CN104513478A - Integrated nano-toughened PA6 nanocomposite material - Google Patents
Integrated nano-toughened PA6 nanocomposite material Download PDFInfo
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- CN104513478A CN104513478A CN201410794555.8A CN201410794555A CN104513478A CN 104513478 A CN104513478 A CN 104513478A CN 201410794555 A CN201410794555 A CN 201410794555A CN 104513478 A CN104513478 A CN 104513478A
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- coupling agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/12—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to nitrogen-containing macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an integrated nano-toughened PA6 nanocomposite material. The integrated nano-toughened PA6 nanocomposite material comprises the following raw materials in parts by mass: 70-90 parts of PA6, 10-20 parts of PE, 0.5-5 parts of maleic anhydride, 0.1-0.3 part of an antioxygen, 0.05-0.1 part of a catalyst I, 0.05-0.1 part of a catalyst II and 1-3 parts of nanoemulsion, wherein the nanoemulsion is prepared in the following steps: 1), adding 1-3 parts of nanopowder into a coupling agent solution, and uniformly mixing; 2) regulating pH to be 6.5-7.5; 3) performing ultrasonic dispersion into the uniform emulsion. Through integral formula design, the catalyst I and the catalyst II are introduced into a system; in the preparation process of the composite material, in-situ grafting can be achieved; through cooperation of a matrix and various functional auxiliary agents, the toughness of nylon is greatly improved.
Description
Technical field
The present invention relates to the toughness reinforcing PA6 nano composite material of a kind of integrated nanometer.
Background technology
Nylon is the general designation of polymeric amide, is the extrusion resin that in five large general engineering plastic, output is maximum, kind is maximum, most widely used, over-all properties is the most excellent.In polyamide resin, output and the consumption of nylon 6 and nylon66 fiber are maximum, account for about 90% of total polymeric amide, and nylon mainly has outstanding feature in mechanics, chemistry, thermal property etc.
The tenacity increased nylon main raw material now commercially applied is: POE grafting, EPDM grafting, PE grafted material etc., but is mainly all first by plastics grafting, and then with plastics twin-screw extrusion granulation, increase the toughness of plastics.But this technique is simple not, and the degree that the toughness of nylon improves is inadequate.
Improve the toughness of nylon, key point is also overall formula, must consider the consistency of toughner, other various functional agents and matrix resin, the problems such as viscosity coupling.
Summary of the invention
The object of the invention is to the toughness reinforcing PA6 nano composite material of a kind of integrated nanometer.
The technical solution used in the present invention is:
The toughness reinforcing PA6 nano composite material of integration nanometer, it is made up of the raw material of following mass parts: the maleic anhydride of PE, 0.5-5 part of PA6,10-20 part of 70-90 part, the oxidation inhibitor of 0.1-0.3 part, 0.05-0.1 part I class catalyzer, 0.05-0.1 part II class catalyzer, the nanoemulsions of 1-3 part, described nanoemulsions is preparation like this:
1) 1-3 part nano-powder joins in coupling agent solution, mixes;
2) pH to 6.5-7.5 is adjusted;
3) ultrasonic disperse becomes homogeneous emulsion.
Described oxidation inhibitor is at least one in Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant, composite antioxidant.
Described I class catalyzer is solubility bi-metal oxide catalyst, and II described class catalyzer is sodium caprolactam(ate).
Described nano-powder is nano imvite.
Described coupling agent solution is coupling agent with ethanol contend than being 1:(0.8-1.2) mixture.
Described coupling agent is at least one in silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, rare-earth coupling agent.
Described oxidation inhibitor is 1010,1076,168,264,1098,300,1024,2246,697,3114,330,412S, 626,835, at least one in B1171, B215, B225, B900, DLTP, DSTP, TNPP.
Described coupling agent is at least one in KH550, KH560, KH570, KH580, KH602, KH792, NDZ-101, NDZ-102, NDZ-105, NDZ-130, NDZ-131, NDZ-132, NDZ-133, NDZ-201, NDZ-401, NDZ-311, NDZ-311W.
The invention has the beneficial effects as follows: the present invention is designed by integral formula, by in maleic anhydride, I class catalyzer, II class catalyzer introducing system, in the process of composite processing, situ-formed graft can be realized, and by the coordinated of matrix and various functional agent, greatly improve the toughness of nylon.
