CN1178985C - Process for preparing nano-class polyester/laminated silicate composition - Google Patents
Process for preparing nano-class polyester/laminated silicate composition Download PDFInfo
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- CN1178985C CN1178985C CNB01120284XA CN01120284A CN1178985C CN 1178985 C CN1178985 C CN 1178985C CN B01120284X A CNB01120284X A CN B01120284XA CN 01120284 A CN01120284 A CN 01120284A CN 1178985 C CN1178985 C CN 1178985C
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Abstract
The present invention provides a preparation method of polyester/layer silicate nanometer composite material. Layer silicate materials and a polyester matrix are compounded and homogeneously dispersed over the polyester matrix in a nanometer scale by adopting a melt intercalation method and utilizing environment having an affinity for organic and high-activity reactive groups provided by functional co-intercalation organified layer silicate materials, so the high-performance polyester nanometer composite material is prepared. The preparation method of the present invention is simple to operate and has the advantages of high productive efficiency, low cost and no environmental pollution, and the obtained nanometer composite material has superior performance.
Description
The present invention relates to a kind of polyester/phyllosilicate nano-composite material, specially refer to and adopt melt intercalated method, utilize organise layered silicate material and polyester matrix is compound and be dispersed in the polyester matrix with nanoscale of functional intercalation altogether, thereby prepare high performance nanometer composite polyester material.
1. background of invention
The present invention relates to a kind of nanometer composite polyester material, specially refer to the matrix material that saturated polyester and mineral filler are formed.Saturated polyester is a kind of widely used engineering plastics, is widely used in aspects such as automobile component, electrical part, fiber, beverage bottle and film.But its heat-drawn wire is lower, and hygrothermal environment easily decomposes down, causes the mechanical and physical performance deterioration, has limited application.The very low course of processing that influences of its melt viscosity.In addition, even under drying conditions, the mechanical and physical performance of polyester is also inadequate slightly, and deficiency is used under heavy lift.Early stage method of modifying is to adopt the Inorganic Fillers Filled polyester, for example, with fiberglass reinforced polyethyleneterephthalate (PET), can improve its intensity, rigidity and dimensional stability, but the density of material is increased.Add mineral fillers such as lime carbonate or mica in addition in addition and improve performance.An approach that improves performance is to adopt the inorganics filled polymer composites of superfine.But when packing material size size during less than 0.1 micron, the great surface energy of particle makes that interparticle self aggregation effect is very big, adopts traditional blend method, can not offset the self aggregation effect, can not make filler obtain homodisperse on the superfine nano level; On the other hand, for improving the bonding interface of filler and polymkeric substance, common employing silane coupling agent or titante coupling agent or other have the interfacial compatibilizers such as organic polymer grafts to the similar group of matrix macromolecular chain, to improve the consistency of filler in polymeric matrix.Yet it is very big that the chemical structure of filler and polymkeric substance and physical condition differ, and existing interface modification technology is difficult to eliminate fully the interfacial tension between filler and polymeric matrix, homodisperse of realizing ideal and bonding interface.Therefore, differ greatly apart from the INTERFACE DESIGN of molecular scale, matrix material does not reach the nano-dispersed level, and only belongs to class microcosmic matrix material, has influenced the improvement of reinforcing effect and resistance toheat.
A kind of novel method of Chu Xianing is to utilize layered silicate to prepare polymer nanocomposites in recent years.As everyone knows, polynite such as sodium-based montmorillonite or the calcium-base montmorillonite mineral of layered silicate-for example, can be by organic cation ammonium salt intercalation in dispersion medium such as water, organic molecule is introduced between the silicate lamella of nanoscale, hydrophilic silicate lamella organises thereby increased sheet interlayer spacing and made originally, and organism or high molecular polymer are had good consistency.Or/and under the effect of shearing force, when organic polymer inserts between the silicate lamella, further increase interlamellar spacing in heat, the silicate granules with 30-200 silicate lamella composition is dissociated, promptly silicate is dispersed in the polymeric matrix with single lamella.The basic thickness of silicate lamella is 0.96 nanometer, and the definition of nano material is to have unidimensional scale in the material at least less than 100 nanometers, and apparent, dissociative type layered silicate/polymer composites is a nano composite material.In layered silicate/polymer nanocomposites, polymer molecular chain and silicate lamella are at nanoscale-be compound on the molecular scale, and this will greatly promote the performance of polymer materials.
