CN102108122A - Preparation method of high-tenacity high-flowability nylon 6 compound material - Google Patents
Preparation method of high-tenacity high-flowability nylon 6 compound material Download PDFInfo
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- CN102108122A CN102108122A CN 201110000906 CN201110000906A CN102108122A CN 102108122 A CN102108122 A CN 102108122A CN 201110000906 CN201110000906 CN 201110000906 CN 201110000906 A CN201110000906 A CN 201110000906A CN 102108122 A CN102108122 A CN 102108122A
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Abstract
The invention relates to a preparation method of a high-tenacity high-flowability nylon 6 compound material. The preparation method comprises the following steps: adding a nano inorganic particle subjected to carbonylation in a system so that a carboxyl group on the surface of the particle and the end amino group of nylon 6 are subjected to condensation reaction, thereby increasing the compatability of the nano particle and a nylon 6 substrate and improving the mechanical property of the nylon 6; on the basis of the previous step, adding a polyamide derivative with low molecular weight in the nylon 6 substrate, wherein the derivative can be used for improving the flowability of the nylon 6 within a certain range and simultaneously maintaining the original mechanical property of the nylon 6; and in the way, simultaneously adding the nylon 6 and the polyamide derivative in a high-pressure reaction kettle, so as to prepare the nylon 6 compound material by using an in-situ polymerization method. The high-tenacity high-flowability nylon 6 compound material can be widely applied to small or thin fine nylon products.
Description
Technical field
The present invention relates to a kind of preparation method with high tenacity, high workability nylon 6 matrix materials.
Technical background
Nylon 6 has isostatic intensity, hardness properties and resistance to chemical attack character, is one of kind of output maximum in the present polyamide plastics.But nylon 6 molecular weight that general polymerization obtains are low, and as engineering plastics, because the needs of mechanical property require its molecular weight higher.Because nylon has excellent barrier, be usually used in preparing nylon container or precision instrument parts, and this needs also it that lower viscosity is arranged in addition.The nylon 6 of low viscosity, higher molecular weight is developed in expectation.But method of modifying such as usually rubber plastic blend, chemical chain extension, copolymerization, filling, enhancing, the molecule that adopts be compound often can not accomplish that flowing property and mechanical property meet the requirements simultaneously.
High tenacity, high workability nylon 6 matrix materials are meant that notched Izod impact strength that matrix material obtains is big and have high melt flow index, are easy to moulding and weak point consuming time, energy consumption and cost are low.High tenacity, high workability nylon 6 is because its toughness height usually is used to replace common fragility nylon 6 material, and high workability gives material and have the fast characteristics of the mold filling demoulding, can design thinner component, saves material.
Summary of the invention
The objective of the invention is to develop a kind of preparation method, utilize nanometer SiO with high tenacity, high workability nylon 6 matrix materials
2The end amino of carboxyl and nylon 6 reacts on the surface, simultaneously, drops into low-molecular-weight amide derivatives in reactor, prepares high tenacity, high workability nylon 6 matrix materials, and the toughness height and the melt flow index of products obtained therefrom increase significantly.
The present invention includes functional modification, the high tenacity of inorganic nano-particle, the preparation of high workability nylon 6 matrix materials.The step of this method comprises:
Step 1: inorganic nano particle modified
With γ-An Bingjisanjiayangjiguiwan (AMTPS) and Succinic anhydried inorganic nano-particle is carried out modification, make its surface be with carboxylic acid functional;
Step 2: the preparation of high tenacity, high workability nylon 6 matrix materials
(1) prescription and consumption
Component: hexanolactam, carboxylated nano silicon (SiO
2-COOH), ethylene bis stearamide (EBS), deionized water;
Consumption: press hexanolactam: SiO
2The weight ratio of-COOH is 500: 0.1～5 definite hexanolactam and SiO
