CN1927938A - Polyester/fibrous clay nano composite material, preparation method and application thereof - Google Patents
Polyester/fibrous clay nano composite material, preparation method and application thereof Download PDFInfo
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Abstract
The present invention discloses one kind of nanometer polyester/fibrous clay composite material and its preparation process and application. The nanometer polyester/fibrous clay composite material consists of polyester base and fibrous clay, which accounts for 0.1-10 wt% of the composite material and is rod crystals of 10-500 nm size dispersed in the polyester base. The nanometer polyester/fibrous clay composite material has relatively great molecular weight and less degradation after melt spinning. After the fiber of the composite material is drafted and oriented, the clay rod crystals with high length/diameter ratio are arranged in the drafting direction to strength the polyester fiber and raise the mechanical performance greatly. In addition, the clay rod crystals serve as the physical cross-linking points to limit the motion of great molecular chain, raise the heat resistance of the fiber and lower the dry heat shrinkage of the fiber.
Description
Technical field
The present invention relates to matrix material and preparation method thereof, particularly relate to a kind of polyester/fibrous clay nano composite material and preparation method thereof and application.
Background technology
Saturated polyester PET is cheap, and excellent combination property is mainly used in fields such as fiber, beverage bottle and engineering plastics.Pure PET exists heat-drawn wire low as engineering plastics, and crystallization velocity is slow, and the shortcoming of poor dimensional stability in order to enlarge its range of application, need be carried out modification and handle.Early stage method of modifying is mainly and adopts glass fibre, mineral filler etc. to fill polyester.Reported with glass fibre and talcum powder filling PET that as patent JP06049344 can improve its intensity, rigidity and dimensional stability etc., but the density of material increases simultaneously, the surface luster property and the transparency reduce significantly; Patent RU2052473 has reported and has utilized kaolin, wollastonite etc. to fill PET, can improve the PET dimensional stability, improves rigidity, and but, because the melt blended compound energy consumption height of PET, equipment attrition is big, easily degraded.Also there is a common shortcoming in the matrix material of above-mentioned method of modifying preparation: though glass fibre that is added or mineral filler are handled through means such as pulverizing, grindings, but most of sizes still are in micron level, orifice and filter screen aperture with respect to melt-spinning, oversize, cause easily stopping up, can't carry out spinning smoothly.
In recent years, a kind of novel method of utilizing layered silicate to prepare nanometer composite polyester material appears, Chinese invention patent CN1272513A, and CN1597776A, CN1396204A etc. all have report.The layered silicate of being taken if you would take off stone, mica, Meccah stone, rhombspar, saponite, illite, kaolin etc., because there is textural defect in layered crystal, interlayer has adsorbed a large amount of positively charged ions that can exchange, as Na
+, Ca
2+, Mg
2+, Al
3+Deng.Utilize organic cations such as organic ammonium salt, pyridinium salt, imidazole salts, organophosphorated salt, cationic exchange between clay seam can be come out, these larger-size organic cations then enter between the silicate lamella, thus the enlargement layer spacing.At external actions such as grinding, mechanical stirring, perhaps under the internal action such as heat of polymerization, polymer monomer, solution or melt can enter into the silicate plate interlayer, and at the interlayer polymerization reaction take place, impel the clay seam spacing further to enlarge.But, layered silicates such as polynite, there is stronger ionic linkage effect between lamella and the lamella, because the polarity of polyester is fainter, relatively poor with the consistency of clay, clay is difficult in polyester realize peeling off fully between the lamella that form large-sized reunion easily, the amplitude that causes polyester/clay nano composite material performance to improve is limited.
Summary of the invention
The purpose of this invention is to provide a kind of polyester/fibrous clay nano composite material that large size is reunited that is uniformly dispersed, do not have.
Polyester/fibrous clay nano composite material provided by the present invention, include polyester matrix and fibrous clay, wherein, fibrous clay is the 0.1-10% of polyester/fibrous clay nano composite material gross weight, is scattered in the polyester matrix with the excellent crystalline form attitude of 10-500 nano-scale.
Wherein, fibrous clay preferably accounts for the 0.1-5% of described polyester/fibrous clay nano composite material gross weight.