Embodiment
The toughness reinforcing PA6 nano composite material of integration nanometer, it is made up of the raw material of following mass parts: the maleic anhydride of PE, 0.5-5 part of PA6,10-20 part of 70-90 part, the oxidation inhibitor of 0.1-0.3 part, 0.05-0.1 part I class catalyzer, 0.05-0.1 part II class catalyzer, the nanoemulsions of 1-3 part, described nanoemulsions is preparation like this:
1) 1-3 part nano imvite joins in coupling agent solution, mixes;
2) with hydrochloric acid adjustment pH to 7;
3) ultrasonic disperse becomes homogeneous emulsion.
Described coupling agent solution is coupling agent with ethanol contend than being 1:(0.8-1.2) mixture; Preferably, be the mixture of 1:1.
Described coupling agent is at least one in silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, rare-earth coupling agent; Preferably, described coupling agent is at least one in KH550, KH560, KH570, KH580, KH602, KH792, NDZ-101, NDZ-102, NDZ-105, NDZ-130, NDZ-131, NDZ-132, NDZ-133, NDZ-201, NDZ-401, NDZ-311, NDZ-311W.
Described oxidation inhibitor is at least one in Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant, composite antioxidant; Preferably, described oxidation inhibitor is 1010,1076,168,264,1098,300,1024,2246,697,3114,330,412S, 626,835, at least one in B1171, B215, B225, B900, DLTP, DSTP, TNPP.
Described I class catalyzer is solubility bi-metal oxide catalyst, and II described class catalyzer is sodium caprolactam(ate).
Preferably, described I class catalyzer has μ-oxygen and connects bimetallic alkoxide structure: (RO)
n-M-O-M '-O-M (OR)
n; Wherein M ' can be divalent metal as Cr, Mn, Fe, Co, Zn, Mo; M is Al(III) or Ti(IV), R is generally a kind of alkyl.
The preparation method of the toughness reinforcing PA6 nano composite material of above-mentioned integrated nanometer, step is:
Various raw material is mixed, melt extrudes, granulation.
Below in conjunction with specific embodiment, formula of the present invention is described further:
embodiment 1:
The toughness reinforcing PA6 nano composite material of integration nanometer, its table composed as follows of filling a prescription:
table 1: the formula composition of the toughness reinforcing PA6 nano composite material of integrated nanometer
Described nanoemulsions is preparation like this:
1) 1 mass parts nano imvite joins in the coupling agent solution (ethanol and coupling agent KH550 volume ratio are the mixture of 1:1) of 50 mass parts, mixes;
2) with hydrochloric acid adjustment pH to 7;
3) ultrasonic disperse becomes homogeneous emulsion.
embodiment 2:
The toughness reinforcing PA6 nano composite material of integration nanometer, its table composed as follows of filling a prescription:
table 2: the formula composition of the toughness reinforcing PA6 nano composite material of integrated nanometer
Described nanoemulsions is preparation like this:
1) 1 mass parts nano imvite joins in the coupling agent solution (ethanol and coupling agent KH550 volume ratio are the mixture of 1:1) of 50 mass parts, mixes;
2) with hydrochloric acid adjustment pH to 7;
3) ultrasonic disperse becomes homogeneous emulsion.
comparative example:
A kind of toughness reinforcing PA6 nano composite material, its table composed as follows of filling a prescription:
table 3: the formula composition of toughness reinforcing PA6 nano composite material
test the performance of embodiment and comparative example and PA6, its result is as following table:
table 4: the performance of matrix material and blank PA6
In described embodiment, the structural formula of I class catalyzer is: (i-PrO)
2al-O-Fe-O-Al (O-i Pr)
2.
Claims (8)
1. the toughness reinforcing PA6 nano composite material of integrated nanometer, it is characterized in that: it is made up of the raw material of following mass parts: the maleic anhydride of PE, 0.5-5 part of PA6,10-20 part of 70-90 part, the oxidation inhibitor of 0.1-0.3 part, the nanoemulsions of 0.05-0.1 part I class catalyzer, 0.05-0.1 part II class catalyzer, 1-3 part, described nanoemulsions is preparation like this:
1) 1-3 part nano-powder joins in coupling agent solution, mixes;
2) pH to 6.5-7.5 is adjusted;
3) ultrasonic disperse becomes homogeneous emulsion.
2. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 1, is characterized in that: described oxidation inhibitor is at least one in Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester kind antioxidant, composite antioxidant.
3. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 1, is characterized in that: described I class catalyzer is solubility bi-metal oxide catalyst, and II described class catalyzer is sodium caprolactam(ate).
4. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 1, is characterized in that: described nano-powder is nano imvite.
5. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 1, is characterized in that: described coupling agent solution is coupling agent with ethanol contend than being 1:(0.8-1.2) mixture.
6. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 1, is characterized in that: described coupling agent is at least one in silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, rare-earth coupling agent.
7. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 2, is characterized in that: described oxidation inhibitor is 1010,1076,168,264,1098,300,1024,2246,697,3114,330,412S, 626,835, at least one in B1171, B215, B225, B900, DLTP, DSTP, TNPP.
8. the toughness reinforcing PA6 nano composite material of integrated nanometer according to claim 6, is characterized in that: described coupling agent is at least one in KH550, KH560, KH570, KH580, KH602, KH792, NDZ-101, NDZ-102, NDZ-105, NDZ-130, NDZ-131, NDZ-132, NDZ-133, NDZ-201, NDZ-401, NDZ-311, NDZ-311W.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685985A (en) * | 2022-04-11 | 2022-07-01 | 海信（山东）冰箱有限公司 | High-strength high-wear-resistance easy-to-mold PA66 material, preparation method thereof and refrigerator door hinge |
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| KR20110040490A (en) * | 2009-10-14 | 2011-04-20 | 현대자동차주식회사 | Polyamid/polyolefin/nano-clay composites for the fuel tube outer layer automotive parts improving permeable-resistance of fuel |
| CN102108205A (en) * | 2009-12-25 | 2011-06-29 | 上海普利特复合材料股份有限公司 | Low-smell toughening polyamide (PA) 6 material and preparation method thereof |
| CN102775777A (en) * | 2012-03-12 | 2012-11-14 | 东莞市信诺橡塑工业有限公司 | Supernylon 6 alloy and method for prearing supernylon 6 alloy by means of in-situ reaction compatibilization |
| CN102796340A (en) * | 2012-09-05 | 2012-11-28 | 东莞市信诺橡塑工业有限公司 | High-density polyethylene/polyamide 6 laminated barrier material prepared by in-situ reaction compatibilization method and preparation method thereof |
| CN103122142A (en) * | 2013-01-25 | 2013-05-29 | 上海瑞尔实业有限公司 | Preparation method of nano reinforced and toughened PA6 modified alloy |
-
2014
- 2014-12-19 CN CN201410794555.8A patent/CN104513478A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110040490A (en) * | 2009-10-14 | 2011-04-20 | 현대자동차주식회사 | Polyamid/polyolefin/nano-clay composites for the fuel tube outer layer automotive parts improving permeable-resistance of fuel |
| CN102108205A (en) * | 2009-12-25 | 2011-06-29 | 上海普利特复合材料股份有限公司 | Low-smell toughening polyamide (PA) 6 material and preparation method thereof |
| CN102775777A (en) * | 2012-03-12 | 2012-11-14 | 东莞市信诺橡塑工业有限公司 | Supernylon 6 alloy and method for prearing supernylon 6 alloy by means of in-situ reaction compatibilization |
| CN102796340A (en) * | 2012-09-05 | 2012-11-28 | 东莞市信诺橡塑工业有限公司 | High-density polyethylene/polyamide 6 laminated barrier material prepared by in-situ reaction compatibilization method and preparation method thereof |
| CN103122142A (en) * | 2013-01-25 | 2013-05-29 | 上海瑞尔实业有限公司 | Preparation method of nano reinforced and toughened PA6 modified alloy |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114685985A (en) * | 2022-04-11 | 2022-07-01 | 海信（山东）冰箱有限公司 | High-strength high-wear-resistance easy-to-mold PA66 material, preparation method thereof and refrigerator door hinge |
| CN114685985B (en) * | 2022-04-11 | 2024-01-23 | 海信冰箱有限公司 | High-strength high-wear-resistance easy-forming PA66 material, preparation method thereof and refrigerator door hinge |
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