QiZongNengs etc. have been reported the method (J.Appl.Polym.Sci.71,1139,1999) for preparing polyester/polynite (polynite-a kind of natural layer silicate mineral) nano composite material by polymerization.The implementation process of this method is at first the intercalation expansionization processing-processing that promptly organises to be carried out in polynite, then the common polymerization acquisition nano composite material in reactor with organo montmorillonite and polyester monocase.The mechanical property and the thermal characteristics of the nano composite material that obtains are improved.The shortcoming of aforesaid method is that carrying out intercalation polymeric in reactor needs main equipment, and expends a large amount of time and energy, causes production cost rising, production efficiency to descend.
Melt intercalated method prepares nano composite material can enhance productivity, and reduces production costs, and does not need special reaction equipment, is a kind of novel method that occurs in recent years.For example United States Patent (USP) 5760121, with silicate and the direct fusion intercalation of PET, obtain nano composite material.But the not raising of illustrative material on performance of this patent.In the above method, adopt intercalation polymeric method or melt intercalated method no matter be, what all use is the organic intercalation agent of non-activity functional group or without the inorganic materials of organic modification, just utilizes electrostatic force or Van der Waals force that silicate lamella and polyester molecule chain are linked together.And have only mineral filler and polymeric matrix that the chemical bonding of strong interaction-is for example arranged, and reach the dispersion of nanoscale, just may be with the rigidity of inorganics, toughness, the workability of dimensional stability and thermotolerance and polymkeric substance ideally combine, the Organic of obtained performance excellence.
In order to overcome the shortcoming in the prior art, the invention provides and a kind ofly utilize melt intercalated method preparation to have polyester/phyllosilicate nano-composite material of excellent mechanical property and preparation method thereof.The layered silicate that adopts has the characteristics of close organic property and reactable simultaneously through processings that organise of intercalation altogether, makes polyester molecule chain and sheet interlayer generation chemical bonding.
2. main points of the present invention
Melt intercalated method is jointly at forcing machine or similarly shearing force can be provided and polyester be heated in the equipment more than the fusing point with polyester and layered silicate material, under the effect of shearing force, make the polyester molecule chain be inserted into layered silicate material sheet interlayer, it is compound that polyester molecule chain and silicate lamella are carried out on nanoscale, obtains high molecular polymer/layered silicate material nano composite material.Wherein the inorganic silicate component provides excellent mechanics, thermostability to reach water and micromolecular iris action, and organic polymer has guaranteed good workability.The present invention adopts melt intercalated method to prepare polyester/phyllosilicate nano-composite material, has made full use of the scorification simple equipments, advantages such as technology is simple, production efficiency is high, environmentally safe.Adopt simultaneously and more effectively be total to intercalation organosilicate stratified material, this material is to carry out modification on the basis of inorganic silicate stratified material, utilize organic quaternary ammonium salt and epoxy compounds to carry out common intercalation processing, layered silicate material is organised, strengthen with the organic macromolecule consistency making the polyester molecule chain be easy to enter the sheet interlayer; Simultaneously can and polyester backbone on the epoxy compounds of radical reaction insert between the silicate lamella, exothermic heat of reaction under melting condition between functional group can make the intercalation dispersion effect better, and polyester chain is connected on the silicate lamella securely, further improves the performance of product.The nano composite material that obtains has following characteristics: excellent oxygen and water vapour barrier property, agent of low hygroscopicity, high strength and rigidity, high heat resistance, high transparent, grease resistance, resistance to chemical attack and high-dimensional stability.
3. to the method involved in the present invention and the detailed description of material
The present invention relates to the organise preparation of layered silicate material and corresponding nanometer composite polyester material of functional altogether intercalation.The functional altogether intercalation that the present invention relates to layered silicate material that organises is to organise to handle and obtain by inorganic laminated silicate material being carried out common intercalation.The inorganic laminated silicate material that the present invention relates to is meant the material with sheet crystalline structure, lamellar spacing is between 0.5 nanometer to 2 nanometer, lamella length and width are between 10 nanometer to 1000 nanometers, and lamella and lamella rely on Intermolecular Forces or electrostatic force to pile up.This type of material comprises sodium-based montmorillonite (sodium montmorillonite), calcium-base montmorillonite (calcium montmorillonite), magnesium base montmorillonite polynite classes (smectite) such as (magnesium montmorillonite), nontronite (nontronite), beidellite (beidelite), rich volchonskoite (volkonskoite), hectorite (hectorite), saponite (saponite), sauconite (sauconite), stevensite (stevensite), bentonite (bentonite), illite (illite), kaolin (kaolin), polynite and illitic mixture are as the tired stone (rectorite) etc. that takes off.Except above natural mineral, artificial hydro-thermal synthetic polynite and saponite are also included among the inorganic laminated silicate material of indication of the present invention.Be applicable to that best materials of the present invention is the polynite class, its single lamellar spacing is about 1 nanometer.Its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two, and structure cell continuous growth on length and width constitutes single lamella.Because the isomorphous substitution phenomenon, the montmorillonite layer surface has negative charge, is present in the Na between the lamella
+, Ca
2+, Mg
2+Play the balancing charge effect etc. the interchangeability positively charged ion, utilize the organic cation ammonium salt can be Na
+, Ca
2+, Mg
2+Deng exchanging, thereby sheet surfaces is organised.Polynite preferably is crushed to suitable particle diameter before using, and available ball mill, vibration mill, jet mill etc. are broken into desirable particle size to clay powder, and general particle diameter should be at 200 orders-400 order.
