CN102391632A - Graphene oxide/unsaturated polyester composite material and preparation method thereof - Google Patents
Graphene oxide/unsaturated polyester composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene oxide/unsaturated polyester composite material and a preparation method of the composite material. The composite material comprises the raw materials: dihydric alcohol, graphene oxide, saturated binary acid or acid anhydride, unsaturated binary acid or acid anhydride, vinyl monomer, and normal polymerization inhibitor, initiator and accelerant, wherein the content of the graphene oxide is 0.06-0.5wt%. The preparation method of the graphene oxide/unsaturated polyester composite material comprises the following steps of: adding the graphene oxide into the dihydric alcohol to directly and ultrasonically disperse, or adding the dihydric alcohol into graphene oxide water solution to ultrasonically disperse and remove water in a fractional distillation way so as to obtain graphene oxide/dihydric alcohol solution which is evenly dispersed; performing polycondensation between the obtained graphene oxide/dihydric alcohol solution and the saturated binary acid or acid anhydride, unsaturated binary acid or acid anhydride and polymerization inhibitor with metering ratio, and diluting by adding the vinyl monomer after the polymerization so as to prepare graphene oxide/unsaturated polyester resin; and adding the initiator and the accelerant, and curing and crosslinking to prepare the graphene oxide/unsaturated polyester composite material.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of short-cut method for preparing graphene oxide/unsaturated polyester composite.
Background technology
Unsaturated polyester resin (UPR) has good mechanical performance, electrical property and chemical resistance, is the maximum a kind of resin of usage quantity in the composite reinforcing material, and its matrix material is widely used in industry such as boats and ships, automobile, building materials industry.Compare with other thermosetting resin, it is low that UPR has viscosity, easy to process, both can solidify at normal temperatures and pressures, also can under warming and pressurizing, react; Solidify and do not emit small molecules, can produce more uniform product; Moderate; Or the like.But the toughness of common UPR, thermotolerance and erosion resistance etc. are also not satisfactory.Therefore the study on the modification work such as mechanical property and tolerance that improve UPR are significant.
A fine way improving performance adds filler exactly, if you would take off soil, aerosil, sepiolite, kaolin, nano aluminum nitride, nano titanium oxide, nanometer potter's clay and carbon nanotube (Chinese patent CN 101407622) etc.According to investigating, also there is not report at present both at home and abroad about utilizing grapheme material to strengthen the matrix material of unsaturated polyester resin.Graphene is to have sp
2The two-dimentional carbon atom crystal of hybridized orbital is equaled to find in 2004 by Geim, and can stable existence, is the inorganic nano material of at present the thinnest in the world material-monatomic thickness.Graphene not only has excellent electric property, and light weight, and thermal conductivity is good, and tensile strength and modulus are respectively 125 GPa and 1060 GPa, and intensity is more than 100 times of steel.Compare with carbon nanotube with the soccerballene of costliness, graphene oxide is cheap, and raw material is easy to get, and is expected to become the high quality filler of polymer nanocomposites.In recent years, Ruoff etc. develop Graphene/polymer conductive nanometer compound material and unsupported graphene oxide paper (Nature, 2006,442 (7100): 282 in succession with chemical process; Nature. 2007,448:457), started the upsurge of graphene oxide applied research.
(Graphite Oxide GO) is considered to the strategic starting point of extensive synthesizing graphite alkene to prepare graphite oxide from graphite.The preparation method of GO has Brodie method, Standenmaier method and Hummers method usually.GO can further use mechanical means, as pyrolysis expand or in solvent ultra-sonic dispersion, prepare stable accurate two dimensional oxidation graphene suspension.Graphene oxide will be filled in the middle of the non-hydrophilic material, generally need it carried out after the modification it being dissolved in the organic solvent.
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Summary of the invention
The object of the invention is to provide that a kind of technology is simple, easy to operate, graphene oxide/unsaturated polyester composite capable of being industrialized and preparation method thereof.
