CN107096869A - A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand - Google Patents
A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand Download PDFInfo
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- CN107096869A CN107096869A CN201710480481.4A CN201710480481A CN107096869A CN 107096869 A CN107096869 A CN 107096869A CN 201710480481 A CN201710480481 A CN 201710480481A CN 107096869 A CN107096869 A CN 107096869A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
- B22C1/02—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by additives for special purposes, e.g. indicators, breakdown additives
Abstract
The invention discloses a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, comprise the following steps：（1）According to mass ratio 80 100:2‑4:1‑3:0.5‑1:0.3‑0.6:0.01 0.02 weigh matrix sand material, conductive polycrystalline mullite fiber, modified epoxy, polyamide, diluent and silane coupler；（2）Modified epoxy is mixed with diluent, 3 6min are stirred under 300 600r/min rotating speed, the modified epoxy of dilution is produced；（3）Conductive polycrystalline mullite fiber, matrix sand material, silane coupler are added in puddle mixer, 3 4min of stirring mixing under 800 1200r/min rotating speed, then the modified epoxy of dilution is added, 2 3min of stirring mixing under 500 1000r/min rotating speed, it is eventually adding polyamide, 1 2min of stirring mixing, shakes out under 400 700r/min rotating speed.Resin sand produced by the present invention has high-temperature bending strength high, and the up time is long, and collapsibility is good, and antistatic property is excellent, the advantages of good corrosion resistance.
Description
Technical field
The present invention relates to a kind of preparation method of resin casting, and in particular to a kind of conductive polycrystalline mullite fiber increases
The preparation method of strong epoxy resin sand.
Background technology
It is a new technology developed in recent years with resin sand coremaking, moulding.Resin sand and common clay sand, water glass
Glass sand facies ratio has many advantages, and can create more preferable economic benefit and social benefit, can both improve casting matter
Amount, can reduce production cost, the advantage of resin sand is as follows again：（1）Improve casting quality：A, dimensional accuracy are improved, wheel is cleaned up
It is clear；B, surface quality of continuous castings are improved；C, the consistency of casting are improved；（2）Capital construction investment is few, and production cost is relatively low.
The appearance of various organic binder bonds, has effectively promoted resin sand in moulding and the application of core manufacturing craft, wherein with furan
Furane resins sand it is with the fastest developing speed.Now the furan resin-sand that largely uses because its intensity for furfuryl alcohol addition it is excessive according to
Rely, it is difficult to cost is reduced, and the up time is too short, only 5 ~ 10 min, seriously restricts its application in heavy castings.
Epoxy resin refers to that molecular structure contains two or more epoxide groups, organic with aliphatic or aromatic series etc.
Compound is skeleton, and can react the one of the thermoset products being formed with by epoxide group and a variety of polyamides
Family macromolecule oligomer.It has the premium properties such as adhesive property good, shrinkage factor is low, good processability, mechanical property height.At present also
The rare report that epoxy resin is applied to casting resin sand as binding agent, not seen in casting antistatic epoxide resin sand
Report.
The content of the invention
It is an object of the invention to provide a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, sheet
The obtained resin sand of invention has high-temperature bending strength high, and the up time is long, and collapsibility is good, and antistatic property is excellent, corrosion resistant
The advantages of corrosion is good.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, comprises the following steps：
（1）According to mass ratio 80-100:2-4:1-3:0.5-1:0.3-0.6:0.01-0.02 weighs matrix sand material, conductive polycrystalline
Mullite fiber, modified epoxy, curing agent, diluent and silane coupler；
（2）Modified epoxy is mixed with diluent, 3-6min is stirred under 300-600r/min rotating speed, produces dilution
Modified epoxy；
（3）Conductive polycrystalline mullite fiber, matrix sand material, silane coupler are added in puddle mixer, 800-1200r/min's
Stirring mixing 3-4min, then adds the modified epoxy of dilution under rotating speed, stirs mixed under 500-1000r/min rotating speed
2-3min is closed, curing agent is eventually adding, stirring mixing 1-2min, shakes out under 400-700r/min rotating speed.
Described matrix sand material is selected from quartz sand, zircon sand, magnesite clinker, chromite sand, forsterite sand, aquamaine stone sand, stone
One kind in grey stone sand, graphite sand, nice foundry sand, Task-size Controlling is at 10-20 μm.
