CN103304803A - Method for preparing casting type nylon/modified graphite oxide nanocomposite - Google Patents
Method for preparing casting type nylon/modified graphite oxide nanocomposite Download PDFInfo
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- CN103304803A CN103304803A CN2013102781218A CN201310278121A CN103304803A CN 103304803 A CN103304803 A CN 103304803A CN 2013102781218 A CN2013102781218 A CN 2013102781218A CN 201310278121 A CN201310278121 A CN 201310278121A CN 103304803 A CN103304803 A CN 103304803A
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Abstract
The invention discloses a method for preparing a casting type nylon/modified graphite oxide nanocomposite. According to the method, graphite oxide is modified by diamine, and amido is introduced into the graphite oxide, so that an interface action between the graphite oxide and nylon is enhanced, and the mechanical property and the heat performance of the casting nylon are comprehensively improved. The preparation technology disclosed by the invention is simple, and the cost is low; due to the little modified graphite oxide, the impact intensity of the composite is obviously improved; when the hexanediamine modified graphite oxide content is 0.1 percent, the impact intensity of the composite is improved by 62 percent than that of pure nylon, and the tensile strength of the composite is also obviously improved; the glass-transition temperature is up to 93.9 DEG C and is improved by 16.3 DEG C than that of pure nylon, and the heat performance is obviously improved.
Description
Technical field
The present invention relates to the preparation method of a kind of monomer cast nylon/modified Nano oxidized graphite composite material, belong to the polymer composite preparation field.
Technical background
Monomer cast nylon (MC nylon) is one of present most widely used engineering plastics, and it has advantages such as low cost, high yield, high reaction rate, high molecular and favorable mechanical performance.But, compare with metallic substance, MC nylon still exists the Young's modulus height, low-temperature flexibility is relatively poor, and shock strength is on the low side, and dimensional stability is bad, wear resistance under the high loading, self lubricity is not good enough, shortcomings such as wear rate is bigger make the application of MC nylon be subjected to a certain degree restriction, have carried out research widely at antifriction, enhancing, aspect such as toughness reinforcing both at home and abroad for this reason.Yet traditional properties-correcting agent and method mostly can only be improved MC nylon performance in a certain respect, and are cost to weaken other performance to a certain extent.As, add the mineral powder in toughness reinforcing, often make intensity reduce (Wang Xinhua etc. the application [J] of ultra-fine ice smoothers in MC nylon. engineering plastics are used, 2001,29 (10): 4-7); Add copolymer elastomer toughness reinforcing often with the rigidity of expendable material preciousness and thermotolerance be cost (Wang Xinhua, Zhang Qing, Zhang Xiaobin .MC copolymer nylon elastomeric properties characterization research [J]. plastics industry, 1996, (6): 55-62).
Graphite has laminate structure, after the oxygenant oxidation, obtains graphite oxide, and abundant oxygen-containing functional group is contained on the graphite oxide surface, as hydroxyl, carboxyl, epoxy group(ing) etc.Because the existence of these polar groups, graphite oxide has bigger interlamellar spacing than graphite, make some molecules can be easy to intercalation in graphite oxide and obtain intercalated nano-composite, become the important channel of polymer modification with graphite oxide and the compound preparation high-performance nano of superpolymer matrix material.
Summary of the invention
The present invention is primarily aimed at this deficiency that tensile strength, shock strength and thermotolerance can not improve simultaneously in the current MC modified nylon technology, proposes to use the graphite oxide modified MC nylon.In order to strengthen the interaction of graphite oxide and nylon, at first with the nano level particle of the ultrasonic one-tenth of graphite oxide, use the modified oxidized graphite of diamine again, so just in graphite oxide, introduced amido.Amido has two effects, the one, can with the activator isocyanate reaction; The 2nd, amido can with the nylon molecule in amide group form hydrogen bond, the interface interaction of oxidation reinforced graphite and nylon thus comprehensively improves mechanical property and the thermal characteristics of monomer cast nylon.Preparation technology of the present invention is simple, and is with low cost.
