CN1583879A - Ion polyester/laminated silicate nanometer composite materials and preparing method thereof - Google Patents
Ion polyester/laminated silicate nanometer composite materials and preparing method thereof Download PDFInfo
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- CN1583879A CN1583879A CN 200410024651 CN200410024651A CN1583879A CN 1583879 A CN1583879 A CN 1583879A CN 200410024651 CN200410024651 CN 200410024651 CN 200410024651 A CN200410024651 A CN 200410024651A CN 1583879 A CN1583879 A CN 1583879A
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Abstract
A kind of ion and polyester/the silicic acid nanometer composite of one layer of forms, its characteristic lies in the raw materials group one of the stated composite It is the weight percentage as follows with the content: Ion type Polyester: One layer of forms silicate=100:0.1-20. It prepares the method In be able to offer the strength of shearing and heat the polyester to the point at the same time The above-mentioned one equipment among, 0.1-20 copy layers of form silicate and Push out of and make one, can get in 100 particle type polyester melting The polyester is before gathering the things/the silicate nanometer composite of one layer of forms.
Description
Technical field
The present invention relates to and adopt melting intercalation method to prepare the ionic polyester/phyllosilicate nano-composite material.
Background technology
Since institute of central authorities of Japanese Toyota report in 1987 prepares nylon 6/ clay nanocomposites with graft process, the research of nano composite polymer/laminated silicate material receives much concern, and the system of research relates to polystyrene (PS), polypropylene (PP), polyacrylonitrile (PAN) and polyester (PET) etc.
Layered silicate is a kind of natural mineral, has laminated structure, constitutes by carrying the layer of aluminum oxygen octahedra secretly in the middle of two silicon-oxy tetrahedrons, connects by shared Sauerstoffatom between the two.The about 100nm of each lamella length and width, thick about 1nm in conjunction with very firm, has only that each layer separately just becomes the nano-grade particle with it.The method for preparing at present nano composite polymer/laminated silicate material mainly is an intercalation compounding, being about to monomer or polymkeric substance injects between the silicate lamella, destroy the laminated structure of silicate, and then make it peel off into the elementary cell of 1-dimention nano size, and be evenly dispersed in the polymeric matrix, realize compound on nano-scale of polymer and layered silicate lamella.
According to the compound process, intercalation compounding can be divided into polymerization graft process and melting intercalation method.The polymerization graft process is earlier polymer monomer to be disperseed, intercalation enters layered silicate sheet interlayer, in-situ polymerization then, a large amount of heats of emitting when utilizing polymerization, overcome the Coulomb's force of silicate plate interlayer, thereby make the silicate lamella with nanoscale and polymer-based carbon volume recombination.It is many to adopt the polymerization graft process to prepare the report of polyester/phyllosilicate nano-composite material, having reported as QiZongNeng etc. and to have adopted in-situ inserted polymerization, is feedstock production polyester/phyllosilicate nano-composite material (Chinese patent application number 97104055.9) with the PET polycondensation monomer; Yizheng Fiber Optical plant company has also obtained PET/ Nano composite material of montmorillonite (Chinese patent publication number CN1324890) with in-situ inserted polymerization.But, in still, add layered silicate and produce nano combined PET, need main equipment, and need PET technology is changed, cause production efficiency to descend, production cost increases.In addition, in long high temperature polymerization process, also can cause the degraded of layered silicate intercalator, and then influence the color and luster of product.