Technical scheme of the present invention is: a kind of graphene oxide/unsaturated polyester composite; Raw material is: divalent alcohol, graphene oxide, monounsaturated dicarboxylic acid or acid anhydrides, unsaturated dibasic acid or acid anhydrides, vinyl monomer and conventional stopper, initiator and promotor; Wherein the content of graphene oxide is 0.06-0.5 wt%.
The method for preparing described graphene oxide/unsaturated polyester composite; Graphene oxide added directly carries out ultra-sonic dispersion in the divalent alcohol, or with divalent alcohol add carry out in the graphite oxide aqueous solution ultra-sonic dispersion again fractionation remove to anhydrate and obtain homodisperse graphene oxide/glycol solution; Carry out polycondensation with monounsaturated dicarboxylic acid or acid anhydrides, unsaturated dibasic acid or acid anhydrides and the stopper of metering ratio, polymerization is accomplished the back and is added and prepare graphene oxide/unsaturated polyester resin after vinyl monomer dilutes; Obtain graphene oxide/unsaturated polyester composite after adding initiator and promotor curing cross-linked at last again.
The described method for preparing graphene oxide/unsaturated polyester composite is characterized in that concrete steps comprise:
The first step adds the graphene oxide of 0.1-0.9 weight part in the divalent alcohol of 40 weight parts, and 20-50 ℃ of following vigorous stirring and ultrasonic 0.5-2h obtain homodisperse graphene oxide/glycol solution.Or add the divalent alcohol of 40 weight parts toward the graphite oxide aqueous solution that prepared, the back ultrasonic half a hour of stirring, obtain homodisperse graphene oxide/water/glycol solution; This solution is transferred in the four neck flasks that have TM, gas tube, mechanical stirring and separation column; Stir and logical nitrogen after connecting water distilling apparatus, be warming up to 100-180 ℃, be incubated several hours; Distill until anhydrous, obtain homodisperse graphene oxide/glycol solution;
Second step; The monounsaturated dicarboxylic acid or acid anhydrides, unsaturated dibasic acid or acid anhydrides and the stopper that add the metering ratio in graphene oxide/glycol solution that the first step is obtained; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 20 ~ 60 mgKOH/g, be cooled to 70 ~ 120 ℃, add the vinyl monomer that is dissolved with stopper, weight is that 1/3 of whole system is diluted, and is uniformly dispersed to obtain graphene oxide/unsaturated polyester resin;
The 3rd step, get resulting graphene oxide/unsaturated polyester resin 100 weight parts of second step, the initiator that adds the 2-4 weight part stirs, and adds the promotor of≤0.5 weight part again and stirs; Above curing system is poured in the mould, vacuum stripping bubble, at≤100 ℃ but＞0 ℃ of following curing molding, obtain graphene oxide/unsaturated polyester composite.
Said divalent alcohol is any or several kinds in terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether or the DPG.
Described monounsaturated dicarboxylic acid is any one or a few in phthalic acid, m-phthalic acid, terephthalic acid, the hexanodioic acid, and described monounsaturated dicarboxylic acid acid anhydride is any one or a few in Tetra hydro Phthalic anhydride or the halobenzoyl anhydride.
Described unsaturated dicarboxylic acid anhydride is maleic acid or acid anhydrides, and described unsaturated dibasic acid is any one or a few in FUMARIC ACID TECH GRADE, methylene-succinic acid, citraconic acid and the halo maleic acid.
Described stopper is Resorcinol, para benzoquinone or 2, any in the 6-di-tert-butyl methyl phenol or several kinds.
Described vinyl monomer is any or several kinds in vinylbenzene, Vinylstyrene, acrylic acid or the like, methacrylic, chloropropyl, butene dioic acid or the vinylcarbinol.
Described initiator is tert-butyl hydroperoxide two lauryl, isopropyl benzene hydroperoxide, di-t-butyl peroxide, Di Cumyl Peroxide 99, dilauroyl peroxide, BPO, peroxo-dichloro to any or several kinds in benzoyl, the peroxidation acid tert-butyl ester, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide or the cyclohexanone peroxide etc.
