added in the nano-cellulose aqueous solution prepared to step 1.1) and distilled water identical weight in step 1.1)
The absolute ethyl alcohol of part carries out centrifugation displacement, removes water therein by displacement, obtains the ethanol solution of nano-cellulose；Again
Carry out sonic oscillation to handle 20 minutes, until nano-cellulose is evenly spread in ethanol；
1.3) epoxy resin of 100 parts by weight is added in the solution prepared to step 1.2), it is small to carry out magnetic agitation scattered 6
When, afterwards temperature adjusting to 80 DEG C heat 4 hours, ethanol is volatilized and removed；
2) preparation of nano-cellulose/thermoplastic resin/epoxy resin composite system：
2.1) in the dispersed epoxy resin of the nano-cellulose that step 1.3) obtains, 7~33.3 parts by weight are added
Thermoplastic resin in 120~150 DEG C of oil baths, carry out mechanical agitation after 2~4 hours, be cooled to 60~110 DEG C of back stirrings
Side adds the curing agent of 27~33 parts by weight, continues stirring 10~30 minutes, obtains nano-cellulose, thermoplastic resin and epoxy
Resin blend；
2.2) blend of gained vacuumizes 20~40 minutes removing bubbles in vacuum drying oven in step 2.1), pours afterwards
Note in Teflon mould, be heating and curing at being 60~200 DEG C in normal pressure, temperature, nano-cellulose and heat is made
The epoxy resin composite material of plastic resin modified synergic.
Described step 1.3) heat 4 hours after, then be placed in 80 DEG C of vacuum drying ovens carry out vacuumize process 4 it is small
When, ethanol is removed completely.
Described epoxy resin is liquid bisphenol A type epoxy resin E51, and epoxide equivalent is 185~200g/eq.
Described curing agent is amine curing agent, specially 4,4 '-diaminodiphenylsulfone (DDS), 3,3 '-diaminourea two
Benzene sulfone, 4,4 '-MDA (DDM) or polyetheramine (D230), prioritizing selection 4,4 '-diaminodiphenylsulfone (DDS).
The thermoplastic resin is polyimides (PI), PEI (PEI), polysulfones (PSF) or polycaprolactone
(PCL), prioritizing selection polysulfones.
Described nano-cellulose is averaged using the high aspect fibers element nanofiber for being easy to run through and tangling, its fiber
Length is 300-600um, average diameter 50-100nm.
It is contemplated that by regulate and control in phase separation nano-cellulose mutually running through between different phase regions and its
Mutual entanglement with thermoplastic resin acts on, and improves interfacial adhesion, and then improve Material reinforcement toughening effect.
The present invention is from excellent in mechanical performance, green and abundance high length-diameter ratio nano-cellulose, by molten
The method that agent exchange and melt blending are combined is dispersed in epoxy resin-base, high length-diameter ratio nanometer in phase separation
Cellulose, thermoplastic resin macromolecular chain easily tangle.By nano-cellulose running through between different phase regions and with
Entanglement between thermoplastic resin macromolecular chain, improve interfacial adhesion.Meanwhile nano-cellulose can regulate and control domain size
Size.The raising of phase interface bonding strength and the regulation and control of domain size, are advantageous to the raising of material mechanical performance.
The epoxy resin composite material mechanical property of the modified synergic of gained of the invention purer epoxy-resin systems or list
Pure nano-cellulose or thermoplastic resin modified epoxy resin composite system increase.
The present invention has the advantages that：
1. the present invention replaces CNT etc. to comply with environmental requirement, reduction come reinforced epoxy using nano-cellulose
Environmental pollution, meanwhile, also avoid the safety and health problem that may be induced using inorganic nano-filler.
2. its nano-cellulose does not carry out any chemical modification, so as to prevent the reduction of nano-cellulose mechanical property.
3. the control of nanofiber cellulose content makes it as equal as possible than relatively low scope, and by the method for exchange of solvent
It is even scattered, avoid reuniting because nanofiber cellulose content is high and causing composite materials property to reduce.
4. using high length-diameter ratio nano-cellulose fiber and thermoplastic resin modified synergic, pass through nano-cellulose difference phase
Section runs through and its mutual entanglement with thermoplastic resin macromolecular chain, improves interfacial adhesion, and then improve material property.
Brief description of the drawings
Fig. 1 is the SEM figures for the composite section that the embodiment of the present invention 1 is prepared.
Fig. 2 is to scheme with the SEM of the epoxy resin composite material section of the polysulfones modification in proportion of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment is described in further detail to the present invention.