Melting intercalation method is jointly at forcing machine or similarly shearing force can be provided and polymkeric substance be heated in the equipment more than the fusing point with polymkeric substance and layered silicate material, under the effect of shearing force, make polymer molecular chain be inserted into layered silicate sheet interlayer, it is compound that polymer molecular chain and silicate lamella are carried out on nano-scale, thereby obtain nano composite polymer/laminated silicate material.Melting intercalation method prepares the equipment that nano composite material does not need special-purpose reaction, and technology is simple, and the production efficiency height is a kind of novel method that occurred in recent years.Adopt the melt intercalation to prepare the patent of polyamide/laminated silicate, polypropylene/layered silicate and poletene/lamina silicate and report more.Reported employing melt intercalation polymeric method as QiZongNeng etc., will extrude, preparation high-performance nano matrix material (Chinese patent application number 97112237.7) through clay and polymeric amide melt blending on twin screw extruder of intercalation processing; Tang Tao etc. have reported employing melt intercalation polymeric method composite nano polypropylene mixture/montmorillonoid nano-material and preparation method thereof (Chinese patent application number 01133348.0) etc.Correlative study shows that melting intercalation method is difficult to enter the layered silicate interlayer in all directions because polymericular weight is very big, and the lamella degrees of expansion of layered silicate is not enough behind the intercalation, and the ratio of peeling off fully is less, is difficult to obtain the ideal matrix material.Therefore present great majority are applied in the polyester/phyllosilicate nano-composite material that mostly is the preparation of polymerization graft process in engineering plastics and the fiber.This patent makes polyester and silicate plate interlayer have special interaction by introduce ionic group in polyester, increases the consistency of the two, make the silicate lamella in polyester matrix better intercalation, peel off and disperse.
Summary of the invention
The present invention prepares the ionic polyester/phyllosilicate nano-composite material by the method for melt intercalation, and its characteristics are:
The component of ionic polyester/phyllosilicate nano-composite material (weight ratio) is: the ionic polyester: the layered silicate that organises=100: 0.1-20.
Described ionic polyester contains polyethylene terephthalate (PET), the polycarbonate (PC), poly-to naphthalic acid second diester (PEN), copolyester and two kinds or above mixture of ionic group for the molecular chain that makes by the copolycondensation method.
The ionic group that described polyester ionomer molecular chain contains is sulfonic acid group, hydroxy-acid group etc., and the content of ionic group is 0.1-20% (mol ratio).
Described layered silicate is the polynite of handling through organic intercalation agent, organic intercalation agent is the organic cation amine salt, as lauryl amine, hexadecylamine, hexanediamine, lauric acid amine, trolamine, dodecyl trimethylammonium amine bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethylammonium amine bromide and octadecyl benzyl dimethyl amine bromide etc.
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, as twin screw extruder, 0.1-200 part layered silicate material and 100 parts of ionic polyester are melt extruded granulation, can obtain polyester ionomer/laminated nm-silicate composite material.
Pass through in polyester matrix, to introduce the azochlorosulfonate acid ion group among the present invention, the special interaction of polyester and silicate plate interlayer is strengthened, increase the consistency of the two, help in the lamella of polyester molecule chain insertion silicate, its sheet interlayer spacing is increased, and then make the limellar stripping of silicate, and in polyester matrix, disperse equably.Employing fusion intercalation provided by the invention prepares the method simple equipments of polyester ionomer/laminated nm-silicate composite material, and technology is simple, the production efficiency height.
Description of drawings
The X diffracting spectrum of Fig. 1 embodiment 1;
The TEM photo of the PET/ Nano composite material of montmorillonite of Fig. 2 embodiment 2;
The TEM photo of native nano composite material takes off in the ionization PET/ alliance of Fig. 3 embodiment 2;
Embodiment
The invention will be further elaborated with seven specific embodiments below, but embodiment only is used for explanation, does not limit scope of invention.To help to understand the present invention by following examples, but not limit content of the present invention.
