CN100348665C - Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials - Google Patents

Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials Download PDF

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CN100348665C
CN100348665C CNB2006100316048A CN200610031604A CN100348665C CN 100348665 C CN100348665 C CN 100348665C CN B2006100316048 A CNB2006100316048 A CN B2006100316048A CN 200610031604 A CN200610031604 A CN 200610031604A CN 100348665 C CN100348665 C CN 100348665C
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nylon
resins
epoxy
dioxide nano
silicon dioxide
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CN1844242A (en
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张平
王霞瑜
赵才贤
陆绍荣
易兰花
姜勇
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Xiangtan University
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Xiangtan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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

Abstract

The present invention discloses an in-situ polymerization method for the preparation of nylon-6/epoxide resin/silica dioxide nano-composite, which comprises following steps of a) preparing epoxide resin siloxane hydrolysate solution by graft reaction and hydrolytic reaction; b) before or during the ring-open reaction of aminocaprolactam, introducing the epoxide resin siloxane hydrolysate solution into the medium of the ring-open reaction of the aminocaprolactam, and simultaneously, adding water and anti-oxidant; c) opening the ring of the aminocaprolactam and polymerizing the aminocaprolactam to prepare the high-strength and super-ductility nylon-6/epoxide resin/silica dioxide nano-composite. The present invention makes the silicon ester react with the hydroxy group of the epoxide resin under the action of catalyst, and then dissolvent, water and acid (or alkali) are added for hydrolyzation. Because the epoxide resin is grafted and absorbed by the surface of silicasol, the agglomeration of the silica dioxide nano particles can be effectively avoided. On the other hand, because epoxy groups can react with the amino group and the carboxyl of the nylon-6 molecular chain to form partial interpenetration network structure, the diphasic boundary action can be effectively enhanced; the network structure has a good cooperating action with the nano silica dioxide, so the tensile strength of the nano-composite can be greatly enhanced, as well as the impact strength of the material, the tensile strength of the nano-composite is enhanced by 30 % compared with pure nylon-6, and the impact strength is 3-5 times of the pure nylon-6.