Embodiments of the invention are as follows：
As a result of repeated studies by the present inventors, and by the checking of lot of experiments, obtain preparing nano-cellulose/thermoplastic resin
The optimised process of fat/epoxy resin composite material.The present invention is illustrated with reference to several representational embodiments
Performance, but subordinate's embodiment is not construed as limiting the invention.
Embodiment 1
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.1g nano-cellulose fiber is added in the beaker equipped with 100ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 100g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；80 DEG C of vacuum are placed in again to dry
Vacuumize process 4 hours again in case, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 14.1g polysulfones and after 140 DEG C of oil baths carry out mechanical agitation 3 hours, it is cooled to after 110 DEG C and adds while stirring
Enter 27g DDS, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 and be total to
Mixed thing；
E) blend of gained vacuumizes 30 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 6h at 160 DEG C of curing process first stage, 2h at 180 DEG C of second stage
It is heat-treated with the program of 2h at 200 DEG C of phase III, mechanical test batten is obtained after being cooled to the room temperature demoulding.
Composite tensile strength prepared by the present embodiment is 83MPa, tensile modulus of elasticity 2.8GPa, impact strength
For 24KJ/m2；The tensile strength of pure liquid bisphenol A type epoxy resin E51 matrixes is 81MPa, and tensile modulus of elasticity is
2.6GPa, impact strength 18KJ/m2；The tensile strength for the epoxy resin composite material that polysulfones in proportion is modified is 74MPa,
Tensile modulus of elasticity is 2.7GPa, impact strength 20KJ/m2.As can be seen here, nano-cellulose and thermoplastic resin polysulfones are total to
The effect of collaboration activeness and quietness can be played with modified epoxy.
Contrast, the composite prepared in the embodiment of the present invention and polysulfones in proportion are schemed from Fig. 1 and Fig. 2 SEM
Modified epoxy-resin systems have been respectively formed appearance structure of the polysulfones even particulate dispersion in epoxy resin-base, nanofiber
Element does not occur obvious agglomeration, and the addition of nano-cellulose substantially makes interfacial adhesion improve, therefore prepares compound
Material mechanical performance significantly improves, and has significant technique effect.
Embodiment 2
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.2g nano-cellulose fiber is added in the beaker equipped with 200ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 200g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；It is placed in 80 DEG C of vacuum drying ovens
In vacuumize process 4 hours again, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 14.1g polysulfones and after 140 DEG C of oil baths carry out mechanical agitation 3 hours, it is cooled to after 110 DEG C and adds while stirring
Enter 27g DDS, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 and be total to
Mixed thing；
E) blend of gained vacuumizes 30 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 6h at 160 DEG C of curing process first stage, 2h at 180 DEG C of second stage
It is heat-treated with the program of 2h at 200 DEG C of phase III, mechanical test batten is obtained after being cooled to the room temperature demoulding.
Composite tensile strength prepared by the present embodiment is 85MPa, tensile modulus of elasticity 2.8GPa, impact strength
For 31KJ/m2, show that composite materials property continues to increase with nanofiber cellulose content increase.Nano-cellulose and thermoplasticity
The common modified epoxy of resin polysulfones can play the effect of collaboration activeness and quietness.
Embodiment 3
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.3g nano-cellulose fiber is added in the beaker equipped with 300ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 300g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；It is placed in 80 DEG C of vacuum drying ovens
In vacuumize process 4 hours again, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 14.1g polysulfones and after 140 DEG C of oil baths carry out mechanical agitation 3 hours, it is cooled to after 110 DEG C and adds while stirring
Enter 27g DDS, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 and be total to
Mixed thing；
E) blend of gained vacuumizes 30 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 6h at 160 DEG C of curing process first stage, 2h at 180 DEG C of second stage
It is heat-treated with the program of 2h at 200 DEG C of phase III, mechanical test batten is obtained after being cooled to the room temperature demoulding.
Composite tensile strength prepared by the present embodiment is 86MPa, tensile modulus of elasticity 2.8GPa, impact strength
For 26KJ/m2, show that nano-cellulose and the common modified epoxy of thermoplastic resin polysulfones can play collaboration activeness and quietness
Effect.