The preparation method of the conductive polycrystalline mullite fiber is as follows：
（1）According to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into the mixed solution that ethanol and acetone are constituted in equal volume by 70-90
Soaking and washing 1-2h, takes out after drying according still further to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into strong oxidizing solution by 80-100
In, heating water bath is to 70-90 DEG C, the stirring reaction 3-5h under 2000-4000r/min rotating speed, then in 300-500W power
Under ultrasonically treated 1-3h, suction filtration, filter residue is washed with distilled water to neutrality, and 8-14h is dried at 80-90 DEG C, hydroxylating is produced many
Brilliant mullite fiber；
（2）According to solid-to-liquid ratio 1:50-60 adds hydroxylating polycrystalline mullite fibre in distilled water, 1500-3000r/min's
Dispersed with stirring 1-2h under rotating speed, then adds the epoxychloropropane equivalent to polycrystalline mullite fibre quality 15-20%, in 1000-
Dispersed with stirring 0.5-1.5h under 2000r/min rotating speed, sequentially adds dimethylamine and triethylene tetramine, dimethylamine and epoxy chlorine
The mol ratio of propane is 1:1-1.5, the quality of triethylene tetramine is epoxychloropropane and the 1-3% of dimethylamine gross mass, and water-bath adds
Heat is to 60-70 DEG C, the stirring reaction 5-8h under 500-1000r/min rotating speed, then the microwave treatment under 200-400W power
1-3h, suction filtration, filter residue is washed with distilled water to filtrate not chloride ion-containing, and 12-24h is dried at 60-70 DEG C, then in 110-120
1-2h is activated at DEG C, poly-epoxychloropropane dimethylamine cation is produced and is modified polycrystalline mullite fibre；
（3）Add graphene oxide into ultrasonic agitation in distilled water and the graphene oxide dispersion that mass fraction is 1-2% is made；
Again with pH=3-4 of the mass fraction for 15% hydrochloric acid solution regulation graphene oxide dispersion；Then according to mass ratio 1:40-50
Poly-epoxychloropropane dimethylamine cation is modified into polycrystalline mullite fibre to add in the graphene oxide dispersion after regulation pH,
30-40min is stood, is during which lifted 2-3 times, 2-3h is then irradiated under ultraviolet lamp, irradiation intensity is 80-100 μ W/cm2, take
Neutrality is washed with distilled water to after going out, 12-24h is dried at 60-70 DEG C, graphene coated polycrystalline mullite fibre is produced and is combined
Conductive material.
The preparation method of the modified epoxy is as follows：
（1）According to mol ratio 1：1.5-2：0.0008-0.0014：0.0002-0.0004 by 2,5- furandicarboxylic acids, ethylene glycol,
Butyl titanate and trimethyl phosphate mixing, slow heating, and be stirred continuously, while being passed through nitrogen at ambient pressure as protection gas
Body, esterification temperature control is at 170-210 DEG C, and reaction system is gradually transparent by muddiness steering, represents that esterification is anti-when reaching articulation point
It should terminate；Then esterification products are continued to heat up, and be stirred continuously, reacted at a temperature of 60-80Pa vacuums and 220-240 DEG C
4-7h, produces polycondensation product, and polycondensation product finally is dissolved in into tetrachloroethanes, precipitated in methyl alcohol, supernatant is removed after centrifugation,
So 2-4 times repeatedly, then 24-48h is dried in vacuo at 120-140 DEG C, produce poly- FDCA glycol ester；
（2）According to mass ratio 4-5:0.8-1.4:0.25-0.3:1.7-2.2 is by poly- 2,5- furandicarboxylic acids glycol ester, propylene
Acid, ferrous sulfate heptahydrate and water are well mixed, stand and lead to nitrogen 20-30min after 10-15h, are subsequently placed in60Co gamma-radiations are radiated
Irradiated in source radiation, radiation dose rate is 1-1.5kGy/h, irradiation total absorbed dose is 20-25kGy；Irradiation terminates
Afterwards, washed 3-4 times with hot distilled water, constant weight is dried under vacuum at 60-70 DEG C, produce acrylic acid-grafted poly- 2,5- furans diformazan
Sour glycol ester；
（3）According to mass ratio 3-7:Epoxychloropropane, acrylic acid-grafted poly- 2,5- furandicarboxylic acids glycol ester are mixed equal by 1
It is even, lead to nitrogen as protective gas, heating water bath adds the tetramethyl equivalent to epoxychloropropane quality 1-2% to 90-100 DEG C
Then base ammonium bromide, constant temperature stirring reaction 2-4h is cooled to 75-85 DEG C, adds mass fraction water-soluble for 45% sodium hydroxide
Liquid so that the quality of sodium hydroxide is the 3-6% of epoxychloropropane, continues constant temperature stirring reaction 1-3h, while normal pressure azeotropic is sloughed
Part moisture content in system, filters out the solid salt of system, then vacuum distillation is removed at 0.1-0.2MPa, 110-120 DEG C
The resin of remaining aqueous phase and synthesis is removed, is then dissolved with toluene, then is washed with deionized 3-4 times, except sub-cloud aqueous phase, then
With pH test paper come the acid-base property in test solution, and the dibastic sodium phosphate aqueous solution regulation system for being 10% with mass fraction is neutral
Solution, then be washed with deionized 3-4 times and remove aqueous phase, finally distillation removes toluene and water, produces required poly- 2,5- furans
Mutter naphthalate modified epoxy.