Described promotor does
N,
N-xylidine,
N,
N-Diethyl Aniline,
N,
N-dimethyl-p-toluidine, cobalt naphthenate, cobalt iso-octoate, manganese naphthenate, manganese iso-octoate; In lauryl mercaptan, UVNUL MS-40, st-yrax and the ethers thereof any or several kinds.
Beneficial effect
(1) proposes a kind of easy method and prepared graphene oxide/unsaturated polyester composite; Not needing in advance graphene oxide to be carried out the modification processing makes it be dissolved in organic solvent; But pass through the direct ultra-sonic dispersion of graphene oxide in divalent alcohol; Or divalent alcohol added carry out fractionation behind graphene oxide/aqueous solution and handle, obtain finely disseminated graphene oxide/glycol solution as the divalent alcohol raw material;
(2) adopt the multistep processes synthetic technology, processing ease, constant product quality, technology is simple, is easy to industry and enlarges production, and is practical;
(3) resulting resin has air-drying property, does not need to add end-capping reagent again, and is corrosion-resistant and aging, and the mechanics of material, calorifics and electric property satisfy the requirement of versatility unsaturated polyester resin various fields.
(4) composite modification material of preparing method's employing of the present invention derives from graphite, and price is lower, helps reducing cost.Lower by 1 ~ 5% than the unsaturated polyester resins for general purpose cost of similar not modification, but mechanical property, thermal property and electric property all have raising by a relatively large margin.
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Embodiment
Embodiment below the present invention is only as the further specifying of content of the present invention, can not be as scope perhaps in the qualification of the present invention.Below in conjunction with embodiment the present invention is made further detailed description.
A kind of preparation method of graphene oxide/unsaturated polyester composite; At first directly add graphene oxide in the divalent alcohol; Vigorous stirring and ultra-sonic dispersion; Or after the aqueous solution of a certain amount of graphene oxide and divalent alcohol mixed solution carried out fractionation and handle, make the graphene oxide/glycol solution of good dispersibility; Then with this glycol solution as the divalent alcohol raw material, with polycondensations such as monounsaturated dicarboxylic acid (acid anhydride), unsaturated dibasic acid (acid anhydride), stoppers, polymerization is accomplished the back and is added and prepare graphene oxide/unsaturated polyester resin after vinyl monomer dilutes; Add initiator and promotor etc. toward resin more at last, prepare graphene oxide/unsaturated polyester composite behind the curing cross-linked.Its concrete steps comprise:
The first step adds the graphene oxide of 0.1-0.9 weight part in the divalent alcohol of 40 weight parts, and 20-50 ℃ of following vigorous stirring and ultrasonic 0.5-2h obtain homodisperse graphene oxide/glycol solution.Or add the divalent alcohol of 40 weight parts toward the graphite oxide aqueous solution that prepared, the back ultrasonic half a hour of stirring, obtain homodisperse graphene oxide/water/glycol solution; This solution is transferred in the four neck flasks that have TM, gas tube, mechanical stirring and separation column; Stir and logical nitrogen after connecting water distilling apparatus, be warming up to 100-180 ℃, be incubated several hours; Distill until anhydrous, obtain homodisperse graphene oxide/glycol solution.
Second step; Graphene oxide/glycol solution that the first step is obtained is as the divalent alcohol raw material; And add monounsaturated dicarboxylic acid (acid anhydride), unsaturated dibasic acid (acid anhydride) and the stopper etc. that measure ratio, be warming up to 150-160 ℃, insulation 0.5 ~ 1.5h; Be warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 20 ~ 60 mgKOH/g, be cooled to 70 ~ 120 ℃, add the vinyl monomer be dissolved with stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step, get resulting resin 100 weight parts of second step, the initiator that adds the 2-4 weight part stirs, and adds the promotor of 0-0.5 weight part again and stirs; Above curing system is poured in the mould, and the vacuum stripping bubble at 0-100 ℃ of following curing molding, obtains graphene oxide/unsaturated polyester composite.