The polyester that the present invention is suitable for can comprise terephthalic acid (dimethyl ester), 2,6-naphthalic acid (dimethyl ester) and ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 1, the polycondensation product of 4-cyclohexanedimethanol or copolycondensation product, it also can be the multipolymer of these di-carboxylic acid (dimethyl ester) and dibasic alcohol and other di-carboxylic acid (dimethyl ester) or dibasic alcohol, these other di-carboxylic acid (dimethyl ester) or dibasic alcohol have m-phthalic acid (dimethyl ester), P-hydroxybenzoic acid, 4,4 '-the xenyl dicarboxylic acid, glycol ether, molecular weight is lower than 2000 polyoxyethylene glycol, molecular weight is lower than 3000 PTMG etc., and preferred polyester is a polyethylene terephthalate.Fibrous clay is natural needle-like of a class or fibrous hydration aluminium magensium silicate, mainly comprises polygorskite and sepiolite etc., is preferably palygorskite clay.
The preparation method of this polyester/fibrous clay nano composite material comprises the steps:
1) palygorskite clay is organised with the treatment agent that organises handles and/or, obtain organized clay with the surface treatment agent processing that organises; The described treatment agent that organises is alkylammonium salt, organophosphorated salt, pyridinium salt or water-soluble polymers; Described surface treatment agent is titanate coupling agent or silane coupling agent;
2) organized clay is dewatered after the drying, be scattered in the ethylene glycol, obtain described polyester/fibrous clay matrix material through in-situ polymerization.
Wherein, the used palygorskite clay of step 1) is that palygorskite clay raw ore, dispersion agent and water are mixed, and obtains after stirring, sedimentation, drying; Described dispersion agent is water glass, sodium aluminate, Trisodium Citrate, tripoly phosphate sodium STPP, trisodium phosphate or sodium-metaphosphate, and its consumption is the 0.1-5% of described palygorskite clay raw ore weight; The consumption of water is 1-50 a times of described palygorskite clay raw ore weight.
When step 1) prepared organized clay, palygorskite clay was suspended in the solvent, and common solvent can be selected from one or more in water, ethanol, methyl alcohol, ethylene glycol and the toluene, and its consumption is 1-100 a times of palygorskite clay weight.In the treating processes, the consumption of organise treatment agent or surface treatment agent is a 0.1-1mmol/ gram palygorskite clay; The described temperature of handling that organises is 0-100 ℃.The treatment agent that organises commonly used has cetyl trimethylammonium bromide, hexadecyl tri-phenyl-phosphorus bromide, hexadecyl pyridinium bromide, polyvinyl alcohol or Polyvinylpyrolidone (PVP) etc.Surface treatment agent commonly used has silane coupling agent KH560, KH550, KH570 and titanate coupling agent NDZ102, NDZ109 etc., adds acetic acid in use as hydrolyst.
Step 2) method of in-situ polymerization is ester interchange polymerization method or direct esterification polymerization:
The ester interchange polymerization method is carried out polyreaction with ethylene glycol, dimethyl terephthalate (DMT), organized clay described in the reaction: ethylene glycol: the weight ratio of dimethyl terephthalate (DMT) is 1: 7.5-750: 10-1000.
The direct esterification polymerization is carried out polyreaction with ethylene glycol, terephthalic acid, organized clay described in the reaction: ethylene glycol: the weight ratio of terephthalic acid is 1: 4.5-450: 8.54-854.
Another object of the present invention provides the purposes of matrix material of the present invention.
Polyester/fibrous clay nano composite material of the present invention has better spinnability, behind drying, crystallization, the solid phase polycondensation, under 260～300 ℃, carry out melt-spinning, through oiling, after the coiling, drawing-off, heat setting type, can preparing the polyester/fibrous clay nano composite material fiber of excellent performance.Above-mentioned drying temperature is 80～120 ℃, and Tc is 120～200 ℃, and solid phase polycondensation temperature is 180～240 ℃.
The present invention purifies raw ore, obtains the high purity fibrous clay, through organising and surface treatment after, in-situ polymerization prepares polyester/fibrous clay nano composite material, and realizes spinning smoothly, prepares the nanometer composite polyester material fiber.The clay that the present invention is selected because the reactive force between the excellent crystalline substance is more weak, mainly is a Van der Waals force, under effects such as mechanical stirring, ultrasonic, heat of polymerization, can make excellent brilliant cleavage through in-situ polymerization, is well disperseed in polyester matrix.The brilliant diameter of fibrous clay rod is about 10 nanometers, and length is about 200 nanometers, and length-to-diameter ratio is bigger.When disperse phase reaches nanoscale, the interfacial area that contacts with polyester is also very big, after the treatment agent that organises, tensio-active agent are handled, interface adhesion strengthens, utilize nano effect in the organism matrix, to give full play to the performance of inorganics, make matrix material have excellent mechanical property, thermotolerance.Simultaneously,, crystallizing polyester speed is significantly improved, improved the workability of material because nano-scale dispersive clay rod crystalline substance has the heterogeneous nucleation effect.