The preparation method of a kind of monomer cast nylon/modified oxidized graphite nanometer composite material may further comprise the steps:
(1), graphite oxide is put into the reactor that fills alcohol solvent, behind the ultrasonic 10min, add diamine, be warming up to 70 ℃～80 ℃, nitrogen protection behind 3～6h, obtains modified oxidized graphite after filtration, washing, the drying; Quality is than graphite oxide: diamine=1:0.5～3; The amount of described ethanol is for can realize that ultra-sonic dispersion gets final product;
(2), with the hexanolactam of 100 parts of quality at 70 ℃～80 ℃ heating and meltings, and logical nitrogen protection, the modified oxidized graphite of 0.01～1.5 part of quality is added in the above-mentioned fused solution, 70 ℃～80 ℃ were heated ultrasonic 0.5～1.5 hour down, obtain the graphite oxide hexanolactam suspension of favorable dispersity;
(3), the whole modified oxidized graphite hexanolactam suspension that step (2) is obtained adds in the reactor, and temperature remains between 90 ℃～120 ℃, adds the sodium hydroxide of 0.2～1 part of quality after the underpressure distillation, at the water of 130 ℃～140 ℃ following underpressure distillation except the dereaction generation, the activator that adds 0.2～1 part of quality again stirs fast, pours temperature in 160 ℃～180 ℃ mould, be incubated after 30～60 minutes, cooling, the demoulding obtains product.
The described diamine of step (1) meets general molecular formula H
2N (CH
2) nNH
2, n is 4,6,8,12, is specially butanediamine, hexanediamine, octamethylenediamine or dodecyl diamine.
The described activator of step (3) is Toluene-2,4-diisocyanate, 4-vulcabond or diphenylmethanediisocyanate.
It is identical in quality that every part of material recited above represents.
Beneficial effect of the present invention: compared with prior art, the present invention prepares monomer cast nylon/modified oxidized graphite nanometer composite material with the graphite oxide of diamine modification, utilize ultrasonic means to handle modified oxidized graphite, can make it realize that in nylon matrix nano level disperses; By the amido effect on the isocyanate group on the activator and the modified oxidized graphite, can strengthen the bonding action of graphite oxide and matrix nylon resin, obtain the good monomer cast nylon/modified oxidized graphite nanometer composite material of over-all properties.The thermotolerance of prepared matrix material significantly improves, and when modified oxidized content of graphite was 0.1%, the second-order transition temperature of matrix material improved 16.3 ℃ (seeing embodiment 3) than pure nylon; The purer nylon of tensile strength and shock strength also obviously increases.And preparation technology of the present invention is simple, is applicable to the preparation of massive casting.Goods can be used for bearing, gear, pulley etc., at a lot of fields substituted metal material, as copper, aluminium, steel and iron, have favorable industrial application prospect.
Description of drawings
Fig. 1 is the infrared spectrogram of the graphite oxide of hummers method preparation
Fig. 2 is the infrared spectrogram of the modified oxidized graphite of embodiment 1 hexanediamine
Fig. 3 is the pure nylon dynamic thermomechanical analysis apparatus of control group test result.
Fig. 4 is the dynamic thermomechanical analysis apparatus test result of embodiment 3 monomer cast nylons/modified oxidized graphite composite material, wherein: modified oxidized content of graphite 0.1%.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
The mechanical property of monomer cast nylon/modified oxidized graphite composite material and testing standard see attached list 1
Subordinate list 1
Embodiment 1
(1) 0.5g is put into 200ml ethanol according to the graphite oxide of hummers method preparation, behind the ultra-sonic dispersion 20min, add the hexanediamine of 0.5g, 70 ℃～80 ℃ of temperature controls, nitrogen protection, the graphite oxide that behind the 3h, filter, wash, dry back obtains modification.
(2) with the hexanolactam of 100g at 70 ℃～80 ℃ heating and meltings; under the nitrogen protection; the modified oxidized graphite 0.01g that gets step (1) acquisition puts into the fused solution of hexanolactam; 70 ℃～80 ℃ are heated down and ultrasonic 30min, obtain the modified oxidized graphite hexanolactam suspension of favorable dispersity.
(3) will add at whole graphite oxide hexanolactam suspension of step (2) gained in the there-necked flask, (vacuum tightness dewaters in 0.9～0.95MPa) distillation in 90 ℃ of decompressions down, the sodium hydroxide that adds 0.2g, (vacuum tightness is removed the moisture that dereaction produces in 0.9～0.95MPa) distillation half an hour, reenters the Toluene-2,4-diisocyanate of 0.2g 130 ℃ of decompressions, the 4-vulcabond, reaction solution poured in 160 ℃～180 ℃ the mould, be incubated after 30 minutes cooling, the demoulding obtains product.
Accompanying drawing 1 is the infrared spectrogram of graphite oxide, 1717cm
-1The place is the C=O stretching vibration in the carbonyl, 3419cm
-1Be the vibration of a hydroxyl peak clearly, the existence of oxygen-containing functional group in this explanation graphite oxide.Fig. 2 is the infrared spectrum with the modified oxidized graphite of hexanediamine, 2923cm
-1And 2850cm
-1The methylene radical stretching vibration explanation hexanediamine modification at place graphite oxide.