Described graphene oxide obtains through pyrolysis expansion or ultra-sonic dispersion graphite oxide, and graphite oxide then can be by the method preparation of chemical oxidations such as Brodie method, Staudenmaier method or Hummers method.
Described divalent alcohol is one or more in terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether or the DPG etc.
Described monounsaturated dicarboxylic acid (acid anhydride) is one or more in phthalic acid (acid anhydride), m-phthalic acid, terephthalic acid, hexanodioic acid and the halobenzoyl anhydride etc.
Described unsaturated dibasic acid (acid anhydride) is one or more in maleic acid (acid anhydride), FUMARIC ACID TECH GRADE, methylene-succinic acid, citraconic acid and the halo maleic acid etc.
Described stopper is Resorcinol, para benzoquinone and 2, one or more in the 6-di-tert-butyl methyl phenol.
Described vinyl monomer is wherein one or more such as vinylbenzene, Vinylstyrene, acrylic acid or the like, methacrylic, chloropropyl, butene dioic acid and vinylcarbinol.
Described initiator comprises hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyesters or ketone peroxide, like tert-butyl hydroperoxide two lauryl, isopropyl benzene hydroperoxide, di-t-butyl peroxide, Di Cumyl Peroxide 99, dilauroyl peroxide, BPO, peroxo-dichloro in benzoyl, the peroxidation acid tert-butyl ester, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide and the cyclohexanone peroxide etc. one or more.
Described promotor comprises tertiary amines, as
N,
N-xylidine,
N,
N-Diethyl Aniline,
N,
N-dimethyl-p-toluidine; Variable valency metal salt is like cobalt naphthenate, cobalt iso-octoate, manganese naphthenate, manganese iso-octoate; In lauryl mercaptan, UVNUL MS-40, st-yrax and the ethers thereof one or more.
Graphene oxide/unsaturated polyester composite that described method prepares can be used on various fields such as material of construction, mould, automobile, farm equipment, insulation apparatus, marine stores medical facilities, daily necessities, industrial liner.
Embodiment 1:
The first step, the graphite oxide aqueous solution (weight content is 3%) of past 20g adds the terepthaloyl moietie of 40g, ultrasonic half a hour after stirring, obtains homodisperse graphene oxide/water/glycol solution; This solution is transferred in the four neck flasks that have TM, gas tube, mechanical stirring and separation column; Stir and logical nitrogen after connecting water distilling apparatus, be warming up to 100-180 ℃, be incubated several hours; Distill until anhydrous, obtain homodisperse graphene oxide/glycol solution.
In second step, get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 25.9 g cis-butenedioic anhydrides, 39.1g phthalic anhydride and 0.1g Resorcinol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add styrene monomer 50 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step, get resulting resin 100 g of second step, the Lucidol that adds 2g stirs, and adds 0.2 g again
N,
N-xylidine also stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 2:
In the first step, the graphite oxide aqueous solution of past 30g adds the terepthaloyl moietie of 40g, and other are with embodiment 1.
Second step, the 3rd step are with embodiment 1.
Embodiment 3:
In the first step, the graphite oxide aqueous solution of past 40g adds the terepthaloyl moietie of 40g, and other are with embodiment 1.
Second step, the 3rd step are with embodiment 1.
Embodiment 4:
In the first step, the graphite oxide aqueous solution of past 50g adds the terepthaloyl moietie of 40g, and other are with embodiment 1.
Second step, the 3rd step are with embodiment 1.
Embodiment 5:
In the first step, the graphite oxide aqueous solution of past 60g adds the terepthaloyl moietie of 40g, and other are with embodiment 1.
Second step, the 3rd step are with embodiment 1.
Embodiment 6:
In the first step, 300 mg graphene oxides are directly added in the terepthaloyl moietie of 40g, ultrasonic 1 h obtains homodisperse graphene oxide/glycol solution after the vigorous stirring.