2The consumption of-COOH; Weight ratio by hexanolactam: EBS is the content of 500: 1～10 definite EBS of adding; Press hexanolactam: the weight ratio of deionized water 500: 5～50 determines to add the amount of deionized water;
(2) displacement that feeds intake: with hexanolactam, SiO
2-COOH, EBS and deionized water are put in the autoclave, fasten feeding cover, open water of condensation; Charging into high pure nitrogen to polymeric kettle internal pressure is 0.2Mpa～0.6Mpa, and the vent valve of outwarding winding makes the polymeric kettle internal pressure reduce to normal pressure, and above-mentioned steps operate continuously 3～4 times to drain the oxygen in the polymeric kettle fully, is fastened vent valve again;
(3) hydrolysis: when being heated to the polymerization temperature in the kettle and being 80 ℃～100 ℃, start and stir; Continue heating, made the polymerization temperature in the kettle rise to 205 ℃～220 ℃ through 0.5～1 hour again, after the still internal pressure reaches 0.3MPa～0.7MPa, reacted 2～3 hours, make the abundant open loop of hexanolactam;
(4) successive polymerization: keep the polymeric kettle internal pressure at 0.35MPa～0.7MPa, and in 0.5 hour～3 hours, make and be warming up to 250 ℃～260 ℃ in the polymeric kettle; Temperature in the kettle reaches after 250 ℃～260 ℃, opening the slow pressure release of vent valve is normal pressure until the still internal pressure, temperature in the kettle also rises to 260 ℃～270 ℃, be 0.3～0.7MPa with high pure nitrogen punching press to polymeric kettle internal pressure more afterwards, controlled temperature is at 260 ℃～270 ℃, reacts that (this exhaust process can repeat several times in 2 hours～6 hours, but notice that each denitrogen gas is too not fast, prevent that the polymeric kettle internal reaction is too violent, heat release is many, and it is too fast to cause temperature to rise);
(5) balance discharging: open vent valve, make the near normal pressure of pressure in the polymeric kettle, when treating near 225 ℃～240 ℃ of temperature, outward winding bleeder valve at the bottom of the polymeric kettle, allow product flow out naturally,, and pull into thread through the cold rinse bank moulding, products obtained therefrom is put into pan mill pulverize into particle, 90 ℃ of dry 24h of vacuum.
Below the present invention made further specify.
The present invention is the preparation method of a kind of high tenacity, high workability nylon 6 matrix materials, and it utilizes SiO
2The end amino of the carboxyl of inorganic nano-particle sub-surface and nylon 6 reacts, and increases the interface compatibility of nanoparticle and nylon-6 matrix body, and the molecule between the interface connects forges the toughness that has increased matrix material.Ethylene bis stearamide (EBS) contains amido linkage because its molecule connects in the forging, has certain consistency to a certain extent with the nylon-6 matrix body, but also there is certain acid amides permutoid reaction, causes the molecular weight and molecular weight of nylon 6, thereby reduced the mechanical property of nylon 6.In the preparation process of high tenacity, high workability nylon 6 matrix materials, need select SiO
2The optimum content of-COOH and EBS makes the performance of composites of gained reach best.This nylon is having good application prospects aspect production thin-walled device and the Reinforced Nylon significant advantage being arranged aspect automobile, power tool, sports equipment and the equipment component.
Description of drawings
Fig. 1 is the notched Izod impact strength contrast histogram of Comparative Examples of the present invention and embodiment product;
Fig. 2 is the melting index contrast histogram of Comparative Examples of the present invention and embodiment product.
Embodiment
Can explain the present invention with reference to following examples and comparative example, but the present invention is not limited to these embodiment:
Table 1 Example formulations (unit: gram)
Preparation technology:
SiO
2The preparation of-COOH: will soak two days later 4g SiO with aqueous hydrochloric acid
2Nanoparticle joins and fills in the 100mL dry toluene, and ultrasonic 30min adds 4mLAMTPS again in reaction flask, and 100 ℃ of reaction 20h prepare SiO
2-NH
2Particle.Again with 2g SiO
2-NH
2Put into 80mL N, among the N '-dimethyl formamide (DMF), ultrasonic 30min adds 3g Succinic anhydried and 0.5mL triethylamine in system, and 70 ℃ of reaction 14h prepare SiO
2-COOH nanoparticle.
Except adopting SiO
2Beyond the nanoparticle, can also be with other nanoparticle, as TiO
2, CaCO
3Deng.
