CN103304803B - The preparation method of a kind of monomer cast nylon/modified graphite oxide nano composite material - Google Patents
The preparation method of a kind of monomer cast nylon/modified graphite oxide nano composite material Download PDFInfo
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- CN103304803B CN103304803B CN201310278121.8A CN201310278121A CN103304803B CN 103304803 B CN103304803 B CN 103304803B CN 201310278121 A CN201310278121 A CN 201310278121A CN 103304803 B CN103304803 B CN 103304803B
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Abstract
The present invention is the preparation method of a kind of monomer cast nylon/modified graphite oxide nano composite material, present method diamine modified graphite oxide, amido is introduced, thus the interface interaction of oxidation reinforced graphite and nylon, comprehensive mechanical property and the thermal characteristics improving monomer cast nylon in graphite oxide.Preparation technology of the present invention is simple, with low cost, due to adding of a small amount of modified graphite oxide, the shock strength of matrix material just obviously increases, when hexanediamine modified graphite oxide content is 0.1%, the shock strength of matrix material improves 62% than pure nylon, and tensile strength also obviously increases; Second-order transition temperature reaches 93.9 DEG C, and improve 16.3 DEG C than pure nylon, thermal characteristics significantly strengthens.
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 field of high polymer composite material preparation.
Technical background
Monomer cast nylon (MC nylon) is one of current most widely used engineering plastics, and it has the advantages such as low cost, high yield, high reaction rate, high molecular and good mechanical property.But, compared with metallic substance, it is high that MC nylon still also exists Young's modulus, low-temperature flexibility is poor, and shock strength is on the low side, and dimensional stability is bad, wear resistance under high loading, self lubricity is not good enough, the shortcomings such as wear rate is larger, make the application of MC nylon by restriction to a certain extent, for this reason domestic and international antifriction, enhancing, toughness reinforcing etc. in conduct extensive research.But traditional properties-correcting agent and method mostly can only improve MC nylon performance in a certain respect, and to a certain extent to weaken other performance for cost.As, add mineral powder while toughness reinforcing, often make intensity reduce (Wang Xinhua etc. the application of ultra-fine ice smoothers in MC nylon [J]. engineering plastics are applied, 2001,29 (10): 4-7); Add copolymer elastomer toughness reinforcing often with the rigidity of expendable material preciousness and thermotolerance be cost (Wang Xinhua, elastomeric performance characterization research [J] of Zhang Qing, Zhang little Bin .MC copolymer nylon. plastics industry, 1996, (6): 55-62).
Graphite has laminate structure, after oxidizing, obtains graphite oxide, and abundant oxygen-containing functional group is contained, as hydroxyl, carboxyl, epoxy group(ing) etc. in graphite oxide surface.Due to the existence of these polar groups, graphite oxide has larger interlamellar spacing than graphite, make some molecules can be easy to be intercalation in graphite oxide obtain intercalated nano-composite, prepare by graphite oxide and superpolymer compound the important channel that High performance nanometer composite material has become polymer modification.
Summary of the invention
This deficiency that the present invention can not improve mainly for tensile strength, shock strength and thermotolerance in current MC modified nylon technology simultaneously, proposes to use graphite oxide modified MC nylon.In order to strengthen the interaction of graphite oxide and nylon, first by the nano level particle of ultrasonic for graphite oxide one-tenth, then using diamine modified graphite oxide, so just in graphite oxide, introducing amido.Amido has two effects, one be can with activator isocyanate reaction; Two is that amido can form hydrogen bond with the amide group in nylon molecules, the interface interaction of oxidation reinforced graphite and nylon thus, comprehensive mechanical property and the thermal characteristics improving monomer cast nylon.Preparation technology of the present invention is simple, with low cost.
A preparation method for monomer cast nylon/modified graphite oxide nano composite material, comprises the following steps:
(1), graphite oxide is put into the reactor filling alcohol solvent, after ultrasonic 10min, add diamine, be warming up to 70 DEG C ~ 80 DEG C, nitrogen protection, after 3 ~ 6h, after filtration, washing, drying, obtain modified graphite oxide; Quality is than graphite oxide: diamine=1:0.5 ~ 3; The amount of described ethanol is for can realize ultrasonic disperse;
(2), by the hexanolactam of 100 parts of quality at 70 DEG C ~ 80 DEG C heating and meltings, and logical nitrogen protection, the modified graphite oxide of 0.01 ~ 1.5 part of quality is added in above-mentioned fused solution, heat ultrasonic 0.5 ~ 1.5 hour at 70 DEG C ~ 80 DEG C, obtain the graphite oxide hexanolactam suspension of favorable dispersity;
(3), whole modified graphite oxide hexanolactam suspension step (2) obtained add in reactor, and temperature remains between 90 DEG C ~ 120 DEG C, adds the sodium hydroxide of 0.2 ~ 1 part of quality after underpressure distillation, the water that underpressure distillation produces except dereaction at 130 DEG C ~ 140 DEG C, add the activator of 0.2 ~ 1 part of quality again, rapid stirring, pour temperature in the mould of 160 DEG C ~ 180 DEG C, be incubated after 30 ~ 60 minutes, cooling, the demoulding, obtains product.