The organic cation ammonium salt that the present invention relates to has following structure: NH
3 +R
1Or NH
2 +R
2R
3Or NH
+R
4R
5R
6Or N
+R
7R
8R
9R
10R wherein
1To R
10Being organo-functional group, can be aromatic base or alkyl, can be the same or different to each other.Be suitable for most organic cation ammonium salt of the present invention and have the 4th kind of structure, i.e. N
+R
7R
8R
9R
10, as cetyl trimethylammonium bromide.Utilize the ion exchange reaction organic cation ammonium salt can be with Na
+, Ca
2+, Mg
2+Deng exchanging, thereby with R
1To R
10Insert between the inorganic sheet Deng organo-functional group, sheet interlayer spacing is increased, and the sheet surfaces parent is organised.
The epoxy compounds that the present invention relates to comprises organic monomer, oligopolymer and superpolymer, contains an epoxide group on its molecular chain at least.Being suitable for most epoxy compounds of the present invention is the Resins, epoxy that has two epoxide groups on the molecular chain at least.
The polyester that the present invention relates to is meant saturated polyester, comprises polyethylene terephthalate (PET), polybutylene terephthalate (PBT).
The functional altogether intercalation that the present invention relates to layered silicate material that organises is to carry out modification on the basis of inorganic silicate stratified material, utilizes organic cation ammonium salt and epoxy compounds to carry out common intercalation processing.Its method for making is as follows: with the inorganic silicic acid salt material of 0.1-30 part, the water high speed stirring 1-1000 part forms stable suspension earlier; Then the organic cation ammonium salt of 0.1-50 part is joined and continue in the suspension to stir, utilize ion exchange reaction to make ammonium salt insert the silicate plate interlayer and the silicate plate laminar surface is organised; After treating that permutoid reaction is finished, leave standstill silicate material is fully precipitated, remove supernatant liquid and obtain mud shape mixture, the epoxy compounds of 0.1-50 part is joined continue in the mud shape mixture fully to stir then; At last it is dehydrated and product is crushed to 200-400 order particle diameter, this final product is the functional intercalation altogether silicate material that organises.
The preparation method of the nano composite material that the present invention relates to is as follows: can provide simultaneously shearing force and and polyester is heated in the equipment more than the fusing point, as twin screw extruder, organise silicate material and 100 parts of polyester of the functional altogether intercalation of 0.1-30 part are melt extruded granulation, can obtain polyester/phyllosilicate nano-composite material.The functional altogether intercalation silicate material content in the present invention that organises is 0.1-30 (weight part).When content is lower than 0.1 part, silicate material is not enough to produce enough enhancements; When content surpasses 30 parts, nano composite material can not machine-shaping.In the present invention, its optimum content scope is 0.5-20 part.
Method provided by the invention adopts melt intercalated method to prepare polyester/phyllosilicate nano-composite material, and simple equipments, technology is simple, production efficiency is high, environmentally safe.Adopt simultaneously more effectively to be total to intercalation organosilicate stratified material, can make the intercalation dispersion effect better, and polyester chain is connected on the silicate lamella securely, further improve the performance of product, prepare high performance nano composite material.
The present invention makes the layered silicate material disperse phase reach the 10-30 nanoscale, has very large interfacial area, chemical bonding makes inorganic disperse phase and polymer-based carbon body interface have the ideal adhesiveproperties, inorganics and polymeric matrix two material thermal expansivity mismatch problems be can eliminate, the excellent mechanical property of inorganics intrinsic, high heat resistance, barrier given full play to.This nano composite material can have choice widely to polytype forming process.
Nanoscale dispersive silicate lamella has the heterogeneous nucleation effect to polyester among the present invention, and crystallization velocity is significantly improved, and improves the workability of material.