Embodiment 1
With dimethyl terephthalate (DMT), ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 2.5%.After ionic PET vacuum-drying, carry out high-speed stirring in varing proportions with polynite through the hexadecyl trimethyl ammonium bromide organic intercalation.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations.Employing prepares pure PET/ laminated nm-silicate composite material with quadrat method, and the reference ion group is introduced influence with dispersion effect is peeled off in polynite; Please referring to Fig. 1 and table 1:
The intercalation effect of table 1.PET and ionic PET and laminated nm-silicate composite material relatively
| Sample number into spectrum in the diffracting spectrum | Prescription | Laminar silicic acid salts contg (wt%) | X-ray diffraction is surveyed D001 interplanar distance (nm) |
| ????1 | Ionization PET/ polynite | ????2 | ????- |
| ????2 | Ionization PET/ polynite | ????4 | ????3.38 |
| ????3 | The PET/ polynite | ????2 | ????3.33 |
| ????4 | The PET/ polynite | ????4 | ????2.54 |
The ionic PET that contains sulfonic acid group from above-mentioned data as can be seen is inserted in the polynite ground lamella than pure PET is easier, the montmorillonite layer spacing is increased, even become exfoliated nano-composite.The introducing of ionic group is described, has increased the consistency between polymkeric substance and the silicate, make silicate lamella better intercalation and peeling off in polyester matrix.
Embodiment 2
With ethylene glycol terephthalate, ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 5%.After ionic PET vacuum-drying, and carry out high-speed stirring through the polynite of octadecyl trimethylammonium amine bromide organic intercalation, the weight ratio of ionic PET and organo montmorillonite is 100 parts: 5 parts.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations.Employing prepares pure PET/ laminated nm-silicate composite material with quadrat method, and the reference ion group is introduced influence with dispersion effect is peeled off in polynite.
Can see that in the PET/ Nano composite material of montmorillonite, the PET molecule can only enter the sheet interlayer of polynite by the part intercalation from Fig. 2,3 TEM photo, the lamella of polynite fluffs diffusing to a certain extent, obtains the intercal type matrix material.And similarity condition preparation under ionization PET/M Nano composite material of montmorillonite in, the sheet interlayer spacing of polynite obviously increases, major part has been peeled off, and is state of disarray and is distributed in the matrix.
Embodiment 3
With dimethyl terephthalate (DMT), ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 2.0%.After ionic PET vacuum-drying, carry out high-speed stirring in varing proportions with polynite through the hexadecyl trimethyl ammonium bromide organic intercalation.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations.See also table 2:
The thermal characteristics of table 2 nano composite material
| Laminar silicic acid salts contg (wt%) | Heat-drawn wire (1.84MPa) (℃) | Heat decomposition temperature (℃) | Fusing point (℃) |
| ????0 | ????70 | ????394 | ????254 |
| ????2 | ????77 | ????403 | ????254 |
| ????3 | ????82 | ????407 | ????252 |
| ????4 | ????90 | ????410 | ????251 |
| ????5 | ????101 | ????416 | ????251 |
Can see that from table behind the adding layered silicate, the resistance toheat of material obviously improves.
Embodiment 4
With ethylene glycol terephthalate, ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 2.0%.After ionic PET vacuum-drying, carry out high-speed stirring in varing proportions with polynite through the hexadecyl trimethyl ammonium bromide organic intercalation.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations, adopt to prepare pure PET/ laminated nm-silicate composite material with quadrat method.Above-mentioned materials is spun into fiber.See also table 3:
The spinning property of table 3 nano composite material and the mechanical property of fiber
| Prescription | Laminar silicic acid salts contg (wt%) | Spinning property | Tensile strength (CN/dtex) | Tensile modulus (CN/dtex) |
| Ionization PET/ polynite | ????2 | Good | ????3.2 | ????64 |
| Ionization PET/ polynite | ????3 | Good | ????3.1 | ????70 |
| Ionization PET/ polynite | ????4 | Good | ????2.8 | ????69 |
| Ionization PET/ polynite | ????5 | Better | ????2.5 | ????61 |
| The PET/ polynite | ????2 | Better | ????2.7 | ????65 |
| The PET/ polynite | ????3 | Generally | ????2.1 | ????62 |
| The PET/ polynite | ????4 | Difference | ????- | ????- |
| The PET/ polynite | ????5 | Difference | ????- | ????- |
Ionic PET/ Nano composite material of montmorillonite makes its spinning property and gained fiber ground mechanical property be better than the PET/ Nano composite material of montmorillonite because polynite is well peeled off in matrix and disperseed.