Second step, the 3rd step are with embodiment 1.
Embodiment 7
In the first step, 500 mg graphene oxides are directly added in the glycol ether of 60g, ultrasonic 1 h obtains homodisperse graphene oxide/glycol solution after the vigorous stirring.
In second step, get divalent alcohol liquid that the 59.8 g the first steps obtain as the divalent alcohol raw material, and add 25.9 g cis-butenedioic anhydrides, 39.1g phthalic anhydride and 0.1g Resorcinol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add styrene monomer 62 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 8
The first step is with embodiment 6.
In second step, get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 30.6 g maleic acids, 39.1g phthalic anhydride and 0.1g Resorcinol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add styrene monomer 52 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 9
The first step is with embodiment 6.
Second step; Get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 34.3 g methylene-succinic acids, 39.1g phthalic anhydride and 0.1g 2,6-di-tert-butyl methyl phenol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add styrene monomer 54 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 10
The first step is with embodiment 6.
In second step, get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 25.9 g maleic anhydrides, 39.1g phthalic anhydride and 0.1g para benzoquinone; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add Vinylstyrene 50 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 11
The first step is with embodiment 6.
Second step; Get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 25.9 g maleic anhydrides, 39.1g phthalic anhydride and 0.1g 2,6-di-tert-butyl methyl phenol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add Acrylic Acid Monomer 50 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 12
The first step is with embodiment 6.
In second step, get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 25.9 g maleic anhydrides, 39.1g phthalic anhydride and 0.1g Resorcinol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add butene dioic acid monomer 50 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 13
The first step is with embodiment 6.
In second step, get divalent alcohol liquid that the 35g the first step obtains as the divalent alcohol raw material, and add 25.9 g maleic anhydrides, 39.1g phthalic anhydride and 0.1g Resorcinol; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add chloropropyl monomer 50 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step is with embodiment 1.
Embodiment 14
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the methylethyl ketone peroxide that adds 2g stirs, and adds 0.5 g cobalt naphthenate again and stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 15
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the peroxidized t-butyl perbenzoate that adds 2g stirs, and adds 0.2 g again
N,
N-dimethyl-p-toluidine also stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 16
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the isopropyl benzene hydroperoxide that adds 2g stirs, and adds 0.2 g again
N,
N-dimethyl-p-toluidine also stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 17
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the di-t-butyl peroxide that adds 2g stirs, and adds 0.2 g again
N,
N-dimethyl-p-toluidine also stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 18
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the dilauroyl peroxide that adds 2g stirs, and adds 0.2 g lauryl mercaptan again and stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 19
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the Di Cumyl Peroxide 99 that adds 2g stirs, and adds 0.2 g UVNUL MS-40 again and stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Embodiment 20
The first step, second step is with embodiment 6.
The 3rd step, get resulting resin 100 g of second step, the Lucidol that adds 2g stirs, and adds 0.2 g st-yrax again and stirs; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
Comparative example 1:
The first step, blank test is ready to the terepthaloyl moietie of oxygen-free Graphene.
Second step, get the divalent alcohol that the 35g the first step is prepared, and add 25.9 g cis-butenedioic anhydrides, 39.1g phthalic anhydride and 0.1g Resorcinol, be warming up to 150-160 ℃, insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 40 mgKOH/g, be cooled to 70 ~ 120 ℃, add styrene monomer 50 g be dissolved with the 0.01g stopper (weight be whole system 1/3) and dilute, being uniformly dispersed obtains graphene oxide/unsaturated polyester resin.
The 3rd step, get resulting resin 100 g of second step, the Lucidol that adds 2g stirs, and adds 0.2 g again
N,
N-xylidine and stir; Above curing system is poured in the mould, and the vacuum stripping bubble rises to 50 ℃ of aftertreatment 12 h behind self-vulcanizing 24 h curing moldings, obtain graphene oxide/unsaturated polyester composite.
The Main physical performance index of embodiment 1-6 and comparative example 1 sample are relatively seen table 1.It is thus clear that its physical index all satisfies the requirement of general universal resin film forming.