Prepared composite property sees attached list 2
Embodiment 2
Substantially with embodiment 1, the amount that only changes modified oxidized graphite in the step (2) is 0.05g.
Prepared composite property sees attached list 2
Embodiment 3
Substantially with embodiment 1, the amount that only changes modified oxidized graphite in the step (2) is 0.1g.The dynamic thermomechanical analysis apparatus test result shows that second-order transition temperature is 93.9 ℃ in the accompanying drawing 4, has improved 16.3 ℃ than 77.6 ℃ of pure nylon among Fig. 2.
Prepared composite property sees attached list 2
Embodiment 4
Substantially with embodiment 1, the amount that only changes modified oxidized graphite in the step (2) is 0.2g.
Prepared composite property sees attached list 2
Embodiment 5
(1) 0.5g is put into 200ml ethanol according to the graphite oxide of hummers method preparation, behind the ultra-sonic dispersion 20min, add the butanediamine of 0.5g, 70 ℃～80 ℃ of temperature controls, nitrogen protection, the graphite oxide that behind the 3h, filter, wash, dry back obtains modification.
(2) with the hexanolactam of 100g at 70 ℃～80 ℃ heating and meltings; under the nitrogen protection; get the modified oxidized graphite 0.01g that step (1) obtains; put into the fused solution of hexanolactam; 70 ℃～80 ℃ are heated down and ultrasonic 30min, obtain the modified oxidized graphite hexanolactam suspension of favorable dispersity.
(3) will add at whole graphite oxide hexanolactam suspension of step (2) gained in the there-necked flask, (vacuum tightness dewaters in 0.9～0.95MPa) distillation in 90 ℃ of decompressions down, the sodium hydroxide that adds 0.2g, (vacuum tightness is removed the moisture that dereaction produces in 0.9～0.95MPa) distillation half an hour, reenters the Toluene-2,4-diisocyanate of 0.2g 130 ℃ of decompressions, the 4-vulcabond, reaction solution poured in 160 ℃～180 ℃ the mould, be incubated after 30 minutes cooling, the demoulding obtains product.
Prepared composite property sees attached list 2
Subordinate list 2
| Performance | Control group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Modified oxidized content of graphite (%) | 0 | 0.01 | 0.05 | 0.10 | 0.20 | 0.01 |
| Tensile strength (MPa) | 78.80 | 78.83 | 82.47 | 84.22 | 71.02 | 78.85 |
| Elongation at break (%) | 12.15 | 13.80 | 19.25 | 23.80 | 5.48 | 13.84 |
| Notched Izod impact strength (kJ/m 2） | 3.58 | 3.81 | 4.46 | 5.80 | 3.05 | 3.92 |
| Second-order transition temperature (℃) | 77.6 | 80.9 | 88.8 | 93.9 | 93.4 | 81.7 |
The data that provided by subordinate list 2 as can be seen, the adding of a spot of modified oxidized graphite, the shock strength of matrix material just obviously increases, when the modified oxidized content of graphite of hexanediamine is 0.1%, the shock strength of matrix material has improved 62% than pure nylon, and tensile strength also obviously increases; Second-order transition temperature has reached 93.9 ℃, has improved 16.3 ℃ than pure nylon, and thermal characteristics significantly strengthens.
Claims (3)
1. the preparation method of monomer cast nylon/modified oxidized graphite nanometer composite material is characterized by and may further comprise the steps:
(1), graphite oxide and diamine are put into the reactor that fills alcohol solvent, behind the ultra-sonic dispersion, be warming up to 70 ℃～80 ℃, nitrogen protection behind 3～6h, obtains modified oxidized graphite after filtration, washing, the drying; Quality is than graphite oxide: diamine=1:0.5～3; The amount of described ethanol is for can realize that ultra-sonic dispersion gets final product;
(2), with the hexanolactam of 100 parts of quality at 70 ℃～80 ℃ heating and meltings, and logical nitrogen protection, the modified oxidized graphite of 0.01～1.5 part of quality is added in the above-mentioned fused solution, 70 ℃～80 ℃ were heated ultrasonic 0.5～1.5 hour down, obtain the graphite oxide hexanolactam suspension of favorable dispersity;
(3), the whole modified oxidized graphite hexanolactam suspension that step (2) is obtained adds in the reactor, and temperature remains between 90 ℃～120 ℃, adds the sodium hydroxide of 0.2～1 part of quality after the underpressure distillation, at the water of 130 ℃～140 ℃ following underpressure distillation except the dereaction generation, the activator that adds 0.2～1 part of quality again stirs fast, pours temperature in 160 ℃～180 ℃ mould, be incubated after 30～60 minutes, cooling, the demoulding obtains product.