Embodiment 1
With 100 parts sodium-based montmorillonite, stirred 2 hours earlier, form the stable suspersion system 1000 parts water high speeds.Then 30 parts cetyl trimethylammonium bromide is joined and continue in the suspension to stir 2 hours.After treating that ion exchange reaction is finished, leave standstill and suspension was fully precipitated in 24 hours, remove supernatant liquid and obtain mud shape mixture, (CIBA-GEIGY company makes with 40 parts of bisphenol A type epoxy resin ARALDITE GY240 then, molecular weight 340-380, oxirane value 0.52-0.56) join in the mud shape mixture and fully stirred 2 hours.At last it is dehydrated and product is crushed to 200-400 order particle diameter, promptly obtain functional intercalation organic montmorillonoid altogether.On the twin screw extruder of 30 mm dias, (the PBT trade mark is ULTRDOUR 2550 with 5 parts of functional altogether intercalation organic montmorillonoids and 100 parts of PBT, the manufacturing of Germany BASF AG) melt extrudes granulation, four sections Heating Zone Temperature are respectively 240,260,260 and 250 degree from the opening for feed to the extruder head, and screw speed is 180 rev/mins.Can obtain the PBT/ laminated nm-silicate composite material.Measure the functional sheet interlayer spacing of intercalation organic montmorillonoid altogether in this material through X-ray diffraction method, the result shows sheet interlayer spacing (as shown in table 1) more than 10 nanometers, this show functional altogether intercalation organic montmorillonoid in the matrix material that makes with the nanoscale homodisperse.Its mechanical property and resistance toheat see Table 1.
Embodiment 2
With example 1, wherein functional intercalation organic montmorillonoid content altogether is respectively 10 parts.Its sheet interlayer spacing and performance see Table 1.
Sheet interlayer spacing, mechanical property and the thermotolerance of table 1 PBT/ laminated nm-silicate composite material
Embodiment PBT body 12
Functional intercalation organic montmorillonoid content 05 10 altogether
(part)
Sheet interlayer spacing (nanometer)-＞10＞10
Tensile strength (MPa) 55.3 62.7 65.3
Tensile modulus (MPa) 2,600 3,100 3520
IZOD notched Izod impact strength (Jiao/rice) 23 37 30
Tension set (%) 6.3 6.7 4.6
Heat-drawn wire (degree) (1.85 MPa load) 55 84 97
Above result shows, functional intercalation organic montmorillonoid altogether in the material that makes with the nanoscale homodisperse, the strength and stiffness of nano composite material long-range with the PBT bulk material, heat-drawn wire has improved nearly 40 degree.In addition, the notched Izod impact strength of nano composite material also is higher than the PBT bulk material.
Embodiment 3
With 100 parts sodium-based montmorillonite, stirred 2 hours earlier, form the stable suspersion system 1000 parts water high speeds.Then 30 parts cetyl trimethylammonium bromide is joined and continue in the suspension to stir 2 hours.After treating that ion exchange reaction is finished, leave standstill and suspension was fully precipitated in 24 hours, remove supernatant liquid and obtain mud shape mixture, (CIBA-GEIGY company makes with 40 parts of bisphenol A type epoxy resin ARALDITE GY240 then, molecular weight 340-380, oxirane value 0.52-0.56) join in the mud shape mixture and fully stirred 2 hours.At last it is dehydrated and product is crushed to 200-400 order particle diameter, promptly obtain functional intercalation organic montmorillonoid altogether.On the twin screw extruder of 30 mm dias, (PET is the Yanshan Petrochemical product with 5 parts of functional altogether intercalation organic montmorillonoids and 100 parts of PET, the wire drawing level) melt extrudes granulation, four sections Heating Zone Temperature are respectively 275,280,280 and 270 degree from the opening for feed to the extruder head, and screw speed is 180 rev/mins.Can obtain the PET/ laminated nm-silicate composite material.Measure the functional sheet interlayer spacing of intercalation organic montmorillonoid altogether in this material through X-ray diffraction method, the result shows sheet interlayer spacing (as shown in table 2) more than 10 nanometers, this show functional altogether intercalation organic montmorillonoid in the matrix material that makes with the nanoscale homodisperse.Its mechanical property and resistance toheat see Table 2.
Sheet interlayer spacing, mechanical property and the thermotolerance of table 2 PET/ laminated nm-silicate composite material
Embodiment PET body 3
Functional intercalation organic montmorillonoid content (part) 05 altogether
Sheet interlayer spacing (nanometer)-＞10
Tensile strength (MPa) 48.1 64.2
Tensile modulus (MPa) 3,010 4060
IZOD notched Izod impact strength (Jiao/rice) 32 47
Tension set (%) 2.3 3.2
Heat-drawn wire (degree) (1.85 MPa load) 67 95
Above result shows, functional intercalation organic montmorillonoid altogether in the material that makes with the nanoscale homodisperse, the strength and stiffness of nano composite material long-range with the PET bulk material, heat-drawn wire has improved nearly 30 degree.In addition, the notched Izod impact strength of nano composite material also is higher than the PET bulk material.