The main performance index of table 1 embodiment 1-6 sample
| Test subject | TP | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example |
| Tensile strength (MPa) | GB/T2568-95 | 36.8 | 39.8 | 44.2 | 43.3 | 46.7 | 41.9 | 35.9 |
| Tensile modulus (GPa) | GB/T2568-95 | 2.23 | 2.57 | 2.63 | 3.19 | 3.85 | 2.89 | 1.98 |
| Breaking ductility (%) | GB/T2568-95 | 1.4 | 1.5 | 1.8 | 1.2 | 1.6 | 1.9 | 1.1 |
| Flexural strength (MPa) | GB/T2570-95 | 75.4 | 86.8 | 92.9 | 87.6 | 98.5 | 95.0 | 60.1 |
| Modulus in flexure (GPa) | GB/T2570-95 | 3.3 | 3.5 | 3.4 | 3.6 | 3.8 | 3.3 | 2.8 |
| Shock strength (KJ/m 2) | GB/T2571-95 | 2.5 | 3.0 | 3.2 | 3.2 | 3.9 | 3.3 | 2.1 |
| Barcol hardness | GB 3854-83 | 38 | 39 | 42 | 47 | 59 | 49 | 26 |
| Heat-drawn wire (℃) | GB 1634-04 | 73.3 | 75.8 | 78.4 | 86.2 | 93.1 | 92.6 | 62.3 |
| Second-order transition temperature (℃) | ? | 96.1 | 99.5 | 107.7 | 108.2 | 123.5 | 105.6 | 92.3 |
| Volume specific resistance (10 7Ω/m) | GB/T 15662 | 7.1 | 8.1 | 8.7 | 8.9 | 9.3 | 8.4 | 3.5×10 4 |
| Surface resistivity (10 8Ω/m) | GB/T 15662 | 7.3 | 8.3 | 8.6 | 9.2 | 9.7 | 9.1 | 6.7×10 5 |
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.
Claims (10)
1. graphene oxide/unsaturated polyester composite; It is characterized in that; Raw material is: divalent alcohol, graphene oxide, monounsaturated dicarboxylic acid or acid anhydrides, unsaturated dibasic acid or acid anhydrides, vinyl monomer and conventional stopper, initiator and promotor, wherein the content of graphene oxide is 0.06-0.5 wt%.
2. the method for preparing the described graphene oxide/unsaturated polyester composite of claim 1; It is characterized in that; Graphene oxide added directly carries out ultra-sonic dispersion in the divalent alcohol, or with divalent alcohol add carry out in the graphite oxide aqueous solution ultra-sonic dispersion again fractionation remove to anhydrate and obtain homodisperse graphene oxide/glycol solution; Carry out polycondensation with monounsaturated dicarboxylic acid or acid anhydrides, unsaturated dibasic acid or acid anhydrides and the stopper of metering ratio, polymerization is accomplished the back and is added and prepare graphene oxide/unsaturated polyester resin after vinyl monomer dilutes; Obtain graphene oxide/unsaturated polyester composite after adding initiator and promotor curing cross-linked at last again.
