CN1176138C - Nylon 6/inorganic particle nano composite material direct preparation method - Google Patents

Nylon 6/inorganic particle nano composite material direct preparation method Download PDF

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Publication number
CN1176138C
CN1176138C CNB021398364A CN02139836A CN1176138C CN 1176138 C CN1176138 C CN 1176138C CN B021398364 A CNB021398364 A CN B021398364A CN 02139836 A CN02139836 A CN 02139836A CN 1176138 C CN1176138 C CN 1176138C
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nylon
composite material
polymerization
nano composite
inorganic
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CN1422901A (en
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平 张
张平
王霞瑜
魏珊珊
姜勇
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Xiangtan University
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Xiangtan University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention discloses a method for directly preparing a nylon 6/ inorganic particle nanocomposite material, which comprises: an inorganic acid ester or an inorganic acid salt is hydrolyzed to obtain even liquor; the even liquor is added to caprolactam which presents a melting state after being heated, and the mixture is evenly mixed to obtain liquor; the evenly mixed liquor is gelled under the protection of high purity nitrogen at a temperature range of 20 to 200 DEG C for 0.5 to 720 hours; after the gel is generated, the gel is polymerized into a composite material under the protection of high purity nitrogen; the nylon 6/ inorganic particle nanocomposite material is obtained by purifying the composite material. The nylon 6/ inorganic particle nanocomposite material directly prepared by the method has outstanding properties of mechanical property, heat resistance, compression resistance, solvent resistance, wear resistance, etc., and has the advantage of white product appearance, etc. The present invention has two characteristics that the inorganic nanoparticles are prepared at the original positions, and when the inorganic nanoparticles are prepared, the nylon 6 is prepared nearly simultaneously.