The curing agent is polyamide, and its amine value is 200 ± 20, and relative molecular mass is 600-1100.
The diluent in acetone, ethyl acetate, dimethylbenzene, styrene, dimethylformamide, phenmethylol one
Kind.
The silane coupler be selected from gamma-aminopropyl-triethoxy-silane, γ-（2,3- glycidoxies）Propyl group trimethoxy
One kind in base silane.
Beneficial effects of the present invention：
The present invention is modified using poly- FDCA glycol ester to epoxy resin, and furan nucleus is introduced into epoxy resin
In, the heat-resisting quantity and flame resistance of epoxy resin can be improved；It is fine that the present invention is also modified polycrystalline mullite using graphene coated
Dimension, in polycrystalline mullite fibre Surface coating graphene so that polycrystalline mullite fibre has excellent antistatic property.This hair
It is bright by poly- 2,5- furandicarboxylic acids glycol ester be modified epoxy resin, graphene coated be modified polycrystalline mullite fibre with
The raw materials such as matrix sand material, polyamide, diluent, silane coupler cooperate obtained epoxy resin sand with higher
Combination property, compared with furan resin-sand, with higher high-temperature bending strength and longer up time, also with anti-quiet
Excellent electrical property, good corrosion resistance, strong applicability, collapsibility is good, it is easy to clear up, core cavity any surface finish, and dimensional accuracy is high
The advantages of.
Embodiment
Embodiment 1
A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, comprises the following steps：
（1）According to mass ratio 80:2:1:0.5:0.3:0.01 weighs aquamaine stone sand, conductive polycrystalline mullite fiber, modified epoxy
Resin, polyamide, acetone and gamma-aminopropyl-triethoxy-silane；
（2）Modified epoxy is mixed with acetone, 6min is stirred under 300r/min rotating speed, the modified epoxy of dilution is produced
Resin；
（3）Conductive polycrystalline mullite fiber, aquamaine stone sand, gamma-aminopropyl-triethoxy-silane are added in puddle mixer,
Stirring mixing 4min, then adds the modified epoxy of dilution, is stirred under 500r/min rotating speed under 800r/min rotating speed
Mixing 3min is mixed, polyamide is eventually adding, stirring mixing 1min, shakes out under 400r/min rotating speed.
The kyanite fineness of sand is 10 μm.
The preparation method of the conductive polycrystalline mullite fiber is as follows：
（1）According to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into immersion in the mixed solution that ethanol and acetone are constituted in equal volume by 70
1h is cleaned, is taken out after drying according still further to solid-to-liquid ratio 1:80 are put into polycrystalline mullite fibre in strong oxidizing solution, heating water bath
To 70 DEG C, the stirring reaction 5h under 2000r/min rotating speed, then the ultrasonically treated 3h under 300W power, suction filtration, filter residue steaming
Distilled water is washed to neutrality, and 14h is dried at 80 DEG C, hydroxylating polycrystalline mullite fibre is produced；
（2）According to solid-to-liquid ratio 1:50 add hydroxylating polycrystalline mullite fibre in distilled water, are stirred under 1500r/min rotating speed
Scattered 2h is mixed, the epoxychloropropane equivalent to polycrystalline mullite fibre quality 15% is then added, under 1000r/min rotating speed
Dispersed with stirring 1.5h, sequentially adds dimethylamine and triethylene tetramine, and the mol ratio of dimethylamine and epoxychloropropane is 1:1, three
The quality of ethene tetramine is the 1% of epoxychloropropane and dimethylamine gross mass, and heating water bath is to 60 DEG C, in 500r/min rotating speed
Lower stirring reaction 8h, then the microwave treatment 3h under 200W power, suction filtration, filter residue be washed with distilled water to filtrate it is not chloride from
Son, dries 24h at 60 DEG C, then activates 2h at 110 DEG C, produces poly-epoxychloropropane dimethylamine cation modification polycrystalline and does not come
Mineral wool；
（3）Add graphene oxide into ultrasonic agitation in distilled water and the graphene oxide dispersion that mass fraction is 1% is made；Again
With pH=3 of the mass fraction for 15% hydrochloric acid solution regulation graphene oxide dispersion；Then according to mass ratio 1:40 by polycyclic
Oxygen chloropropane dimethylamine cation is modified polycrystalline mullite fibre and added in the graphene oxide dispersion after regulation pH, stands
30min, is during which lifted 2 times, and 3h is then irradiated under ultraviolet lamp, and irradiation intensity is 80 μ W/cm2, with distillation washing after taking-up
Wash to neutrality, 24h is dried at 60 DEG C, graphene coated polycrystalline mullite fibre composite conducting material is produced.