Description

The in-situ polymerization method for preparing of nylon 6/ Resins, epoxy/silicon dioxide nano composite material
Technical field
The invention belongs to the technical field of high molecule nano composite material, relating to a kind of is the in-situ polymerization method for preparing of the nano composite material of raw material with hexanolactam and Resins, epoxy siloxanes hydrolyzate.
Background technology
Because surface effects, volume effect, the quantum size effect of nanoparticle, add that density polymer is little, intensity is high, good characteristic such as corrosion-resistant, easy processing, nano composite material has caused extensive concern at home and abroad in recent years, becomes the emphasis and the focus of Materials science research.
At present, the preparation method of nano composite material mainly contains sol-gel method, graft process, blending method, situ aggregation method etc., the whole bag of tricks all exists how to avoid being separated in the nano composite material preparation process in various degree, increases the problem of the interface interaction of nanoparticle and body material.At present, as described in CN01139269.x, J.Appl.Poly.Sci.200284, J.Poly.Sci.1998B (84) etc., people generally adopt and add the degree of scatter that expensive silane coupling agent or interface modifier improve nanoparticle and strengthen two alternate interactions.After aforesaid method is handled, though the tensile strength of material has lifting to a certain degree, but then, also make complex manufacturing, production cost increases, and its shock resistance increase rate is not very good.
Chinese patent CN021398369.4 discloses the method that a kind of hydrolyzate by hexanolactam and inorganic acid ester or inorganic acid salt directly prepares nylon 6/ inorganic particulate nano composite material, it is simple to have production technique, product is a white, is easy to realize advantages such as industrialization.
Employing different methods such as domestic patent CN90106778, CN97100554, CN97108021.6, CN99109924, CN00129200.5, CN03115279.1 and foreign patent EP0377511, EP0400964, EP0455507, US6303691, US6444754 come modification of nylon 6, though its impact property significantly improves, there is decline in various degree in its tensile strength.
Summary of the invention
The in-situ polymerization novel preparation method that the purpose of this invention is to provide a kind of nylon 6/ Resins, epoxy/silicon dioxide nano composite material, make this matrix material under the prerequisite of the good tensile property of maintenance, has excellent toughness again, to satisfy the demand of special dimension.
The objective of the invention is to realize in the following way: the in-situ polymerization method for preparing of a kind of nylon 6/ Resins, epoxy/silicon dioxide nano composite material: comprise the following steps:
(a) prepare Resins, epoxy siloxanes hydrolyzed solution by grafting and hydrolysis reaction;
(b) before the hexanolactam ring-opening reaction or in the process, Resins, epoxy siloxanes hydrolyzed solution is incorporated in the described hexanolactam ring-opening reaction medium, adds entry and oxidation inhibitor simultaneously;
(c) make hexanolactam open loop and polymerization, be prepared into nylon 6/ Resins, epoxy/silicon dioxide nano composite material.
Resins, epoxy siloxanes hydrolyzed solution, behind 80 ℃～160 ℃ reaction 1～10h, is added solvent, water, acid (or alkali) and prepares through hydrolysis reaction under catalyst action by Resins, epoxy and silicon ester; Said Resins, epoxy is bisphenol A type epoxy resin; Said catalyzer is the titanate ester compound; Said solvent is tetrahydrofuran (THF) or acetone or alcohol.
The ring-opening polymerization of hexanolactam is carried out under the effect of water and catalyzer; Said catalyzer is amino acids or protonic acid.
Caprolactam polymerization be with reactant at 20 ℃～180 ℃ degree thermal treatment 0.5～800h, be 180 ℃～300 ℃ in temperature then, pressure is-0.1MPa～2MPa under, polyase 13～50h.
The present invention under catalyst action, under 80 ℃～160 ℃, makes the hydroxyl reaction of silicon ester and Resins, epoxy with Resins, epoxy and silicon ester, adds solvent, water, acid (or alkali) hydrolysis then.Because silicon sol surface grafting and absorption Resins, epoxy, thereby effectively avoid the reunion of Nano particles of silicon dioxide.On the other hand and since epoxide group can with the amino and the carboxyl reaction of nylon 6 molecular chains, form the partial interpenetrating network structure, thereby effectively improve the interface interaction of two-phase.There is good " synergy " in itself and nano silicon, thereby can be when improving the matrix material tensile strength, significantly improve the shock resistance of material, it is about 30% that the purer nylon of its tensile strength 6 improves, and its shock strength is 3～5 times of pure nylon 6 simultaneously.
The present invention has following positively effect:
1. adopt cheap Resins, epoxy, in same operation, realize the in-situ polymerization of original position generation, finishing and the nylon 6 of nano-silicon dioxide particle;
Characteristics the such as 2. Nano particles of silicon dioxide in the matrix material has narrow diameter distribution, and size is controlled;