Description

The direct preparation method of nylon 6/ inorganic particulate nano composite material
Technical field
Content of the present invention relates to the direct preparation method of nylon 6/ inorganic particulate nano composite material, is the direct preparation method of the nano composite material of raw material by hexanolactam and inorganic acid ester or inorganic acid salt hydrolysate particularly.
Background technology
At present, the research of the nano composite material of nylon 6/ inorganic particulate has obtained a lot of achievements, the industrialization of part matrix material, but generally all use relatively classic methods such as solution-gel method at present, the intercalation polymeric method, blending methods etc. are preparation method's nano composite material directly, the whole bag of tricks all exists deficiency to some extent, for example nylon 6/ Nano composite material of montmorillonite of the employing intercalation polymeric method of suitability for industrialized production production also exists some as the product variable color, deficiencies such as complex manufacturing, blending method also exists inorganic nano-particle easily to reunite, disperse inhomogeneous, shortcoming such as size distribution is wide.
Summary of the invention
The objective of the invention is to be to seek a kind of nanoparticle and be evenly distributed, narrow diameter distribution and can control product nondiscoloration, the direct preparation method of nylon 6/ inorganic particulate nano composite material that cost is low.
The objective of the invention is to realize in the following way: the direct preparation method of a kind of nylon 6/ inorganic particulate nano composite material; with positive silicon ester; positive titanic acid ester or water glass be hydrolyzed solution uniformly; the solution of hydrolysis gained added in heating is the hexanolactam of molten be mixed into uniform solution; under the high pure nitrogen protection, carried out gel 0.5~720 hour at 20~200 ℃ then; treat that gel generates the back and aggregate into matrix material under the high pure nitrogen protection, again matrix material is carried out purifying and promptly get nylon 6/ inorganic particulate nano composite material.
In being hydrolyzed process, inorganic acid ester or inorganic acid salt add acid or alkali is made catalyzer.
Polymerization methods is a hydrolytic polymerization, uses catalyzer in the polymerization process.
Adopt successive polymerization or batchwise polymerization when hydrolytic polymerization prepares nylon 6, the different steps of polymerization process adopts different polymerization pressure and temperature, and polymerization pressure is-0.1Mpa~1Mpa that polymerization temperature is 200~280 ℃.
Advantages such as the present invention has following beneficial effect, has excellent mechanics, heat-resisting, resistance to compression, anti-solvent, performance such as wear-resisting by nylon 6/ inorganic particulate nano composite material of present method preparation, and product appearance is white.The generation of inorganic nano-particle is carried out in position among the present invention; The generation of the generation of nanoparticle and nylon 6 almost is these two characteristics of carrying out simultaneously.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment 1
Nylon 6/SiO 2The direct preparation method of nano composite material
In the 500ml there-necked flask, add the 11.3ml tetraethoxy, the acetone that adds 3.6ml water and 5ml again, the hydrochloric acid that under agitation adds 1 1M is regulated its acidity, at room temperature be hydrolyzed clear solution, add the 400 lactan fusions under 70~80 ℃ temperature of restraining oneself again, treat the whole fusions of hexanolactam after, violent stirring mixes both, the ethanol of hydrolysis generation and the acetone of adding are extracted in decompression simultaneously out.Again with the solution of gained gel 6 hours under the protection at high pure nitrogen about 100 ℃, till the solution of original homogeneous transparent becomes the clear gel that solidifies.Add the amino n-caproic acid of 6 gram 6-in the direct preparation method's of institute gel; under the protection of high pure nitrogen, gel was carried out polymerization under atmospheric pressure 15 hours at 250~260 ℃; turn off and fill the nitrogen mouth, the decompression polymerization is 14 hours under the pressure of-0.1MPa, promptly gets nylon 6/SiO behind the purifying 2Nano composite material.
Embodiment 2
Nylon 6/SiO 2The direct preparation method of nano composite material
In the 500ml there-necked flask, add the 22.6ml tetraethoxy, the acetone that adds 7.2ml water and 10ml again, the hydrochloric acid that under agitation adds 2 1M is regulated its acidity, at room temperature be hydrolyzed clear solution, add the 400 lactan fusions under 70~80 ℃ temperature of restraining oneself again, treat the whole fusions of hexanolactam after, violent stirring mixes both, the ethanol of hydrolysis generation and the acetone of adding are extracted in decompression simultaneously out.Again with the solution of gained gel 6 hours under the protection at high pure nitrogen about 100 ℃, till the solution of original homogeneous transparent becomes the clear gel that solidifies.Add the amino n-caproic acid of 6 gram 6-in the direct preparation method's of institute gel; under the protection of high pure nitrogen, gel was carried out polymerization under atmospheric pressure 15 hours at 250~260 ℃; turn off and fill the nitrogen mouth, the decompression polymerization is 14 hours under the pressure of-0.1MPa, promptly gets nylon 6/SiO behind the purifying 2Nano composite material.
Embodiment 3
Nylon 6/SiO 2The direct preparation method of nano composite material
In the 500ml there-necked flask, add the 56.5ml methyl silicate, the acetone that adds 18ml water and 20ml again, the hydrochloric acid that under agitation adds 5 1M is regulated its acidity, at room temperature be hydrolyzed clear solution, add the 400 lactan fusions under 70~80 ℃ temperature of restraining oneself again, treat the whole fusions of hexanolactam after, violent stirring mixes both, the methyl alcohol of hydrolysis generation and the acetone of adding are extracted in decompression simultaneously out.Again with the solution of gained gel 6 hours under the protection at high pure nitrogen about 100 ℃, till the solution of original homogeneous transparent becomes the clear gel that solidifies.Add the amino n-caproic acid of 6 gram 6-in the direct preparation method's of institute gel; under the protection of high pure nitrogen, gel was carried out polymerization under atmospheric pressure 15 hours at 250~260 ℃; turn off and fill the nitrogen mouth, the decompression polymerization is 14 hours under the pressure of-0.1MPa, promptly gets nylon 6/SiO behind the purifying 2Nano composite material.
Embodiment 4
Nylon 6/SiO 2The direct preparation method of nano composite material
In the beaker of 3000ml, add 565ml tetraethoxy and 180ml acetone, 180mlH 2O, the hydrochloric acid that drips 2ml1M when stirring is regulated its acidity, at room temperature be hydrolyzed clear solution, in the 10L reactor, add the 2000 lactan fusions under 70~80 ℃ temperature of restraining oneself, solution with the hydrolysis gained under agitation slowly adds in the molten caprolactam again, violent stirring mixes both, decompression 20 minutes when-0.08MPa again, and the ethanol that hydrolysis is generated and the acetone of adding are extracted out.With the solution of gained gel 6 hours under the protection at high pure nitrogen about 100 ℃; with gel under the protection of high pure nitrogen at 250~260 ℃, carried out high pressure polymerisation under 1~5atm 10 hours, turn off again and fill the nitrogen mouth; polymerization is 10 hours under-0.08MPa, promptly gets nylon 6/SiO behind the purifying 2Nano composite material.
Embodiment 5
Nylon 6/TiO 2The direct preparation method of nano composite material
Be to add positive titanium ethanolate and H at 4: 1 in molar ratio in the beaker of 3000ml 2O, 180ml acetone, add the 2000 lactan fusions under 70~80 ℃ temperature of restraining oneself, solution with the hydrolysis gained under agitation slowly adds in the molten caprolactam again, violent stirring mixes both, decompression 20 minutes when-0.08MPa again, the ethanol that hydrolysis is generated and the acetone of adding are extracted out.With the solution of gained gel 6 hours under the protection at high pure nitrogen about 100 ℃; with gel under the protection of high pure nitrogen at 250~260 ℃, carried out high pressure polymerisation under 1~5atm 15 hours, turn off again and fill the nitrogen mouth; polymerization is 8 hours under-0.08MPa, promptly gets nylon 6/TiO behind the purifying 2Nano composite material.
Embodiment 6
Nylon 6/SiO 2The direct preparation method of nano composite material
In the beaker of 3000ml, add sodium silicate and H 2The O wiring solution-forming, the hydrochloric acid that adds 1M is regulated its PH=8~10, adds the tetrahydrofuran (THF) extraction, adds 2000 lactan of restraining oneself in the tetrahydrofuran (THF) liquid that extracts, fusion under 70~80 ℃ temperature, violent stirring mixes both; Tetrahydrofuran (THF) is extracted in decompression 30 minutes when-0.08MPa again out.With the solution of gained gel 6 hours under the protection at high pure nitrogen about 100 ℃; with gel under the protection of high pure nitrogen at 250~260 ℃, carried out high pressure polymerisation under 1~5atm 15 hours, turn off again and fill the nitrogen mouth; polymerization is 8 hours under-0.08MPa, promptly gets nylon 6/SiO behind the purifying 2Nano composite material.