Polyester/the fibrous clay nano composite material of the present invention's preparation has higher molecular weight, and degraded is less behind the melt-spinning.The prepared nano composite material fiber, after draw orientation, the clay rod is brilliant in drawing-off direction orientations, and rod is brilliant itself to have higher length-to-diameter ratio, and trevira is had stronger enhancement, and the mechanical property of fiber is greatly enhanced.Simultaneously, clay rod crystalline substance has the effect of physical crosslinking point, has limited the motion of macromolecular chain, thereby has improved the resistance toheat of fiber, has reduced the dry-hot shrinkage of fiber, and excellent property is with a wide range of applications.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of clay;
Fig. 2 is the TEM photo of embodiment 1 resulting matrix material C;
Fig. 3 is the DSC collection of illustrative plates of embodiment 2 resulting matrix material D.
Embodiment
Embodiment 1,
One, the preparation of organized clay
Palygorskite clay is commonly called as attapulgite, and its typical chemical formula is Si
8Mg
5O
20(OH)
2(OH
2)
44H
2O.Its structure can be divided into three layers, and two-layer up and down is silicon-oxy tetrahedron, and middle one deck is alumina or magnesia octahedron, and these structural units are staggered by the grid form and constitute double-stranded shape channel-type crystalline structure.Owing to have the lattice displacement in the structure, so contain the commutative Na of non-quantitative in the crystal
+, Ca
2+, Mg
2+, Al
3+Plasma.Crystal is needle-like, fibrous coacervate.The rod brilliant diameter be about 5～50 nanometers, length is about 100～1000 nanometers, length-to-diameter ratio is bigger, because of the place of production different.
With 400 gram polygorskite raw ores (abundance is about 30%), 1.0 gram water glass add in 2000 ml waters, and high-speed stirring two hours is removed the throw outs such as grit of sub-cloud after the sedimentation.The suspension on upper strata is after centrifugal, and 100 ℃ of dryings are prepared the polygorskite after the purification.Fig. 1 is the X-ray diffractogram of the polygorskite after raw ore and the purification, shows that the polygorskite content after the purification reaches more than 90%.
Get polygorskite 10.0 grams after the purification, add hexadecyl pyridinium bromide 2.0 grams, water 300 grams, 90 ℃ of high-speed stirring four hours, the palygorskite clay that organises was prepared in centrifugal, washing three times.
Get back palygorskite clay 10.0 gram that organises, add 0.1 gram coupling agent KH550,10 gram acetic acid, 200 gram water, vigorous stirring two hours, centrifugal water give a baby a bath on the third day after its birth time to pH be 7,300 mesh sieves are ground, crossed to drying, organized clay 1.
Two, the ester interchange polymerization legal system is equipped with matrix material
Get organized clay 1 powder 0.30 gram, add ethylene glycol 75.0 grams, after vigorous stirring is disperseed, add in the reactor, add dimethyl terephthalate (DMT) (DMA) 100.0g, transesterification catalyst Mn (Ac)
20.030 gram, logical nitrogen is heated to 200 ℃ of reactions three hours, after steaming more than methyl alcohol 30 grams, add antimonous oxide 0.030 gram, at 280 ℃, pressure was lower than under the condition of 200Pa polycondensation 1.5 hours, add the 0.10g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again, the polyester/clay nano composite material A (process that vacuumizes in polycondensation of 0.3% polygorskite content (weight), extract a part of ethylene glycol of reaction product small molecules methyl alcohol and excessive interpolation out, according to the mass conversion of DMA, the theoretical yield of polyester should be 100g, and the content with regard to polygorskite is exactly 0.3% like this).
Get organized clay 1 powder 0.5 gram, add ethylene glycol 75.0 grams, after vigorous stirring is disperseed, add in the reactor, add dimethyl terephthalate (DMT) 100.0g, with reference to aforesaid method, obtain the polyester/clay nano composite material B of 0.5% polygorskite content (weight).