Diamine described in 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.
Activator described in step (3) is Toluene-2,4-diisocyanate, 4-vulcabond or diphenylmethanediisocyanate.
It is identical in quality that every serving matter recited above represents.
Beneficial effect of the present invention: compared with prior art, the graphite oxide of the present invention's diamine modification prepares monomer cast nylon/modified graphite oxide nano composite material, utilize ultrasonic means process modified graphite oxide, can make it in nylon matrix, realize nano-scale dispersion; By the isocyanate group on activator and the amido effect on modified graphite oxide, the bonding action of graphite oxide and base nylon resin can be strengthened, obtain monomer cast nylon/modified graphite oxide nano composite material that over-all properties is good.The thermotolerance of prepared matrix material significantly improves, and when modified graphite oxide content is 0.1%, the second-order transition temperature of matrix material improves 16.3 DEG C (see embodiments 3) than pure nylon; Tensile strength and the purer nylon of shock strength also obviously increase.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 good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the standby graphite oxide of hummers legal system
Fig. 2 is the infrared spectrogram of embodiment 1 hexanediamine modified graphite oxide
Fig. 3 is control group pure nylon dynamic thermomechanical analysis apparatus test result.
Fig. 4 is the dynamic thermomechanical analysis apparatus test result of embodiment 3 monomer cast nylons/modified graphite oxide matrix material, wherein: modified graphite oxide content 0.1%.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Mechanical property and the testing standard of monomer cast nylon/modified graphite oxide matrix material see attached list 1
Subordinate list 1
Embodiment 1
(1) 0.5g is put into 200ml ethanol according to graphite oxide prepared by hummers method, after ultrasonic disperse 20min, add the hexanediamine of 0.5g, temperature control 70 DEG C ~ 80 DEG C, nitrogen protection, after 3h, filtration, washing, the dry rear graphite oxide obtaining modification.
(2) by the hexanolactam of 100g at 70 DEG C ~ 80 DEG C heating and meltings; under nitrogen protection; get the fused solution that modified graphite oxide 0.01g that step (1) obtains puts into hexanolactam; heat and ultrasonic 30min at 70 DEG C ~ 80 DEG C, obtain the modified graphite oxide hexanolactam suspension of favorable dispersity.
(3) the whole graphite oxide hexanolactam suspension in step (2) gained are added in there-necked flask, (vacuum tightness is at 0.9 ~ 0.95MPa) distillation of reducing pressure at 90 DEG C dewaters, add the sodium hydroxide of 0.2g, distill the moisture produced except dereaction half an hour 130 DEG C of decompressions (vacuum tightness is at 0.9 ~ 0.95MPa), reenter the Toluene-2,4-diisocyanate of 0.2g, 4-vulcabond, reaction solution is poured in the mould of 160 DEG C ~ 180 DEG C, be incubated after 30 minutes, cooling, the demoulding, obtains product.
Accompanying drawing 1 is the infrared spectrogram of graphite oxide, 1717cm
-1place is the C=O stretching vibration in carbonyl, 3419cm
-1be the vibration of a hydroxyl peak clearly, this illustrates the existence of oxygen-containing functional group in graphite oxide.Fig. 2 is the infrared spectrum with hexanediamine modified graphite oxide, 2923cm
-1and 2850cm
-1the methylene radical stretching vibration at place illustrates hexanediamine modification graphite oxide.
Obtained composite property sees attached list 2
Embodiment 2
Basic with embodiment 1, the amount only changing modified graphite oxide in step (2) is 0.05g.
Obtained composite property sees attached list 2
Embodiment 3
Basic with embodiment 1, the amount only changing modified graphite oxide in step (2) is 0.1g.In accompanying drawing 4, dynamic thermomechanical analysis apparatus test result display second-order transition temperature is 93.9 DEG C, improves 16.3 DEG C than 77.6 DEG C of nylon pure in Fig. 2.
Obtained composite property sees attached list 2
Embodiment 4
Basic with embodiment 1, the amount only changing modified graphite oxide in step (2) is 0.2g.