Claims (4)

1, the direct preparation method of a kind of nylon 6/ inorganic particulate nano composite material; it is characterized in that: with positive silicon ester; positive titanic acid ester or water glass be hydrolyzed solution uniformly; the solution of hydrolysis gained added in heating is the hexanolactam of molten be mixed into uniform solution; under the high pure nitrogen protection, carried out gel 0.5~720 hour at 20~200 ℃ then; treat that gel generates the back and aggregate into matrix material under the high pure nitrogen protection, again matrix material is carried out purifying and promptly get nylon 6/ inorganic particulate nano composite material.
2, the direct preparation method of nylon 6/ inorganic particulate nano composite material according to claim 1 is characterized in that: add acid or alkali is made catalyzer in inorganic acid ester or inorganic acid salt are hydrolyzed process.
3, the direct preparation method of nylon 6/ inorganic particulate nano composite material according to claim 1 is characterized in that: the polymerization methods hydrolytic polymerization, use catalyzer in the polymerization process.
4, as the direct preparation method of nylon 6/ inorganic particulate nano composite material as described in the claim 3, it is characterized in that: adopt successive polymerization or batchwise polymerization when hydrolytic polymerization prepares nylon 6, the different steps of polymerization process adopts different polymerization pressure and temperature, polymerization pressure is-0.1Mpa~1Mpa that polymerization temperature is 200~280 ℃.
CNB021398364A 2002-12-12 2002-12-12 Nylon 6/inorganic particle nano composite material direct preparation method Expired - Fee Related CN1176138C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130108453A (en) * 2010-12-28 2013-10-02 상하이 지니어스 어드밴스트 머티리얼 코퍼레이션, 리미티드. Nano particle/polyamide composite material, preparation method therefor, and use thereof

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CN100348665C (en) * 2006-04-28 2007-11-14 湘潭大学 Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials
CN101768351B (en) * 2008-12-29 2012-05-30 合肥杰事杰新材料股份有限公司 Method for preparing mesoporous nano particle-enhanced nylon composite material
CN103160119B (en) * 2011-12-19 2016-08-03 合肥杰事杰新材料股份有限公司 A kind of Polyamide nanometer barrier material and preparation method thereof
CN103073715B (en) * 2013-01-17 2014-12-17 湖南工业大学 Preparation method of composite material for inorganic modified melamine chlorinated isocyanurate flame-retardant nylon 6
CN103387665B (en) * 2013-07-12 2016-04-20 东华大学 A kind of preparation method of fire-retardant polyamide material
CN107383916A (en) * 2017-08-21 2017-11-24 安徽旺旺禽业科技有限公司 A kind of resistance to compression, degradable lunch box and preparation method thereof
CN107325315A (en) * 2017-08-21 2017-11-07 安徽旺旺禽业科技有限公司 A kind of antibacterial ventilative fruit-vegetable plastic wrap and preparation method thereof
CN107513215A (en) * 2017-08-21 2017-12-26 安徽旺旺禽业科技有限公司 A kind of preparation method of the polypropylene expanded insulation material containing wheat stalk
CN107353501A (en) * 2017-08-21 2017-11-17 安徽旺旺禽业科技有限公司 A kind of bamboo-plastic combined sash stuff of light durable and preparation method thereof
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130108453A (en) * 2010-12-28 2013-10-02 상하이 지니어스 어드밴스트 머티리얼 코퍼레이션, 리미티드. Nano particle/polyamide composite material, preparation method therefor, and use thereof
KR101582132B1 (en) * 2010-12-28 2016-01-04 상하이 지니어스 어드밴스트 머티리얼 코퍼레이션, 리미티드. Nano particle/polyamide composite material, preparation method therefor, and use thereof

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