The preparation method of the modified epoxy is as follows：
（1）According to mol ratio 1：1.5：0.0008：0.0002 by 2,5- furandicarboxylic acids, ethylene glycol, butyl titanate and phosphoric acid
Trimethyl is mixed, slow heating, and is stirred continuously, while being passed through nitrogen at ambient pressure as protective gas, esterification temperature control
At 170-210 DEG C, reaction system is gradually transparent by muddiness steering, represents that esterification terminates when reaching articulation point；Then by ester
Change product to continue to heat up, and be stirred continuously, react 7h at a temperature of 80Pa vacuums and 220 DEG C, produce polycondensation product, finally will
Polycondensation product is dissolved in tetrachloroethanes, precipitates in methyl alcohol, and supernatant is removed after centrifugation, so repeatedly 2 times, then at 120 DEG C
48h is dried in vacuo, poly- FDCA glycol ester is produced；
（2）According to mass ratio 4:0.8:0.25:1.7 by poly- 2,5- furandicarboxylic acids glycol ester, acrylic acid, ferrous sulfate heptahydrate
It is well mixed with water, stand and lead to nitrogen 20min after 10h, be subsequently placed in60Irradiated in Co gamma-radiation radiation source radiation fields, spoke
It is 1kGy/h according to close rate, irradiation total absorbed dose is 20kGy；After irradiation terminates, washed with hot distilled water 3 times, at 60 DEG C
Constant weight is dried under vacuum to, acrylic acid-grafted poly- FDCA glycol ester is produced；
（3）According to mass ratio 3:1 is well mixed epoxychloropropane, acrylic acid-grafted poly- FDCA glycol ester,
Logical nitrogen is as protective gas, and heating water bath adds the 4 bromide equivalent to epoxychloropropane quality 1% to 90 DEG C,
Constant temperature stirring reaction 4h, is then cooled to 75 DEG C, adds the sodium hydrate aqueous solution that mass fraction is 45% so that sodium hydroxide
Quality be epoxychloropropane 3%, continue constant temperature stirring reaction 3h, while normal pressure azeotropic sloughs the part moisture content in system, mistake
The solid salt of system is filtered out, then vacuum distillation removes the resin of remaining aqueous phase and synthesis at 0.2MPa, 110 DEG C, so
Dissolved, then be washed with deionized 3 times with toluene afterwards, except sub-cloud aqueous phase, then with pH test paper come the acid-base property in test solution,
And the dibastic sodium phosphate aqueous solution regulation system for mass fraction being 10% is neutral solution, then it is washed with deionized 3 times and removes
Aqueous phase, finally distillation removes toluene and water, produces required poly- FDCA glycol ester modified epoxy.
The amine value of the polyamide is 280, and relative molecular mass is 600.
Embodiment 2
A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, comprises the following steps：
（1）According to mass ratio 90:3:2:0.8:0.4:0.015 weighs chromite sand, conductive polycrystalline mullite fiber, modified epoxy
Resin, polyamide, ethyl acetate and γ-（2,3- glycidoxies）Propyl trimethoxy silicane；
（2）Modified epoxy is mixed with ethyl acetate, 3-6min is stirred under 300-600r/min rotating speed, dilution is produced
Modified epoxy；
（3）By conductive polycrystalline mullite fiber, chromite sand, γ-（2,3- glycidoxies）Propyl trimethoxy silicane is added
In puddle mixer, stirring mixing 3-4min, then adds the modified epoxy of dilution under 800-1200r/min rotating speed,
Stirring mixing 2-3min, is eventually adding polyamide, under 400-700r/min rotating speed under 500-1000r/min rotating speed
Stirring mixing 1-2min, shakes out.
The chromite sand granularity is 15 μm.