Displacement feeds intake: with hexanolactam, SiO
2-COOH, EBS and deionized water are put in the autoclave, fasten feeding cover, open water of condensation; Charging into high pure nitrogen to polymeric kettle internal pressure is 0.2MPa～0.6MPa, and the vent valve of outwarding winding makes the polymeric kettle internal pressure reduce to normal pressure, and above-mentioned steps operate continuously 3～4 times to drain the oxygen in the polymeric kettle fully, is fastened vent valve again;
Hydrolysis: when being heated to the polymerization temperature in the kettle and being 80 ℃～100 ℃, start and stir; Continue heating, made the polymerization temperature in the kettle rise to 205 ℃～220 ℃ through 0.5～1 hour again, after the still internal pressure reaches 0.3MPa～0.7MPa, reacted 2～3 hours, make the abundant open loop of hexanolactam;
Successive polymerization: keep the polymeric kettle internal pressure at 0.35MPa～0.7MPa, and in 0.5 hour～3 hours, make and be warming up to 250 ℃～260 ℃ in the polymeric kettle; Temperature in the kettle reaches after 250 ℃～260 ℃, opening the slow pressure release of vent valve is normal pressure until the still internal pressure, temperature in the kettle also rises to 260 ℃～270 ℃, be 0.3～0.7MPa with high pure nitrogen punching press to polymeric kettle internal pressure more afterwards, controlled temperature is at 260 ℃～270 ℃, reacts that (this exhaust process can repeat several times in 2 hours～6 hours, but notice that each denitrogen gas is too not fast, prevent that the polymeric kettle internal reaction is too violent, heat release is many, and it is too fast to cause temperature to rise);
(5) balance discharging: open vent valve, make the pressure in the polymeric kettle reduce to normal pressure, when treating near 225 ℃～240 ℃ of temperature, outward winding bleeder valve at the bottom of the polymeric kettle, allow product flow out naturally,, and pull into thread through the cold rinse bank moulding, products obtained therefrom is put into pan mill pulverize into particle, 90 ℃ of dry 24h of vacuum.
By table 1～3 and Fig. 1, Fig. 2 as seen, the notched Izod impact strength of the above embodiment of the present invention II, embodiment III and embodiment IV product increases a lot than Comparative Examples I, shows toughness the improving a lot than Comparative Examples product of the embodiment product of product.And the melting index of embodiment II, embodiment III and embodiment IV product also is significantly increased than Comparative Examples I, shows fluidity of molten the improving a lot than Comparative Examples product of the embodiment product of product.
Enclose notch shock performance test and the melt flow index test result of each embodiment below:
The notch shock The performance test results of the nylon 6 of the different embodiment of table 2
The melt flow index test result of the nylon 6 of the different embodiment of table 3
Claims (9)
1. the preparation method of a high tenacity, high workability nylon 6 matrix materials is characterized in that following steps:
Step 1: inorganic nano particle modified
With γ-An Bingjisanjiayangjiguiwan and Succinic anhydried inorganic nano-particle is carried out modification, make its surface be with carboxylic acid functional;
Step 2: the preparation of high tenacity, high workability nylon 6 matrix materials
Utilize hexanolactam in the presence of the amide derivatives of oligopolymer and surperficial carboxylated inorganic nano-particle, in-situ polymerization is prepared high tenacity, high workability nylon 6 matrix materials.
2. according to claim 1, the modification of inorganic nano-particle, it is characterized in that described reaction conditions is: temperature of reaction is 80～150 ℃, the reaction times is 15～30h.
3. according to claim 1, the component that the preparation process of high tenacity, high workability nylon 6 matrix materials is used comprises hexanolactam, carboxylated nano silicon (SiO
2-COOH), ethylene bis stearamide (EBS) and deionized water.
4. according to claim 1, each amounts of components of preparation high tenacity, high workability nylon 6 matrix materials is hexanolactam and SiO
2The weight ratio of-COOH is 500: 0.5～2.5; The weight ratio of hexanolactam and EBS is 500: 1～10; The weight ratio of hexanolactam and deionized water 500: 10～15.
5. according to claim 1, in the process of preparation high tenacity, high workability nylon 6 matrix materials reaction system oxygen (air) is replaced: with hexanolactam, SiO
2-COOH, EBS and deionized water are put in the autoclave, fasten feeding cover, open water of condensation; Charging into high pure nitrogen to polymeric kettle internal pressure is 0.2MPa～0.6MPa, and the vent valve of outwarding winding makes the polymeric kettle internal pressure reduce to normal pressure, above-mentioned steps operate continuously 3～4 times, and displacement drains the air in the polymeric kettle fully, fastens vent valve again.
6. according to claim 1, the hydrolysis in the process of preparation high tenacity, high workability nylon 6 matrix materials: when being heated to the polymerization temperature in the kettle and being 80 ℃～100 ℃, start and stir; Continue heating, made the polymerization temperature in the kettle rise to 205 ℃～220 ℃ through 0.5～1 hour again, after the still internal pressure reaches 0.3MPa～0.7MPa, reacted 2-3 hour, make the abundant open loop of hexanolactam;
7. according to claim 1, the successive polymerization in the process of preparation high tenacity, high workability nylon 6 matrix materials: keep the polymeric kettle internal pressure at 0.35MPa～0.7MPa, and in 0.5 hour～3 hours, make and be warming up to 250 ℃～260 ℃ in the polymeric kettle; Temperature in the kettle reaches after 250 ℃～260 ℃, opening the slow pressure release of vent valve is normal pressure until the still internal pressure, temperature in the kettle also rises to 260 ℃～270 ℃, be 0.3～0.7MPa with high pure nitrogen punching press to polymeric kettle internal pressure more afterwards, controlled temperature reacted 2 hours～6 hours at 260 ℃～270 ℃;
8. according to claim 1, balance discharging in the process of preparation high tenacity, high workability nylon 6 matrix materials: open vent valve, make the near normal pressure of pressure in the polymeric kettle, when treating near 225 ℃～240 ℃ of temperature, outward winding bleeder valve at the bottom of the polymeric kettle allows product flow out naturally, through the cold rinse bank moulding, and pull into threadly, products obtained therefrom is put into pan mill pulverize into particle.