3. the method for preparing graphene oxide/unsaturated polyester composite as claimed in claim 2 is characterized in that concrete steps comprise:
The first step adds the graphene oxide of 0.1-0.9 weight part in the divalent alcohol of 40 weight parts, and 20-50 ℃ of following vigorous stirring and ultrasonic 0.5-2h obtain homodisperse graphene oxide/glycol solution; Or add the divalent alcohol of 40 weight parts toward the graphite oxide aqueous solution that prepared, the back ultrasonic half a hour of stirring, obtain homodisperse graphene oxide/water/glycol solution; This solution is transferred in the four neck flasks that have TM, gas tube, mechanical stirring and separation column; Stir and logical nitrogen after connecting water distilling apparatus, be warming up to 100-180 ℃, be incubated several hours; Distill until anhydrous, obtain homodisperse graphene oxide/glycol solution;
Second step; The monounsaturated dicarboxylic acid or acid anhydrides, unsaturated dibasic acid or acid anhydrides and the stopper that add the metering ratio in graphene oxide/glycol solution that the first step is obtained; Be warming up to 150-160 ℃; Insulation 0.5 ~ 1.5h is warming up to 190 ~ 210 ℃ of dehydration esterifications after the end, control separation column temperature≤105 ℃; When acid number reaches 20 ~ 60 mgKOH/g, be cooled to 70 ~ 120 ℃, add the vinyl monomer that is dissolved with stopper, weight is that 1/3 of whole system is diluted, and is uniformly dispersed to obtain graphene oxide/unsaturated polyester resin;
The 3rd step, get resulting graphene oxide/unsaturated polyester resin 100 weight parts of second step, the initiator that adds the 2-4 weight part stirs, and adds the promotor of≤0.5 weight part again and stirs; Above curing system is poured in the mould, vacuum stripping bubble, at≤100 ℃ but＞0 ℃ of following curing molding, obtain graphene oxide/unsaturated polyester composite.
4. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite, it is characterized in that said divalent alcohol is any or several kinds in terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether or the DPG.
5. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite; It is characterized in that; Described monounsaturated dicarboxylic acid is any one or a few in phthalic acid, m-phthalic acid, terephthalic acid, the hexanodioic acid, and described monounsaturated dicarboxylic acid acid anhydride is any one or a few in Tetra hydro Phthalic anhydride or the halobenzoyl anhydride.
6. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite; It is characterized in that; Described unsaturated dicarboxylic acid anhydride is maleic acid or acid anhydrides, and described unsaturated dibasic acid is any one or a few in FUMARIC ACID TECH GRADE, methylene-succinic acid, citraconic acid and the halo maleic acid.
7. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite, it is characterized in that described stopper is Resorcinol, para benzoquinone or 2, any in the 6-di-tert-butyl methyl phenol or several kinds.
8. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite; It is characterized in that described vinyl monomer is any or several kinds in vinylbenzene, Vinylstyrene, acrylic acid or the like, methacrylic, chloropropyl, butene dioic acid or the vinylcarbinol.
9. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite; It is characterized in that described initiator is tert-butyl hydroperoxide two lauryl, isopropyl benzene hydroperoxide, di-t-butyl peroxide, Di Cumyl Peroxide 99, dilauroyl peroxide, BPO, peroxo-dichloro to any or several kinds in benzoyl, the peroxidation acid tert-butyl ester, peroxidized t-butyl perbenzoate, methylethyl ketone peroxide or the cyclohexanone peroxide etc.
10. like claim 2 or the 3 described methods that prepare graphene oxide/unsaturated polyester composite, it is characterized in that described promotor does
N,
N-xylidine,
N,
N-Diethyl Aniline,
N,
N-dimethyl-p-toluidine, cobalt naphthenate, cobalt iso-octoate, manganese naphthenate, manganese iso-octoate; In lauryl mercaptan, UVNUL MS-40, st-yrax and the ethers thereof any or several kinds.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110046252A1 (en) * | 2008-04-22 | 2011-02-24 | Stefan Bahnmueller | Reaction resin based on an unsaturated polyester, vinyl compounds and hydrocarbon nanotubes that can be cured radically |
| US20110163275A1 (en) * | 2008-06-07 | 2011-07-07 | Hexcel Composites, Ltd. | Conductivity of resin materials and composite materials |
-
2011
- 2011-09-14 CN CN2011102701178A patent/CN102391632B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110046252A1 (en) * | 2008-04-22 | 2011-02-24 | Stefan Bahnmueller | Reaction resin based on an unsaturated polyester, vinyl compounds and hydrocarbon nanotubes that can be cured radically |
| US20110163275A1 (en) * | 2008-06-07 | 2011-07-07 | Hexcel Composites, Ltd. | Conductivity of resin materials and composite materials |
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