Get organized clay 1 powder 1.0 grams, add ethylene glycol 75.0 grams, after vigorous stirring is disperseed, add in the reactor, add dimethyl terephthalate (DMT) 100.0g, with reference to aforesaid method, obtain the polyester/clay nano composite material C of 1% polygorskite content (weight).
Transmission electron microscope (TEM) photo of the polyester/clay nano composite material C of 1% polygorskite content can clear view be uniformly dispersed in polyester matrix to clay as shown in Figure 2, disperses yardstick between 10-500nm, does not have tangible agglomeration.The brilliant part of fibrous clay rod is peeled off, and length is about 200 nanometers, and diameter is about 20 nanometers.
Embodiment 2,
One, the preparation of palygorskite clay
With 400 gram polygorskite raw ores (abundance is about 30%), 1.0 gram trisodium phosphates add in 2000 ml waters, and vigorous stirring two hours is removed the throw outs such as grit of sub-cloud after the sedimentation.The suspension on upper strata is after centrifugal, and 100 ℃ of dryings are prepared the polygorskite after the purification.
Get polygorskite 10.0 grams after the purification, add hexadecyl tri-phenyl-phosphorus bromide 2.0 grams, water 300 grams, vigorous stirring, 90 ℃ of constant temperature four hours, the palygorskite clay that organises is prepared in centrifugal, washing three times.
Get back palygorskite clay 10.0 gram that organises, add 0.1 gram titanate coupling agent NDZ102,50 milliliters of toluene, vigorous stirring two hours, centrifugal water give a baby a bath on the third day after its birth time to PH be 7,300 mesh sieves are ground, crossed to drying, organized clay 2.
Two, direct esterification polymerization prepares matrix material
Get organized clay 2 powder 3.0 grams, add ethylene glycol 45.0 grams, after vigorous stirring is disperseed, add in the reactor, add monomers terephthalic acid (PTA) 85.4g, 0.030g antimony acetate catalyzer, intensification 250-260 ℃, pressurization 0.3-0.1MPa carries out esterification.Be lower than under the condition of 200Pa polycondensation at 280 ℃, pressure 1.5 hours, add the 0.10g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again, polyester/clay nano composite material D that must 3.0% polygorskite content.
This material is carried out thermal performance analysis, and compare with pure PET, its DSC collection of illustrative plates as shown in Figure 3, two curves above among the figure are temperature-rise period, from the figure as can be seen: the fusing point of polyester/clay composite material PET-D is close with the fusing point of pure polyester PET, and illustrating does not influence the polymerization fusing point after adding clay; Can learn that from two following temperature lowering curves the Tc of polyester/fibrous clay nano composite material is about 215 ℃, far above the Tc of pure PET, the crystallization velocity of this explanation nano composite material is very fast.
Embodiment 3,
One, the preparation of organized clay
With 400 gram polygorskite raw ores (abundance is about 30%), 1.0 gram sodium-metaphosphates add in 2000 ml waters, and vigorous stirring two hours is removed the throw outs such as grit of sub-cloud after the sedimentation.The suspension on upper strata is after centrifugal, and 100 ℃ of dryings are prepared the polygorskite after the purification.
Get polygorskite 10.0 grams after the purification, add 0.1 gram coupling agent KH570,10 gram acetic acid, 200 gram water, vigorous stirring two hours, centrifugal water give a baby a bath on the third day after its birth time to PH be 7, prepare the palygorskite clay after the surface treatment.
Get palygorskite clay 10.0 grams after the surface treatment, add polyvinylpyrrolidone 2.0 grams, water 300 grams, vigorous stirring, 90 ℃ of constant temperature four hours, centrifugal, washing three times, 300 mesh sieves are ground, crossed to drying, organized clay 3.
Two, direct esterification polymerization prepares matrix material
Get above-mentioned organized clay 3 powder 3.00 grams, add ethylene glycol 45.0 grams, after vigorous stirring is disperseed, add in the reactor, add monomers terephthalic acid (PTA) 85.4g, 0.030g antimony acetate catalyzer, intensification 250-260 ℃, pressurization 0.3-0.1MPa carries out esterification.Be lower than under the condition of 200Pa polycondensation at 280 ℃, pressure 1.5 hours, add the 0.10g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again, polyester/clay nano composite material E that must 3.0% polygorskite content.