The preparation method of the conductive polycrystalline mullite fiber is as follows：
（1）According to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into immersion in the mixed solution that ethanol and acetone are constituted in equal volume by 80
1.5h is cleaned, is taken out after drying according still further to solid-to-liquid ratio 1:90 are put into polycrystalline mullite fibre in strong oxidizing solution, and water-bath adds
Heat is to 80 DEG C, the stirring reaction 4h under 3000r/min rotating speed, then the ultrasonically treated 2h under 400W power, suction filtration, and filter residue is used
Water washing is distilled to neutrality, and 11h is dried at 85 DEG C, hydroxylating polycrystalline mullite fibre is produced；
（2）According to solid-to-liquid ratio 1:55 add hydroxylating polycrystalline mullite fibre in distilled water, are stirred under 2500r/min rotating speed
Scattered 1.5h is mixed, the epoxychloropropane equivalent to polycrystalline mullite fibre quality 18% is then added, in 1500r/min rotating speed
Lower dispersed with stirring 1h, sequentially adds dimethylamine and triethylene tetramine, and the mol ratio of dimethylamine and epoxychloropropane is 1:1.2,
The quality of triethylene tetramine is the 2% of epoxychloropropane and dimethylamine gross mass, and heating water bath is to 65 DEG C, in turning for 800r/min
The lower stirring reaction 6h of speed, then the microwave treatment 2h under 300W power, suction filtration, filter residue be washed with distilled water to filtrate it is not chloride from
Son, dries 18h at 65 DEG C, then activates 1.5h at 115 DEG C, produces poly-epoxychloropropane dimethylamine cation and is modified polycrystalline not
Carry out mineral wool；
（3）Add graphene oxide into ultrasonic agitation in distilled water and the graphene oxide dispersion that mass fraction is 1.5% is made；
Again with pH=3.5 of the mass fraction for 15% hydrochloric acid solution regulation graphene oxide dispersion；Then according to mass ratio 1:45 will
Poly-epoxychloropropane dimethylamine cation is modified polycrystalline mullite fibre and added in the graphene oxide dispersion after regulation pH, quiet
35min is put, is during which lifted 3 times, 2.5h is then irradiated under ultraviolet lamp, irradiation intensity is 90 μ W/cm2, with distillation after taking-up
Water washing dries 18h at 65 DEG C, produces graphene coated polycrystalline mullite fibre composite conducting material to neutrality.
The preparation method of the modified epoxy is as follows：
（1）According to mol ratio 1：1.8：0.001：0.0003 by 2,5- furandicarboxylic acids, ethylene glycol, butyl titanate and tricresyl phosphate
Methyl esters is mixed, slow heating, and is stirred continuously, while being passed through nitrogen at ambient pressure as protective gas, esterification temperature control exists
190 DEG C, reaction system is gradually transparent by muddiness steering, represents that esterification terminates when reaching articulation point；Then by esterification products
Continue to heat up, and be stirred continuously, react 6h at a temperature of 70Pa vacuums and 230 DEG C, produce polycondensation product, finally produce polycondensation
Thing is dissolved in tetrachloroethanes, precipitates in methyl alcohol, and supernatant is removed after centrifugation, so repeatedly 3 times, then vacuum is done at 130 DEG C
Dry 36h, produces poly- FDCA glycol ester；
（2）According to mass ratio 4.5:1.1:0.28:1.9 is sub- by poly- 2,5- furandicarboxylic acids glycol ester, acrylic acid, seven water sulfuric acid
Iron and water are well mixed, stand and lead to nitrogen 25min after 12h, are subsequently placed in60Irradiated in Co gamma-radiation radiation source radiation fields,
Radiation dose rate is 1.2kGy/h, and irradiation total absorbed dose is 22kGy；After irradiation terminates, washed with hot distilled water 4 times, 65
Constant weight is dried under vacuum at DEG C, acrylic acid-grafted poly- FDCA glycol ester is produced；
（3）According to mass ratio 5:1 is well mixed epoxychloropropane, acrylic acid-grafted poly- FDCA glycol ester,
Logical nitrogen is as protective gas, and heating water bath adds the tetramethyl bromination equivalent to epoxychloropropane quality 1.5% to 95 DEG C
Then ammonium, constant temperature stirring reaction 3h is cooled to 80 DEG C, adds the sodium hydrate aqueous solution that mass fraction is 45% so that hydroxide
The quality of sodium is the 4.5% of epoxychloropropane, continues constant temperature stirring reaction 2h, while normal pressure azeotropic sloughs the part water in system
Part, the solid salt of system is filtered out, then vacuum distillation removes the tree of remaining aqueous phase and synthesis at 0.15MPa, 115 DEG C
Fat, is then dissolved with toluene, then is washed with deionized 4 times, except sub-cloud aqueous phase, then with pH test paper come the acid in test solution
Alkalescence, and the dibastic sodium phosphate aqueous solution regulation system for being 10% with mass fraction is neutral solution, then be washed with deionized 4 times
And aqueous phase is removed, finally distillation removes toluene and water, produces required poly- FDCA glycol ester modified epoxy tree
Fat.