Claims (7)
1. a polyester/functional intercalation altogether nano composite material of layered silicate material that organises, this functional altogether intercalation organise layered silicate material by inorganic laminated silicate material is carried out organic cation ammonium salt and epoxy compounds altogether intercalation organise to handle and obtain, it is characterized in that the feed composition of described nano composite material and content are as follows: (weight part)
Polyester 100
Layered silicate material 0.1-30
Organic cation ammonium salt 0.1-50
Epoxy compounds 0.1-50.
2. a kind of polyester according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described inorganic laminated silicate material is meant the material with sheet crystalline structure, lamellar spacing is between 0.5 nanometer to 2 nanometer, and lamella length and width are between 10 nanometer to 1000 nanometers; This type of material comprises sodium-based montmorillonite, calcium-base montmorillonite, magnesium base montmorillonite, polynite class, nontronite, beidellite, rich volchonskoite, hectorite, saponite, sauconite, stevensite, bentonite, illite, kaolin, polynite and illitic mixture, except above natural mineral, artificial hydro-thermal synthetic polynite and saponite are also included among the inorganic laminated silicate material of indication of the present invention.
3. a kind of polyester according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described organic cation ammonium salt has following structure: NH
3 +R
1Or NH
3 +R
2R
3Or NH
+R
4R
5R
6Or N
+R
7R
8R
9R
10, R wherein
1To R
10Be aromatic base or alkyl, can be the same or different to each other.
4. a kind of polyester according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described epoxy compounds comprises organic monomer, oligopolymer and superpolymer, contain an epoxide group on the epoxy compounds molecular chain at least.
5. a kind of polyester according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that described polyester is a saturated polyester, comprises polyethylene terephthalate or polybutylene terephthalate.
6. a kind of polyester according to claim 1/functional is the organise nano composite material of layered silicate material of intercalation altogether, it is characterized in that the functional altogether intercalation layered silicate material preparation method that organises is as follows: earlier with the inorganic laminated silicate material of 0.1-30 part, water high speed 1-1000 part stirs, and forms the stable suspersion system; Then the organic cation ammonium salt of 0.1-50 part is joined and continue in the suspension to stir, utilize ion exchange reaction to make ammonium salt insert the silicate plate interlayer and the silicate plate laminar surface is organised; After treating that permutoid reaction is finished, leave standstill silicate material is fully precipitated, remove supernatant liquid and obtain mud shape mixture, the epoxy compounds of 0.1-50 part is joined continue in the mud shape mixture fully to stir then; At last it is dehydrated and product is crushed to 200-400 order particle diameter, this final product is the functional intercalation altogether layered silicate material that organises.
7. the described polyester of claim 1/functional intercalation altogether preparation method of nano composite material of layered silicate material that organises, it is characterized in that the nano composite material preparation method is as follows: in shearing force being provided simultaneously and polyester being heated to equipment more than the fusing point, organise layered silicate material and 100 parts of polyester of the functional altogether intercalation of 0.1-30 part are melt extruded granulation, can obtain polyester/phyllosilicate nano-composite material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01120284XA CN1178985C (en) | 2001-07-16 | 2001-07-16 | Process for preparing nano-class polyester/laminated silicate composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01120284XA CN1178985C (en) | 2001-07-16 | 2001-07-16 | Process for preparing nano-class polyester/laminated silicate composition |
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|---|---|
| CN1396204A CN1396204A (en) | 2003-02-12 |
| CN1178985C true CN1178985C (en) | 2004-12-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9060420B2 (en) | 2007-11-01 | 2015-06-16 | Western Digitial Technologies, Inc. | Method of manufacturing a double sided flex circuit for a disk drive wherein a first side lead provides an etching mask for a second side lead |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525477B (en) * | 2008-03-04 | 2012-04-11 | 东丽纤维研究所（中国）有限公司 | Nanometer composite material of polyester and inorganic silicate |
| CN112573531B (en) * | 2019-09-27 | 2023-01-31 | 清华大学 | Method for preparing negative active material |
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2001
- 2001-07-16 CN CNB01120284XA patent/CN1178985C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9060420B2 (en) | 2007-11-01 | 2015-06-16 | Western Digitial Technologies, Inc. | Method of manufacturing a double sided flex circuit for a disk drive wherein a first side lead provides an etching mask for a second side lead |
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