9. according to claim 1, the drying conditions in the process of preparation high tenacity, high workability nylon 6 matrix materials is: 90 ℃ of dry 24h of vacuum.
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Cited By (6)
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| CN105906803A (en) * | 2016-04-22 | 2016-08-31 | 扬州赛尔达尼龙制造有限公司 | Preparation method of nano silicon dioxide surface-grafted MC nylon composite material |
| CN106000207A (en) * | 2016-07-20 | 2016-10-12 | 江苏海阳锦纶新材料有限公司 | Caprolactam additive solution preparation device and method |
| CN106062090A (en) * | 2013-10-07 | 2016-10-26 | Ppg工业俄亥俄公司 | Treated fillers, compositions containing same, and articles prepared therefrom |
| CN110054811A (en) * | 2019-03-11 | 2019-07-26 | 常州瑞坦商贸有限公司 | A kind of rubber wear-resisting floor |
| CN115232302A (en) * | 2022-08-30 | 2022-10-25 | 杭州聚合顺新材料股份有限公司 | Method for simply and rapidly preparing nylon 66 nano composite material |
| CN115521611A (en) * | 2022-10-25 | 2022-12-27 | 厦门市嘉能科技有限公司 | High-fluidity nylon material for sealing ring and preparation method thereof |
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| US6979704B1 (en) * | 2002-10-29 | 2005-12-27 | Jds Uniphase Corporation | Optical polymer blend with bimodal particle sizes |
| CN1844242A (en) * | 2006-04-28 | 2006-10-11 | 湘潭大学 | Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials |
| CN101570590A (en) * | 2009-05-27 | 2009-11-04 | 湘潭大学 | Preparation method for organically-modified nano-silica/nylon 66 composite material |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6979704B1 (en) * | 2002-10-29 | 2005-12-27 | Jds Uniphase Corporation | Optical polymer blend with bimodal particle sizes |
| CN1844242A (en) * | 2006-04-28 | 2006-10-11 | 湘潭大学 | Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106062090A (en) * | 2013-10-07 | 2016-10-26 | Ppg工业俄亥俄公司 | Treated fillers, compositions containing same, and articles prepared therefrom |
| TWI657109B (en) * | 2013-10-07 | 2019-04-21 | 片片堅俄亥俄州工業公司 | Treated fillers, compositions containing same, and articles prepared therefrom |
| CN105906803A (en) * | 2016-04-22 | 2016-08-31 | 扬州赛尔达尼龙制造有限公司 | Preparation method of nano silicon dioxide surface-grafted MC nylon composite material |
| CN106000207A (en) * | 2016-07-20 | 2016-10-12 | 江苏海阳锦纶新材料有限公司 | Caprolactam additive solution preparation device and method |
| CN106000207B (en) * | 2016-07-20 | 2019-04-19 | 江苏海阳锦纶新材料有限公司 | A kind of caprolactam additive solution device for formulating and method |
| CN110054811A (en) * | 2019-03-11 | 2019-07-26 | 常州瑞坦商贸有限公司 | A kind of rubber wear-resisting floor |
| CN115232302A (en) * | 2022-08-30 | 2022-10-25 | 杭州聚合顺新材料股份有限公司 | Method for simply and rapidly preparing nylon 66 nano composite material |
| CN115232302B (en) * | 2022-08-30 | 2024-01-05 | 杭州聚合顺新材料股份有限公司 | Method for simply, conveniently and rapidly preparing nylon 66 nanocomposite |
| CN115521611A (en) * | 2022-10-25 | 2022-12-27 | 厦门市嘉能科技有限公司 | High-fluidity nylon material for sealing ring and preparation method thereof |
| CN115521611B (en) * | 2022-10-25 | 2023-09-19 | 厦门市嘉能科技有限公司 | High-fluidity nylon material for sealing ring and preparation method thereof |
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