The amine value of the polyamide is 200, and relative molecular mass is 800.
Embodiment 3
A kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, comprises the following steps：
（1）According to mass ratio 100:4:3:1:0.6:0.02 weighs nice foundry sand, conductive polycrystalline mullite fiber, modified epoxy tree
Fat, polyamide, phenmethylol and γ-（2,3- glycidoxies）Propyl trimethoxy silicane；
（2）Modified epoxy is mixed with phenmethylol, 3min is stirred under 600r/min rotating speed, the modification ring of dilution is produced
Oxygen tree fat；
（3）By conductive polycrystalline mullite fiber, nice foundry sand, γ-（2,3- glycidoxies）Propyl trimethoxy silicane adds mixed
In sand machine, stirring mixing 3min, then adds the modified epoxy of dilution, in 1000r/min under 1200r/min rotating speed
Rotating speed under stirring mixing 2min, be eventually adding polyamide, under 700r/min rotating speed stirring mixing 1min, shake out i.e.
Can.
The granularity of the nice foundry sand is 20 μm.
The preparation method of the conductive polycrystalline mullite fiber is as follows：
（1）According to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into immersion in the mixed solution that ethanol and acetone are constituted in equal volume by 90
2h is cleaned, is taken out after drying according still further to solid-to-liquid ratio 1:100 are put into polycrystalline mullite fibre in strong oxidizing solution, heating water bath
To 90 DEG C, the stirring reaction 3h under 4000r/min rotating speed, then the ultrasonically treated 1h under 500W power, suction filtration, filter residue steaming
Distilled water is washed to neutrality, and 8h is dried at 90 DEG C, hydroxylating polycrystalline mullite fibre is produced；
（2）According to solid-to-liquid ratio 1:60 add hydroxylating polycrystalline mullite fibre in distilled water, are stirred under 3000r/min rotating speed
Scattered 1h is mixed, the epoxychloropropane equivalent to polycrystalline mullite fibre quality 20% is then added, under 2000r/min rotating speed
Dispersed with stirring 1.5h, sequentially adds dimethylamine and triethylene tetramine, and the mol ratio of dimethylamine and epoxychloropropane is 1.5, three
The quality of ethene tetramine is the 3% of epoxychloropropane and dimethylamine gross mass, and heating water bath is to 70 DEG C, in 1000r/min rotating speed
Lower stirring reaction 8h, then the microwave treatment 1h under 400W power, suction filtration, filter residue be washed with distilled water to filtrate it is not chloride from
Son, dries 12h at 70 DEG C, then activates 1h at 120 DEG C, produces poly-epoxychloropropane dimethylamine cation modification polycrystalline and does not come
Mineral wool；
（3）Add graphene oxide into ultrasonic agitation in distilled water and the graphene oxide dispersion that mass fraction is 2% is made；Again
With pH=4 of the mass fraction for 15% hydrochloric acid solution regulation graphene oxide dispersion；Then according to mass ratio 1:50 by polycyclic
Oxygen chloropropane dimethylamine cation is modified polycrystalline mullite fibre and added in the graphene oxide dispersion after regulation pH, stands
40min, is during which lifted 3 times, and 2h is then irradiated under ultraviolet lamp, and irradiation intensity is 100 μ W/cm2, with distillation washing after taking-up
Wash to neutrality, 12h is dried at 70 DEG C, graphene coated polycrystalline mullite fibre composite conducting material is produced.