Obtained composite property sees attached list 2
Embodiment 5
(1) 0.5g is put into 200ml ethanol according to graphite oxide prepared by hummers method, after ultrasonic disperse 20min, add the butanediamine of 0.5g, temperature control 70 DEG C ~ 80 DEG C, nitrogen protection, after 3h, filtration, washing, the dry rear graphite oxide obtaining modification.
(2) by the hexanolactam of 100g at 70 DEG C ~ 80 DEG C heating and meltings; under nitrogen protection; get the modified graphite oxide 0.01g that step (1) obtains; put into the fused solution of hexanolactam; heat and ultrasonic 30min at 70 DEG C ~ 80 DEG C, obtain the modified graphite oxide hexanolactam suspension of favorable dispersity.
(3) the whole graphite oxide hexanolactam suspension in step (2) gained are added in there-necked flask, (vacuum tightness is at 0.9 ~ 0.95MPa) distillation of reducing pressure at 90 DEG C dewaters, add the sodium hydroxide of 0.2g, distill the moisture produced except dereaction half an hour 130 DEG C of decompressions (vacuum tightness is at 0.9 ~ 0.95MPa), reenter the Toluene-2,4-diisocyanate of 0.2g, 4-vulcabond, reaction solution is poured in the mould of 160 DEG C ~ 180 DEG C, be incubated after 30 minutes, cooling, the demoulding, obtains product.
Obtained composite property sees attached list 2
Subordinate list 2
| Performance | Control group | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Modified graphite oxide content (%) | 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 (DEG C) | 77.6 | 80.9 | 88.8 | 93.9 | 93.4 | 81.7 |
The data provided as can be seen from subordinate list 2, adding of a small amount of modified graphite oxide, the shock strength of matrix material just obviously increases, when hexanediamine modified graphite oxide content is 0.1%, the shock strength of matrix material improves 62% than pure nylon, and tensile strength also obviously increases; Second-order transition temperature reaches 93.9 DEG C, and improve 16.3 DEG C than pure nylon, thermal characteristics significantly strengthens.
Claims (1)
1. a preparation method for monomer cast nylon/modified graphite oxide nano composite material, is characterized by and comprise the following steps:
(1), graphite oxide and diamine are put into the reactor filling alcohol solvent, after ultrasonic disperse, be warming up to 70 DEG C ~ 80 DEG C, nitrogen protection, after 3 ~ 6h, after filtration, washing, drying, obtain modified graphite oxide; Quality is than graphite oxide: diamine=1:0.5 ~ 3; The amount of described ethanol is for can realize ultrasonic disperse;
(2), by the hexanolactam of 100 parts of quality at 70 DEG C ~ 80 DEG C heating and meltings, and logical nitrogen protection, the modified graphite oxide of 0.01 ~ 1.5 part of quality is added in above-mentioned fused solution, heat ultrasonic 0.5 ~ 1.5 hour at 70 DEG C ~ 80 DEG C, obtain the graphite oxide hexanolactam suspension of favorable dispersity;
(3), whole modified graphite oxide hexanolactam suspension step (2) obtained add in reactor, and temperature remains between 90 DEG C ~ 120 DEG C, adds the sodium hydroxide of 0.2 ~ 1 part of quality after underpressure distillation, the water that underpressure distillation produces except dereaction at 130 DEG C ~ 140 DEG C, add the activator of 0.2 ~ 1 part of quality again, rapid stirring, pour temperature in the mould of 160 DEG C ~ 180 DEG C, be incubated after 30 ~ 60 minutes, cooling, the demoulding, obtains product;
Diamine described in step (1) is butanediamine, hexanediamine, octamethylenediamine or dodecyl diamine;
Activator described in step (3) is Toluene-2,4-diisocyanate, 4-vulcabond or diphenylmethanediisocyanate.
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| CN104962026B (en) * | 2015-07-09 | 2017-05-03 | 河北工业大学 | Preparing method of composite compatilizer |
| 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 |
| JP6728976B2 (en) * | 2016-05-25 | 2020-07-22 | 株式会社豊田中央研究所 | Low linear expansion polyamide resin composition and polyamide resin molded article comprising 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 |
| 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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| 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 |
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| US7658901B2 (en) * | 2005-10-14 | 2010-02-09 | The Trustees Of Princeton University | Thermally exfoliated graphite oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| Tribological and mechanical investigation of MC nylon reinforced by modified graphene oxide;Bingli Pan,et al;《Wear》;ELSEVIER;20120803(第294-295期);第395-401页 * |
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