Embodiment 4,
With 400 gram polygorskite raw ores (abundance is about 30%), 1.00 gram tripoly phosphate sodium STPPs add in 2000 ml waters, and vigorous stirring two hours is removed the throw outs such as grit of sub-cloud after the sedimentation.The suspension on upper strata is after centrifugal, and 100 ℃ of dryings are prepared the polygorskite after the purification.
Get polygorskite 10.0 grams after the purification, add cetyl trimethylammonium bromide 2.0 grams, methyl alcohol 300 grams, vigorous stirring, 90 ℃ of constant temperature four hours, centrifugal, washing three times to PH be 7, prepare the palygorskite clay that organises.300 mesh sieves are ground, crossed to drying, gets organized clay 4.
Get above-mentioned organized clay 4 powder 3.0 grams, add ethylene glycol 45.0 grams, after vigorous stirring is disperseed, add in the reactor, add monomers terephthalic acid (PTA) 85.4g, 0.030g antimony acetate catalyzer, intensification 250-260 ℃, pressurization 0.3-0.1MPa carries out esterification.Be lower than under the condition of 200Pa polycondensation at 280 ℃, pressure 1.5 hours, add the 0.10g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again, polyester/clay nano composite material F that must 3.0% polygorskite content.
With 400 gram polygorskite raw ores (abundance is about 30%), 1.00 gram sodium aluminates add in 2000 ml waters, and vigorous stirring two hours is removed the throw outs such as grit of sub-cloud after the sedimentation.The suspension on upper strata is after centrifugal, and 100 ℃ of dryings are prepared the polygorskite after the purification.
Get palygorskite clay 10.0 grams after the purification, add 0.1 gram coupling agent KH550,10 gram acetic acid, 200 gram ethanol, vigorous stirring two hours, centrifugal water give a baby a bath on the third day after its birth time to PH be 7,300 mesh sieves, the clay 5 after must handling are ground, crossed to drying.
Get above-mentioned clay 5 powder 3.0g, with 88.2g dimethyl terephthalate (DMT), 90g1,4-butyleneglycol and 0.0100g zinc acetate drop in the reactor of logical nitrogen together, be warming up to 200 ℃, after theoretical amount methyl alcohol until 95% is steamed, add the positive butyl ester 0.15mL of catalyzer metatitanic acid, be warming up to 260 ℃, vacuumize, be lower than at pressure that polycondensation added 0.10 gram triphenyl phosphite after 1.5 hours under the condition of 200Pa, polycondensation is after 1.5 hours again, reaction finishes, and gets the PBT/ clay nanocomposites G of 3% polygorskite content.
Adopt and use the same method, can prepare polyester matrix is terephthalic acid (dimethyl ester), 2,6-naphthalic acid (dimethyl ester) and ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 1, the polycondensation product of 4-cyclohexanedimethanol or copolycondensation product, it also can be the multipolymer of these di-carboxylic acid (dimethyl ester) and dibasic alcohol and other di-carboxylic acid (dimethyl ester) or dibasic alcohol, these other di-carboxylic acid (dimethyl ester) or dibasic alcohol have m-phthalic acid (dimethyl ester), P-hydroxybenzoic acid, 4,4 '-the xenyl dicarboxylic acid, glycol ether, molecular weight is lower than 2000 polyoxyethylene glycol, molecular weight is lower than the matrix material of 3000 PTMG etc.
Embodiment 6,
With 400 gram polygorskite raw ores (abundance is about 30%), 1.00 gram water glass add in 2000 ml waters, and vigorous stirring two hours is removed the throw outs such as grit of sub-cloud after the sedimentation.The suspension on upper strata is after centrifugal, and 100 ℃ of dryings are prepared the polygorskite after the purification.
Get palygorskite clay 10.0 grams after the purification, add 0.1 gram coupling agent KH560,10 gram acetic acid, 200 gram ethylene glycol, vigorous stirring two hours, centrifugal water give a baby a bath on the third day after its birth time to PH be 7,300 mesh sieves, the clay 6 after must handling are ground, crossed to drying.
Get above-mentioned clay 6 powder 10.0 grams, add ethylene glycol 40.5 grams, after vigorous stirring is disperseed, add in the reactor, add monomers terephthalic acid (PTA) 76.9g, 0.027g antimony acetate catalyzer, intensification 250-260 ℃, pressurization 0.3-0.1MPa carries out esterification.Be lower than under the condition of 200Pa polycondensation at 280 ℃, pressure 1.5 hours, add the 0.09g triphenyl phosphite, polycondensation finishes reaction after 1.5 hours again, polyester/clay nano composite material H that must 10% polygorskite content.