The preparation method of the modified epoxy is as follows：
（1）According to mol ratio 1：2：0.0014：0.0004 by 2,5- furandicarboxylic acids, ethylene glycol, butyl titanate and tricresyl phosphate
Methyl esters is mixed, slow heating, and is stirred continuously, while being passed through nitrogen at ambient pressure as protective gas, esterification temperature control exists
210 DEG C, reaction system is gradually transparent by muddiness steering, represents that esterification terminates when reaching articulation point；Then by esterification products
Continue to heat up, and be stirred continuously, react 4h at a temperature of 60Pa vacuums and 240 DEG C, produce polycondensation product, finally produce polycondensation
Thing is dissolved in tetrachloroethanes, precipitates in methyl alcohol, and supernatant is removed after centrifugation, so repeatedly 4 times, then vacuum is done at 140 DEG C
Dry 24h, produces poly- FDCA glycol ester；
（2）According to mass ratio 5:1.4:0.3:2.2 by poly- 2,5- furandicarboxylic acids glycol ester, acrylic acid, ferrous sulfate heptahydrate
It is well mixed with water, stand and lead to nitrogen 30min after 15h, be subsequently placed in60Irradiated in Co gamma-radiation radiation source radiation fields, spoke
It is 1.5kGy/h according to close rate, irradiation total absorbed dose is 25kGy；After irradiation terminates, washed with hot distilled water 4 times, at 70 DEG C
Under be dried under vacuum to constant weight, produce acrylic acid-grafted poly- FDCA glycol ester；
（3）According to mass ratio 7:1 is well mixed epoxychloropropane, acrylic acid-grafted poly- FDCA glycol ester,
Logical nitrogen is as protective gas, and heating water bath adds the tetramethyl bromination equivalent to epoxychloropropane quality 2% to 100 DEG C
Then ammonium, constant temperature stirring reaction 2h is cooled to 85 DEG C, adds the sodium hydrate aqueous solution that mass fraction is 45% so that hydroxide
The quality of sodium is the 6% of epoxychloropropane, continues constant temperature stirring reaction 1-3h, while normal pressure azeotropic sloughs the part water in system
Part, the solid salt of system is filtered out, then vacuum distillation removes the tree of remaining aqueous phase and synthesis at 0.1MPa, 120 DEG C
Fat, is then dissolved with toluene, then is washed with deionized 4 times, except sub-cloud aqueous phase, then with pH test paper come the acid in test solution
Alkalescence, and the dibastic sodium phosphate aqueous solution regulation system for being 10% with mass fraction is neutral solution, then be washed with deionized 4 times
And aqueous phase is removed, finally distillation removes toluene and water, produces required poly- FDCA glycol ester modified epoxy tree
Fat.
The amine value of the polyamide is 220, and relative molecular mass is 1000.
Claims (7)
1. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand, it is characterised in that comprise the following steps：
（1）According to mass ratio 80-100:2-4:1-3:0.5-1:0.3-0.6:0.01-0.02 weighs matrix sand material, conductive polycrystalline
Mullite fiber, modified epoxy, curing agent, diluent and silane coupler；
（2）Modified epoxy is mixed with diluent, 3-6min is stirred under 300-600r/min rotating speed, produces dilution
Modified epoxy；
（3）Conductive polycrystalline mullite fiber, matrix sand material, silane coupler are added in puddle mixer, 800-1200r/min's
Stirring mixing 3-4min, then adds the modified epoxy of dilution under rotating speed, stirs mixed under 500-1000r/min rotating speed
2-3min is closed, curing agent is eventually adding, stirring mixing 1-2min, shakes out under 400-700r/min rotating speed.
2. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand according to claim 1, it is special
Levy and be, described matrix sand material is selected from quartz sand, zircon sand, magnesite clinker, chromite sand, forsterite sand, aquamaine stone sand, lime
One kind in stone sand, graphite sand, nice foundry sand, Task-size Controlling is at 10-20 μm.
3. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand according to claim 1, it is special
Levy and be, the preparation method of the conductive polycrystalline mullite fiber is as follows：
（1）According to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into the mixed solution that ethanol and acetone are constituted in equal volume by 70-90
Soaking and washing 1-2h, takes out after drying according still further to solid-to-liquid ratio 1:Polycrystalline mullite fibre is put into strong oxidizing solution by 80-100
In, heating water bath is to 70-90 DEG C, the stirring reaction 3-5h under 2000-4000r/min rotating speed, then in 300-500W power
Under ultrasonically treated 1-3h, suction filtration, filter residue is washed with distilled water to neutrality, and 8-14h is dried at 80-90 DEG C, hydroxylating is produced many
Brilliant mullite fiber；
（2）According to solid-to-liquid ratio 1:50-60 adds hydroxylating polycrystalline mullite fibre in distilled water, 1500-3000r/min's
Dispersed with stirring 1-2h under rotating speed, then adds the epoxychloropropane equivalent to polycrystalline mullite fibre quality 15-20%, in 1000-
Dispersed with stirring 0.5-1.5h under 2000r/min rotating speed, sequentially adds dimethylamine and triethylene tetramine, dimethylamine and epoxy chlorine
The mol ratio of propane is 1:1-1.5, the quality of triethylene tetramine is epoxychloropropane and the 1-3% of dimethylamine gross mass, and water-bath adds
Heat is to 60-70 DEG C, the stirring reaction 5-8h under 500-1000r/min rotating speed, then the microwave treatment under 200-400W power
1-3h, suction filtration, filter residue is washed with distilled water to filtrate not chloride ion-containing, and 12-24h is dried at 60-70 DEG C, then in 110-120
1-2h is activated at DEG C, poly-epoxychloropropane dimethylamine cation is produced and is modified polycrystalline mullite fibre；
（3）Add graphene oxide into ultrasonic agitation in distilled water and the graphene oxide dispersion that mass fraction is 1-2% is made；
Again with pH=3-4 of the mass fraction for 15% hydrochloric acid solution regulation graphene oxide dispersion；Then according to mass ratio 1:40-50
Poly-epoxychloropropane dimethylamine cation is modified into polycrystalline mullite fibre to add in the graphene oxide dispersion after regulation pH,
30-40min is stood, is during which lifted 2-3 times, 2-3h is then irradiated under ultraviolet lamp, irradiation intensity is 80-100 μ W/cm2, take
Neutrality is washed with distilled water to after going out, 12-24h is dried at 60-70 DEG C, graphene coated polycrystalline mullite fibre is produced and is combined
Conductive material.
4. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand according to claim 1, it is special
Levy and be, the preparation method of the modified epoxy is as follows：
（1）According to mol ratio 1：1.5-2：0.0008-0.0014：0.0002-0.0004 by 2,5- furandicarboxylic acids, ethylene glycol,
Butyl titanate and trimethyl phosphate mixing, slow heating, and be stirred continuously, while being passed through nitrogen at ambient pressure as protection gas
Body, esterification temperature control is at 170-210 DEG C, and reaction system is gradually transparent by muddiness steering, represents that esterification is anti-when reaching articulation point
It should terminate；Then esterification products are continued to heat up, and be stirred continuously, reacted at a temperature of 60-80Pa vacuums and 220-240 DEG C
4-7h, produces polycondensation product, and polycondensation product finally is dissolved in into tetrachloroethanes, precipitated in methyl alcohol, supernatant is removed after centrifugation,
So 2-4 times repeatedly, then 24-48h is dried in vacuo at 120-140 DEG C, produce poly- FDCA glycol ester；
（2）According to mass ratio 4-5:0.8-1.4:0.25-0.3:1.7-2.2 is by poly- 2,5- furandicarboxylic acids glycol ester, propylene
Acid, ferrous sulfate heptahydrate and water are well mixed, stand and lead to nitrogen 20-30min after 10-15h, are subsequently placed in60Co gamma-radiations are radiated
Irradiated in source radiation, radiation dose rate is 1-1.5kGy/h, irradiation total absorbed dose is 20-25kGy；Irradiation terminates
Afterwards, washed 3-4 times with hot distilled water, constant weight is dried under vacuum at 60-70 DEG C, produce acrylic acid-grafted poly- 2,5- furans diformazan
Sour glycol ester；
（3）According to mass ratio 3-7:Epoxychloropropane, acrylic acid-grafted poly- 2,5- furandicarboxylic acids glycol ester are mixed equal by 1
It is even, lead to nitrogen as protective gas, heating water bath adds the tetramethyl equivalent to epoxychloropropane quality 1-2% to 90-100 DEG C
Then base ammonium bromide, constant temperature stirring reaction 2-4h is cooled to 75-85 DEG C, adds mass fraction water-soluble for 45% sodium hydroxide
Liquid so that the quality of sodium hydroxide is the 3-6% of epoxychloropropane, continues constant temperature stirring reaction 1-3h, while normal pressure azeotropic is sloughed
Part moisture content in system, filters out the solid salt of system, then vacuum distillation is removed at 0.1-0.2MPa, 110-120 DEG C
The resin of remaining aqueous phase and synthesis is removed, is then dissolved with toluene, then is washed with deionized 3-4 times, except sub-cloud aqueous phase, then
With pH test paper come the acid-base property in test solution, and the dibastic sodium phosphate aqueous solution regulation system for being 10% with mass fraction is neutral
Solution, then be washed with deionized 3-4 times and remove aqueous phase, finally distillation removes toluene and water, produces required poly- 2,5- furans
Mutter naphthalate modified epoxy.
5. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand according to claim 1, it is special
Levy and be, the curing agent is polyamide, its amine value is 200 ± 20, and relative molecular mass is 600-1100.
6. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand according to claim 1, it is special
Levy and be, the one kind of the diluent in acetone, ethyl acetate, dimethylbenzene, styrene, dimethylformamide, phenmethylol.
7. a kind of preparation method of conductive polycrystalline mullite fiber reinforced epoxy sand according to claim 1, it is special
Levy and be, the silane coupler be selected from gamma-aminopropyl-triethoxy-silane, γ-（2,3- glycidoxies）Propyl group trimethoxy
One kind in base silane.
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| CN109518530A (en) * | 2018-11-02 | 2019-03-26 | 杭州特种纸业有限公司 | Thick vulcan fibre of a kind of lamination and preparation method thereof |
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