Embodiment 4
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.1g nano-cellulose fiber is added in the beaker equipped with 100ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 100g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；It is placed in 80 DEG C of vacuum drying ovens
In vacuumize process 4 hours again, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 17.3g polysulfones and after 140 DEG C of oil baths carry out mechanical agitation 3 hours, it is cooled to after 110 DEG C and adds while stirring
Enter 27g DDS, continue stirring 30 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 and be total to
Mixed thing；
E) blend of gained vacuumizes 30 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 6h at 160 DEG C of curing process first stage, 2h at 180 DEG C of second stage
It is heat-treated with the program of 2h at 200 DEG C of phase III, mechanical test batten is obtained after being cooled to the room temperature demoulding.
Composite tensile strength prepared by the present embodiment is 76MPa, tensile modulus of elasticity 2.8GPa, impact strength
For 25KJ/m2；The epoxy resin composite material tensile strength that polysulfones is modified in proportion is 66MPa, and tensile modulus of elasticity is
2.8GPa, impact strength 17KJ/m2.As can be seen here, nano-cellulose and the common modified epoxy of thermoplastic resin polysulfones
The effect of collaboration activeness and quietness can be played.
Embodiment 5
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.3g nano-cellulose fiber is added in the beaker equipped with 300ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 300g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；It is placed in 80 DEG C of vacuum drying ovens
In vacuumize process 4 hours again, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 33.3g polycaprolactones and after 120 DEG C of oil baths carry out mechanical agitation 2 hours, it is cooled to 110 DEG C of back stirrings
Side adds 33g DDS, continues stirring 30 minutes, obtains nano-cellulose fiber, polycaprolactone (PCL) and bisphenol type epoxy tree
Fat E51 blends；
E) blend of gained vacuumizes 40 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 6h at 160 DEG C of curing process first stage, 2h at 180 DEG C of second stage
Program be heat-treated, be cooled to room temperature the demoulding after obtain mechanical test batten.
Composite tensile strength prepared by the present embodiment is 34MPa, tensile modulus of elasticity 1.7GPa, impact strength
For 26KJ/m2；Epoxy resin composite material tensile strength Polycaprolactone modified in proportion is 33MPa, and tensile modulus of elasticity is
1.7GPa, impact strength 14KJ/m2.As can be seen here, nano-cellulose and the common modified epoxy of thermoplastic resin polycaprolactone
Resin can play the effect of coordination plasticizing.
Embodiment 6
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.1g nano-cellulose fiber is added in the beaker equipped with 100ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 100g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；It is placed in 80 DEG C of vacuum drying ovens
In vacuumize process 4 hours again, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 14.1g polysulfones and after 140 DEG C of oil baths carry out mechanical agitation 3 hours, added while stirring after being cooled to 80 DEG C
27g DDM, continue stirring 10 minutes, obtain nano-cellulose fiber, polysulfones (PSF) and bisphenol A type epoxy resin E51 blendings
Thing；
E) blend of gained vacuumizes 20 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 2h at 100 DEG C of curing process first stage, 6h at 160 DEG C of second stage
It is heat-treated with the program of 2h at 180 DEG C of phase III, mechanical test batten is obtained after being cooled to the room temperature demoulding.
For the present embodiment compared with the embodiment described above 1, preparation method is identical, and difference is curing agent species difference.It is logical
The purpose of modified synergic can be reached by crossing the composites of embodiment preparation.
Embodiment 7
Raw material and dosage are：
The average length of above-mentioned high length-diameter ratio nano-cellulose fiber is 300-600um, average diameter 50-100nm.
A) 0.1g nano-cellulose fiber is added in the beaker equipped with 100ml distilled water, sonic oscillation 20 minutes
Stable suspension is formed until nano-cellulose fiber is dispersed；
B) 100g absolute ethyl alcohols are added in the nano-cellulose fiber aqueous solution prepared to step a) and carries out centrifugation displacement, passed through
Cross 5 displacements to remove water therein, obtain the ethanol solution of nano-cellulose fiber；Sonic oscillation is carried out again handles 20 points
Clock, until nano-cellulose fiber is evenly spread in ethanol；
C) 100g liquid bisphenol A type epoxy resin E51 are added in the solution prepared to step b), carry out magnetic agitation point
Dissipate 6 hours, to 80 DEG C heat 4 hours by temperature adjusting afterwards, ethanol is volatilized and removed；It is placed in 80 DEG C of vacuum drying ovens
In vacuumize process 4 hours again, further remove ethanol；
D) the dispersed bisphenol A type epoxy resin E51 of the nano-cellulose fiber that obtains in step c) is transferred to flask
In, wherein adding 7g PEIs and after 150 DEG C of oil baths carry out mechanical agitation 3 hours, it is cooled to after 60 DEG C while stirring
31g D230 is added, continues stirring 20 minutes, obtains nano-cellulose fiber, PEI (PEI) and bisphenol type epoxy
Resin E51 blends；
E) blend of gained vacuumizes 20 minutes removing bubbles in vacuum drying oven in step d), is cast in poly- four afterwards
In PVF mould, afterwards at ambient pressure successively according to 2h at 80 DEG C of curing process first stage, at 120 DEG C of second stage 4h and
2h program is heat-treated at 160 DEG C of phase III, and mechanical test batten is obtained after being cooled to the room temperature demoulding.