3. the ring-opening reaction by epoxy group(ing) and nylon 6 molecules, form the partial interpenetrating network structure, there be good " synergy " in itself and nano-silicon dioxide particle, thereby when improving composite material strength, increased the toughness of matrix material greatly, its impact property is 3～5 times of pure nylon 6;
This method has that but monomer conversion high extraction of oligomers content is few, polymerization time is short, plant factor is high, production cost is low, and technology is simple and convenient, is fit to advantages such as suitability for industrialized production.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment one:
The first step: preparation Resins, epoxy siloxanes hydrolyzed solution
By filling a prescription,, add 0.5wt.% four positive butyl (tetra) titanates with a certain amount of tetraethoxy mixing with behind bisphenol A type epoxy resin (EP) heating extraction water and the small molecules; under nitrogen protection; in 110 ℃～130 ℃ reaction 3h, be cooled to 55 ℃ then, add a certain amount of THF; distilled water and catalyzer 1M HCl (TEOS; THF, water, the amount of substance ratio of HCl is 1: 15: 4: 0.002); stir about 6h obtains the solution of clear.
Second step: before the hexanolactam ring-opening reaction or in the process, add Resins, epoxy siloxanes hydrolyzed solution, water and oxidation inhibitor
The Resins, epoxy hydrolyzed silane solution that the last step is prepared joins in the 2.0Kg molten caprolactam, and mixing is warming up to 120 ℃, extracts the ethanol that solvent and hydrolysis produce.Add 50g distilled water, the dense H of 1ml then 3PO 4, 0.5g oxidation inhibitor,
The 3rd step: preparation nylon 6/ Resins, epoxy/silicon dioxide nano composite material
Under high pure nitrogen protection, above-mentioned mixing solutions is warming up to 180～280 ℃, at pressure be-react about 6h under 0.06MPa～0.8MPa.Product promptly gets nylon 6/ Resins, epoxy/silicon dioxide nano composite material (note is made EPA6-1) through poach after the drying.
Embodiment two:
The first step: preparation Resins, epoxy siloxanes hydrolyzed solution
By filling a prescription,, add 0.5wt.% four positive butyl (tetra) titanates with a certain amount of tetraethoxy mixing with behind bisphenol A type epoxy resin (EP) heating extraction water and the small molecules; under nitrogen protection; in 110 ℃～130 ℃ reaction 3h, be cooled to 55 ℃ then, add a certain amount of THF; distilled water and catalyzer 1M HCl (TEOS; THF, water, the amount of substance ratio of HCl is 1: 75: 4: 0.002); stir about 6h obtains the solution of clear.
Second step: before the hexanolactam ring-opening reaction or in the process, add Resins, epoxy siloxanes hydrolyzed solution, water and oxidation inhibitor
The Resins, epoxy hydrolyzed silane solution that the last step is prepared joins in the 2.0Kg molten caprolactam, and mixing is warming up to 120 ℃, extracts the ethanol that solvent and hydrolysis produce.Add 50g distilled water, the dense H of 1ml then 3PO 4, 0.5g oxidation inhibitor,
The 3rd step: preparation nylon 6/ Resins, epoxy/silicon dioxide nano composite material
Under high pure nitrogen protection, above-mentioned mixing solutions is warming up to 180～280 ℃, at pressure be-react about 6h under 0.06MPa～0.8MPa.Product promptly gets nylon 6/ Resins, epoxy/silicon dioxide nano composite material (note is made EPA6-4) through poach after the drying.
Embodiment three:
The first step: preparation Resins, epoxy siloxanes hydrolyzed solution
By filling a prescription,, add 1.5wt.% four positive butyl (tetra) titanates with a certain amount of tetraethoxy mixing with behind bisphenol A type epoxy resin (EP) heating extraction water and the small molecules; under nitrogen protection; in 110 ℃～130 ℃ reaction 3h, be cooled to 55 ℃ then, add a certain amount of THF; distilled water and catalyzer 1M HCl (TEOS; THF, water, the amount of substance ratio of HCl is 1: 5: 4: 0.002); stir about 6h obtains the solution of clear.
Second step: before the hexanolactam ring-opening reaction or in the process, add Resins, epoxy siloxanes hydrolyzed solution, water and oxidation inhibitor
The Resins, epoxy hydrolyzed silane solution that the last step is prepared joins in the 2.0Kg molten caprolactam, and mixing is warming up to 120 ℃, extracts the ethanol that solvent and hydrolysis produce.Add 50g distilled water, the dense H of 1ml then 3PO 4, 0.5g oxidation inhibitor,
The 3rd step: preparation nylon 6/ Resins, epoxy/silicon dioxide nano composite material
Under high pure nitrogen protection, above-mentioned mixing solutions is warming up to 180～280 ℃, at pressure be-react about 6h under 0.06MPa～0.8MPa.Product promptly gets nylon 6/ Resins, epoxy/silicon dioxide nano composite material (note is made EPA6-6) through poach after the drying.
Project Hexanolactam Resins, epoxy Tetraethoxy
PA6 100 0 0
EPA6-1 100 1 3.47
EPA6-4 100 5 3.47
EPA6-6 100 3 10.4
* above data are weight fraction
The matrix material of preparation is made batten test by standard method on injection moulding machine, the result is as follows:
Project Notched Izod impact strength (KJ/m 2) Tensile strength (MPa) Young's modulus (MPa) Elongation at break (100%) Flexural strength (MPa)
PA6 5.8 54.5 1680 220 78.6
EPA6-1 13.4 57.0 1775 235 90.9
EPA6-4 18.3 61.2 1884 238 103.5
EPA6-6 31.2 70.0 2255 325 110.2
The notched Izod impact strength testing method is GB1043
The testing method of tensile strength, Young's modulus is GB1634
The testing method of flexural strength is GB1042