Embodiment 7, material properties test
1, Measurement of Material Mechanical Performance
Measure the preparation-obtained polyester/clay nano composite material of embodiment 1-4 A-H according to ordinary method, the result is as shown in table 1.
The mechanical property of table 1 polyester/palygorskite clay nano composite material
| The sample title | The technical grade polyester | A | B | C | D | E | F | G | H |
| Viscosity | 0.61 | 0.58 | 0.58 | 0.60 | 0.59 | 0.60 | 0.63 | 0.60 | 0.56 |
| Tensile strength/MPa | 59.4 | 65.5 | 58.3 | 49.0 | 54.5 | 52.2 | 53.0 | 49.3 | 43.2 |
| Elongation/% | 46 | 15 | 12 | 8 | 7 | 5 | 7 | 35 | 5 |
| Flexural strength/MPa | 78.1 | 87.5 | 78.1 | 67.7 | 70.2 | 77.4 | 81.4 | 60.3 | 90.4 |
| Modulus in flexure/MPa | 2042 | 2209 | 2231 | 2536 | 2465 | 2534 | 2681 | 2032 | 2750 |
| Notched Izod impact strength/(J/m) | 39 | 50 | 26 | 21 | 31 | 28 | 29 | 36 | 21 |
The result shows that the polyester nano of gained/fibrous clay matrix material is compared with the technical grade polyester, and tensile strength changes little, and elongation obviously reduces along with the increase of addition.In addition, the modulus in flexure of matrix material increases.
2, the melt-spinning of material
Get the prepared polyester/fibrous clay nano composite material A of embodiment 1, through 2 hours 130～150 ℃ of primary crystals, 150～180 ℃ of crystallizations in 2 hours, 8 hours 200～220 ℃ of solid phase polycondensations, at 260～290 ℃ of following melt-spinnings, oil, reel, 0.3% nano compound polyester fibre 1 is prepared polygorskite content and is in drawing-off after the heat setting type.
Adopt same processing method, use embodiment 1 resulting nano composite material B and C respectively, prepare polygorskite content and be respectively 0.5%, 1% nano compound polyester fibre 2 and 3, simultaneously, with the polyester industrial product through in contrast with the melt-spinning of sampling technology.This series fiber is carried out mechanical property, tests such as dry shrinkage, the result is as shown in table 2.
The performance of table 2 polyester/palygorskite clay nano composite material fiber
| The PET fiber | Pure PET | 1 | 2 | 3 |
| Polygorskite content, % | 0 | 03 | 0.5 | 1.0 |
| Limiting viscosity before the spinning | 0.84 | 0.83 | 0.78 | 0.86 |
| Limiting viscosity after the spinning | 0.70 | 0.64 | 0.66 | 0.68 |
| Linear density, dtex | 183.7 | 182.5 | 180.2 | 182.4 |
| Breaking tenacity, cN/dtex | 4.86 | 5.28 | 4.72 | 5.25 |
| Elongation at break, % | 6.8 | 8.7 | 7.4 | 7.0 |
| 4.0cN/dtex the elongation under the load, % | 5.1 | 4.8 | 5.2 | 4.0 |
| Dry-hot shrinkage (177C, 10min), % | 9.8 | 8.9 | 8.1 | 8.8 |
The result shows, compares with the fiber of technical grade polyester spinning gained, adds after the fibriform paligorskite clay, and the breaking tenacity and the modulus of fiber significantly improve, and dry-hot shrinkage descends to some extent.In addition, polyester inherent viscosity descends lessly after the spinning, illustrate that fibrous clay is also not obvious to the thermal destruction influence of polyester.
Claims (11)
1, a kind of polyester/fibrous clay nano composite material, include polyester matrix and fibrous clay, wherein, fibrous clay is the 0.1-10% of polyester/fibrous clay nano composite material gross weight, is scattered in the polyester matrix with the excellent crystalline form attitude of 10-500 nano-scale.
2, polyester/fibrous clay nano composite material according to claim 1 is characterized in that: described fibrous clay accounts for the 0.1-5% of described polyester/fibrous clay nano composite material gross weight.