Embodiment 5
With dimethyl terephthalate (DMT), ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 10%.After ionic PET vacuum-drying, carry out high-speed stirring in varing proportions with polynite through the hexadecyl trimethyl ammonium bromide organic intercalation.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations.
The silicate particles of gained nano composite material is dispersed in the matrix with the 10-100 nano level.
Embodiment 6
With dimethyl terephthalate (DMT), ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 20%.After ionic PET vacuum-drying, carry out high-speed stirring in varing proportions with polynite through the hexadecyl trimethyl ammonium bromide organic intercalation.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations.
The silicate particles of gained nano composite material is dispersed in the matrix with the 10-100 nano level.
Embodiment 7
With dimethyl terephthalate (DMT), ethylene glycol and 5-sodium sulfonate dimethyl isophthalate is raw material, prepares the ionic PET that contains sulfonic acid group by ester-interchange method, and wherein the mol ratio of 5-sodium sulfonate dimethyl isophthalate is 0.1%.After ionic PET vacuum-drying, carry out high-speed stirring in varing proportions with polynite through the hexadecyl trimethyl ammonium bromide organic intercalation.Obtain ionic PET/ laminated nm-silicate composite material with Φ 25 twin screw extruder blend granulations.
The silicate particles of gained nano composite material is dispersed in the matrix with the 10-100 nano level.
Claims (8)
1. an ion polyester/phyllosilicate nano-composite material is characterized in that the feed composition of described matrix material and content are as follows, all is weight percentage:
Ionic polyester: layered silicate=100: 0.1-20
2. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that described ionic polyester is polyethylene terephthalate, the polycarbonate, poly-to naphthalic acid second diester, copolyester and above-mentioned two kinds or above mixture that molecular chain contains ionic group.
3. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 2 is characterized in that described ionic polyester, and ionic group is sulfonic acid group, hydroxy-acid group; The content of ionic group in polyester is 0.1-20% (mol ratio).
4. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that described layered silicate is the polynite of handling through organic intercalation agent.
5. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 4 is characterized in that described organic intercalation agent is the organic cation amine salt.
6. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 5 is characterized in that described organic cation amine salt is lauryl amine, hexadecylamine, hexanediamine, lauric acid amine, trolamine, dodecyl trimethylammonium amine bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethylammonium amine bromide and octadecyl benzyl dimethyl amine bromide.
7. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 1, 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, 0.1-20 part layered silicate and 100 parts of ionic polyester are melt extruded granulation, can obtain polyester ionomer/laminated nm-silicate composite material.
8. a kind of ionic polyester/phyllosilicate nano-composite material according to claim 7 is characterized in that adopting twin screw extruder equipment.
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| CN 200410024651 CN1583879A (en) | 2004-05-26 | 2004-05-26 | Ion polyester/laminated silicate nanometer composite materials and preparing method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558819A (en) * | 2012-01-04 | 2012-07-11 | 洛阳理工学院 | Preparation method of optical grade polycarbonate/phyllosilicate nanocomposite material |
| CN106012504A (en) * | 2015-09-07 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Modified montmorillonite coated polyester fiber composite material |
| CN114437518A (en) * | 2021-12-29 | 2022-05-06 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
-
2004
- 2004-05-26 CN CN 200410024651 patent/CN1583879A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558819A (en) * | 2012-01-04 | 2012-07-11 | 洛阳理工学院 | Preparation method of optical grade polycarbonate/phyllosilicate nanocomposite material |
| CN106012504A (en) * | 2015-09-07 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Modified montmorillonite coated polyester fiber composite material |
| CN114437518A (en) * | 2021-12-29 | 2022-05-06 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
| CN114437518B (en) * | 2021-12-29 | 2023-11-24 | 金发科技股份有限公司 | Low-warpage glass fiber reinforced PBT composition and preparation method and application thereof |
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