2. the preparation method of monomer cast nylon as claimed in claim 1/modified oxidized graphite nanometer composite material, it is characterized by the described diamine of step (1) is butanediamine, hexanediamine, octamethylenediamine or dodecyl diamine.
3. the preparation method of monomer cast nylon as claimed in claim 1/modified oxidized graphite nanometer composite material, it is characterized by the described activator of step (3) is Toluene-2,4-diisocyanate, 4-vulcabond or diphenylmethanediisocyanate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962026A (en) * | 2015-07-09 | 2015-10-07 | 河北工业大学 | Preparing method of novel composite compatilizer |
| CN105801840A (en) * | 2016-04-08 | 2016-07-27 | 河南科技大学 | Nanoparticle reinforced self-lubricated cast nylon composite shaft sleeve and manufacturing method thereof |
| CN106221199A (en) * | 2016-08-04 | 2016-12-14 | 苏州锐特捷化工制品有限公司 | A kind of high strength graphite alkene nylon composite junction brick preparation method |
| CN106243701A (en) * | 2016-08-01 | 2016-12-21 | 苏州锐特捷化工制品有限公司 | A kind of preparation method of high temperature resistant expansion composite environmental-friendly construction substrate |
| CN106497034A (en) * | 2016-11-14 | 2017-03-15 | 河北工业大学 | A kind of oil filled mc nylon/rare earth/graphene oxide composite material |
| JP2017210544A (en) * | 2016-05-25 | 2017-11-30 | 株式会社豊田中央研究所 | Low-linear-expansion polyamide resin composition and polyamide resin molding composed of the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007047084A2 (en) * | 2005-10-14 | 2007-04-26 | The Trustees Of Princeton University | Thermally exfoliated graphite oxide |
| CN101928457A (en) * | 2010-05-18 | 2010-12-29 | 赵明久 | Carbon-based nano cast nylon composite material and in-situ polymerization preparation method thereof |
| CN102942694A (en) * | 2012-10-17 | 2013-02-27 | 河南科技大学 | Oil-filled monomer casting nylon composite material |
-
2013
- 2013-07-04 CN CN201310278121.8A patent/CN103304803B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007047084A2 (en) * | 2005-10-14 | 2007-04-26 | The Trustees Of Princeton University | Thermally exfoliated graphite oxide |
| CN101928457A (en) * | 2010-05-18 | 2010-12-29 | 赵明久 | Carbon-based nano cast nylon composite material and in-situ polymerization preparation method thereof |
| CN102942694A (en) * | 2012-10-17 | 2013-02-27 | 河南科技大学 | Oil-filled monomer casting nylon composite material |
Non-Patent Citations (1)
| Title |
|---|
| BINGLI PAN,ET AL: "Tribological and mechanical investigation of MC nylon reinforced by modified graphene oxide", 《WEAR》, no. 294295, 3 August 2012 (2012-08-03) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962026A (en) * | 2015-07-09 | 2015-10-07 | 河北工业大学 | Preparing method of novel composite compatilizer |
| CN105801840A (en) * | 2016-04-08 | 2016-07-27 | 河南科技大学 | Nanoparticle reinforced self-lubricated cast nylon composite shaft sleeve and manufacturing method thereof |
| CN105801840B (en) * | 2016-04-08 | 2018-03-27 | 河南科技大学 | A kind of nano-particle reinforcement moulded nylon with self-tubricating composite shaft sleeve and its manufacture method |
| JP2017210544A (en) * | 2016-05-25 | 2017-11-30 | 株式会社豊田中央研究所 | Low-linear-expansion polyamide resin composition and polyamide resin molding composed of the same |
| CN106243701A (en) * | 2016-08-01 | 2016-12-21 | 苏州锐特捷化工制品有限公司 | A kind of preparation method of high temperature resistant expansion composite environmental-friendly construction substrate |
| CN106221199A (en) * | 2016-08-04 | 2016-12-14 | 苏州锐特捷化工制品有限公司 | A kind of high strength graphite alkene nylon composite junction brick preparation method |
| CN106497034A (en) * | 2016-11-14 | 2017-03-15 | 河北工业大学 | A kind of oil filled mc nylon/rare earth/graphene oxide composite material |
| CN106497034B (en) * | 2016-11-14 | 2018-12-07 | 河北工业大学 | A kind of oil filled mc nylon/rare earth/graphene oxide composite material |
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