3, polyester/fibrous clay nano composite material according to claim 1 and 2, it is characterized in that: described polyester matrix is a phthalic acid, rutgers, 2,6-naphthalic acid or 2,6-naphthalene diformic acid dimethyl ester and ethylene glycol, 1, ammediol, 1,4-butyleneglycol or 1, the polycondensation product of 4-cyclohexanedimethanol or copolycondensation product, it perhaps is m-phthalic acid, dimethyl isophthalate, P-hydroxybenzoic acid, 4,4 '-xenyl dicarboxylic acid, glycol ether, molecular weight is lower than 2000 polyoxyethylene glycol, molecular weight is lower than the multipolymer of 3000 PTMG; Described polyester matrix is preferably polyethylene terephthalate; Described fibrous clay is natural needle-like or fibrous hydration aluminium magensium silicate, is preferably polygorskite or sepiolite, more preferably palygorskite clay.
4, the preparation method of the described polyester/fibrous clay nano composite material of claim 3 comprises the steps:
1) palygorskite clay is organised with the treatment agent that organises handles and/or, obtain organized clay with the surface treatment agent processing that organises; The described treatment agent that organises is alkylammonium salt, organophosphorated salt, pyridinium salt or water-soluble polymers; Described surface treatment agent is titanate coupling agent or silane coupling agent;
2) organized clay is dewatered after the drying, be scattered in the ethylene glycol, obtain described polyester/fibrous clay matrix material through in-situ polymerization.
5, preparation method according to claim 4 is characterized in that: the described palygorskite clay of step 1) is that palygorskite clay raw ore, dispersion agent and water are mixed, and obtains after stirring, sedimentation, drying; Described dispersion agent is water glass, sodium aluminate, Trisodium Citrate, tripoly phosphate sodium STPP, trisodium phosphate or sodium-metaphosphate, and its consumption is the 0.1-5% of described palygorskite clay raw ore weight; The consumption of water is 1-50 a times of described palygorskite clay raw ore weight.
6, preparation method according to claim 4, it is characterized in that: the described palygorskite clay of step 1) is suspended in the solvent, described solvent is selected from one or more in water, ethanol, methyl alcohol, ethylene glycol and the toluene, and its consumption is 1-100 a times of described palygorskite clay weight; The consumption of described organise treatment agent or surface treatment agent is a 0.1-1mmol/ gram palygorskite clay; The described temperature of handling that organises is 0-100 ℃.
7, preparation method according to claim 6 is characterized in that: the described treatment agent that organises is cetyl trimethylammonium bromide, hexadecyl tri-phenyl-phosphorus bromide, hexadecyl pyridinium bromide, polyvinyl alcohol or Polyvinylpyrolidone (PVP); Described silane coupling agent is KH550, KH560 or KH570; Described titanate coupling agent is NDZ102 or NDZ109.
8, according to the arbitrary described preparation method of claim 4-7, it is characterized in that: step 2) method of described in-situ polymerization is ester interchange polymerization method or direct esterification polymerization.
9, preparation method according to claim 8, it is characterized in that: described ester interchange polymerization method is carried out polyreaction with ethylene glycol, dimethyl terephthalate (DMT), organized clay described in the reaction: ethylene glycol: the weight ratio of dimethyl terephthalate (DMT) is 1: 7.5-750: 10.0-1000.
10, preparation method according to claim 8, it is characterized in that: described direct esterification polymerization is carried out polyreaction with ethylene glycol, terephthalic acid, organized clay described in the reaction: ethylene glycol: the weight ratio of terephthalic acid is 1: 4.5-450: 8.54-854.
11, the conjugated fibre of making by the described polyester/fibrous clay nano composite material of claim 1.
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| CNB2005100984088A CN100465226C (en) | 2005-09-06 | 2005-09-06 | Polyester/fibrous clay nano composite material, preparation method and application thereof |
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| CN100465226C CN100465226C (en) | 2009-03-04 |
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| CN102344653A (en) * | 2010-07-28 | 2012-02-08 | 中国科学院合肥物质科学研究院 | Polyethylene terephthalate (PET)/inorganic/organic nano-composite material and preparation method thereof |
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| AU758538B2 (en) * | 1998-12-07 | 2003-03-27 | University Of South Carolina Research Foundation | A colorant composition, a polymer nanocomposite comprising the colorant composition and articles produced therefrom |
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