For the present embodiment using polyetheramine as curing agent, PEI prepares composite as thermoplastic resin, prepares
Method is basically identical with describing method in previous embodiment.The composites prepared by the embodiment can reach collaboration
Modified purpose.
Claims (5)
1. a kind of epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic, it is characterized in that：By asphalt mixtures modified by epoxy resin
Fat, curing agent, thermoplastic resin and nano-cellulose blending composition, epoxy resin, curing agent, thermoplastic resin and nanofiber
The weight proportion of element is 100:27~33:7~33.3:0.1~0.3, described nano-cellulose is the nanometer of non-chemical modification
Cellulose fibre, the thermoplastic resin are polyimides, PEI, polysulfones or polycaprolactone；Pass through nano-cellulose
Fiber running through between different phase regions and the entanglement between thermoplastic resin macromolecular chain, improve interfacial adhesion；
The average fiber length of described nano-cellulose is 300-600um, average diameter 50-100nm.
2. a kind of preparation method of the epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic, its feature exist
In comprising the following steps：
1）The preparation of nano-cellulose/epoxy-resin systems：
1.1）The nano-cellulose of 0.1~0.3 parts by weight is added to the distilled water of 100~300 parts by weight, described Nanowire
Dimension element is the nano-cellulose fiber of non-chemical modification, and the average fiber length of described nano-cellulose is 300-600um, is put down
A diameter of 50-100nm, sonic oscillation form stable suspension until nano-cellulose is dispersed；
1.2）Add and step 1.1）The absolute ethyl alcohol of middle distilled water identical weight part carries out centrifugation displacement, will wherein by displacement
Water remove, obtain the ethanol solution of nano-cellulose；Carry out sonic oscillation again to handle 20 minutes, until nano-cellulose is equal
It is even to be distributed in ethanol；
1.3）To step 1.2）The epoxy resin of 100 parts by weight is added in the solution of preparation, magnetic agitation is carried out and disperses 6 hours,
Afterwards temperature adjusting to 80 DEG C heat 4 hours, ethanol is volatilized and removed；
2）The preparation of nano-cellulose/thermoplastic resin/epoxy resin composite system：
2.1）In step 1.3）In the dispersed epoxy resin of obtained nano-cellulose, the heat of 7~33.3 parts by weight is added
In 120~150 DEG C of oil baths, the thermoplastic resin is polyimides, PEI, polysulfones or gathered in oneself plastic resin
Ester, mechanical agitation is carried out after 2~4 hours, is cooled to the curing agent for adding 27~33 parts by weight after 60~110 DEG C while stirring,
Continue stirring 10~30 minutes, obtain nano-cellulose, thermoplastic resin and epoxy resin blend；
2.2）Step 2.1）The blend of middle gained vacuumizes 20~40 minutes removing bubbles in vacuum drying oven, is cast in afterwards
In Teflon mould, it is heating and curing at being 60~200 DEG C in normal pressure, temperature, nano-cellulose and thermoplasticity is made
The epoxy resin composite material of resin modified synergic.
A kind of 3. epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic according to claim 2
Preparation method, it is characterised in that：Described step 1.3）After heating 4 hours, then it is placed in 80 DEG C of vacuum drying ovens
Row vacuumize process 4 hours, ethanol is removed completely.
A kind of 4. epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic according to claim 1
A kind of or preparation of the epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic described in claim 2
Method, it is characterised in that：Described epoxy resin is liquid bisphenol A type epoxy resin E51.
A kind of 5. epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic according to claim 1
A kind of or preparation of the epoxy resin composite material of nano-cellulose-thermoplastic resin modified synergic described in claim 2
Method, it is characterised in that：Described curing agent is amine curing agent, specially 4,4 '-diaminodiphenylsulfone, 3,3 '-diamino
Base diphenyl sulphone (DPS), 4,4 '-MDA or polyetheramine.
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| CN113603397B (en) * | 2021-08-16 | 2022-10-18 | 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 |
| 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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