Claims (4)

1, the in-situ polymerization method for preparing of a kind of nylon 6/ Resins, epoxy/silicon dioxide nano composite material is characterized in that: comprise the following steps:
(a) prepare Resins, epoxy siloxanes hydrolyzed solution by grafting and hydrolysis reaction;
(b) before the hexanolactam ring-opening reaction or in the process, Resins, epoxy siloxanes hydrolyzed solution is incorporated in the described hexanolactam ring-opening reaction medium, adds entry and oxidation inhibitor simultaneously;
(c) make hexanolactam open loop and polymerization, be prepared into nylon 6/ Resins, epoxy/silicon dioxide nano composite material.
2, the in-situ polymerization method for preparing of nylon 6/ Resins, epoxy according to claim 1/silicon dioxide nano composite material, it is characterized in that: Resins, epoxy siloxanes hydrolyzed solution by Resins, epoxy and silicon ester under catalyst action, behind 80 ℃～160 ℃ reaction 1～10h, adding solvent, water, acid (or alkali) prepare through hydrolysis reaction; Said Resins, epoxy is bisphenol A type epoxy resin; Said catalyzer is the titanate ester compound; Said solvent is tetrahydrofuran (THF) or acetone or alcohol.
3, the in-situ polymerization method for preparing of nylon 6/ Resins, epoxy according to claim 1/silicon dioxide nano composite material, it is characterized in that: the ring-opening polymerization of hexanolactam is carried out under the effect of water and catalyzer; Said catalyzer is amino acids or protonic acid.
4, the in-situ polymerization method for preparing of nylon 6/ Resins, epoxy according to claim 1/silicon dioxide nano composite material, it is characterized in that: caprolactam polymerization is at 20 ℃～180 ℃ degree thermal treatment 0.5～800h with reactant, it is 180 ℃～300 ℃ in temperature then, pressure is-0.1MPa～2MPa under, polyase 13～50h.
CNB2006100316048A 2006-04-28 2006-04-28 Process for in-situ polymerization preparation of nylon 6/epoxy resin/silicon dioxide nano composite materials Expired - Fee Related CN100348665C (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012089081A1 (en) * 2010-12-28 2012-07-05 上海杰事杰新材料(集团)股份有限公司 Nano particle/polyamide composite material, preparation method therefor, and use thereof
CN102108122B (en) * 2011-01-05 2012-11-07 湖南大学 Preparation method of high-tenacity high-flowability nylon 6 compound material
CN105440669A (en) * 2015-12-22 2016-03-30 合肥仲农生物科技有限公司 Modified casting nylon composite material
CN105778489A (en) * 2016-05-21 2016-07-20 夏百庆 Polyamide modified nano silicon dioxide material and preparation method thereof
CN105778490A (en) * 2016-05-24 2016-07-20 夏百庆 Hard nano silica material and preparation method thereof
CN109972397B (en) * 2019-03-25 2021-07-13 吉林乾仁新材料有限公司 Preparation and application of in-situ synthesized nano-oxide reinforced carbon fiber sizing agent and basalt fiber impregnating compound

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Publication number Priority date Publication date Assignee Title
CN1138593A (en) * 1996-06-05 1996-12-25 中国科学院化学研究所 Polyamide and clay nm composite and its prepn.
CN1422901A (en) * 2002-12-12 2003-06-11 湘潭大学 Nylon 6/inorganic particle nano composite material direct preparation method
CN1454935A (en) * 2003-02-26 2003-11-12 郑州大学 Nylon 66/montmorillonite nano composite material and preparing method thereof
CN1491990A (en) * 2003-09-11 2004-04-28 郑州大学 Nylon 1010/montmorillonite nano composite material and its preparing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1138593A (en) * 1996-06-05 1996-12-25 中国科学院化学研究所 Polyamide and clay nm composite and its prepn.
CN1422901A (en) * 2002-12-12 2003-06-11 湘潭大学 Nylon 6/inorganic particle nano composite material direct preparation method
CN1454935A (en) * 2003-02-26 2003-11-12 郑州大学 Nylon 66/montmorillonite nano composite material and preparing method thereof
CN1491990A (en) * 2003-09-11 2004-04-28 郑州大学 Nylon 1010/montmorillonite nano composite material and its preparing method

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