CN100537659C - Method for preparing PET copolymer ester/clay nano composite material - Google Patents
Method for preparing PET copolymer ester/clay nano composite material Download PDFInfo
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- CN100537659C CN100537659C CNB2004100740341A CN200410074034A CN100537659C CN 100537659 C CN100537659 C CN 100537659C CN B2004100740341 A CNB2004100740341 A CN B2004100740341A CN 200410074034 A CN200410074034 A CN 200410074034A CN 100537659 C CN100537659 C CN 100537659C
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Abstract
This invention discloses a method for prparing PETcopolyester/clay nano composite material. By weight, the method carries through as following:(1)clay is dispersed in dispersion medium to form stable suspension system with dispersion aids ;(2)mixing organic intercalation agent, ionizing additive and dispersion medium uniformly;(3)at stirring, dropwise adding solution of step(2) to clay suspension of step(1),stirring reaction, centrifugation, washing;(4)adding filter cake of step(3),amide polymerization catalyst and additive to polyamide monomer, stirring, atmospheric distillation polymerization, pelleting, extraction, drying, that is polyamide clay agglomerate;(5)BHET and polyamide clay nano agglomerate condensation. This invention improves greatly dispersion homogeneity of montmorillonite.
Description
Technical field
The present invention relates to the preparation method of PET copolyesters matrix material, particularly the preparation method of PET copolyesters/clay nanocomposites.
Background technology
PET is a kind of polymkeric substance of high comprehensive performance, be widely used in fields such as fiber, beverage bottle and engineering plastics, but its crystallization velocity is slow, heat-drawn wire is low, drawbacks limit such as barrier properties for gases difference its range of application.Prepare the polyester/clay nano composite material by in-situ polymerization or melt blending and can improve the above-mentioned shortcoming of polyester.Patent CN1272513 at first utilizes alkylammonium salt as intercalator intercalation processing to be carried out in polynite and obtains organic montmorillonoid, organic montmorillonoid is scattered in PET monomer or the performed polymer then, the adding catalyzer carries out in-situ polymerization and prepares the PET/ clay nanocomposites, the heat-drawn wire of this matrix material, the purer PET of performance such as crystallization rate and modulus in flexure improves to some extent, patent US5876812 adds polynite in the transesterify stage, in-situ polymerization prepares the PET/ clay nanocomposites, they utilize the PET/ clay nanocomposites that is obtained to blow bottle, and this bottle is significantly improved than conventional P ET bottle to the barrier property of oxygen.The preparation of above-mentioned patent be intercal type polyester/clay nano composite material, limited to the performance increase rate of polyester, be difficult to prepare high performance strippable PET/clay nanocomposites.
Nylon 6/ clay nanocomposites is to develop (U.S. Pat 4 the earliest, 739,007 and Chinese patent CN1138593A, CN1300794A), it also is the composite nano polymer/clay material of easy preparation, the consistency of nylon 6 and clay is better, clay can be easy to peel off into monolithic layer when polymerization or melt blending, prepare exfoliated nylon 6/ clay nanocomposites.If the acid amides segment is introduced in the PET macromolecular chain, improve the consistency of itself and clay, then can prepare strippable PET/clay nanocomposites.
Summary of the invention
The objective of the invention is to overcome in the past that polynite disperses shortcomings such as even inadequately in the polyester/clay nano composite material, PET copolyesters/clay nanocomposites preparation method is provided, improve the polynite dispersing uniformity, improve every performance of polyester/clay nano composite material.
The preparation method of PET copolyesters/clay nanocomposites of the present invention, in weight part, undertaken by following step:
(1) be that 0.1～20 part of the clay of 50～200meq/100g is dispersed in 1～400 part the dispersion medium with the cationic exchange total volume, the dispersion aids that adds 0.02～0.5 part simultaneously carries out high-speed stirring, forms stable suspension system;
(2) 0.02～10 part of organic intercalation agent, 0.01～1.0 part of ionization auxiliary agent and 1～400 part of dispersion medium are mixed, form the homogeneous system;
(3) drips of solution that under agitation step (2) is made adds in the slurry that step (1) makes, and in 50～150 ℃ of stirring reactions 0.5～8 hour, centrifugal then, washing, the filter cake solid content is 10～70%;
(4) 5～30 parts, 0.5～20 part acid amides polymerizing catalyst of the filter cake that step (3) is made and additive join in 100 parts of monomer of polyamide for 0～5 part, in ℃ scope of its melting temperature ± 20, stirred 1～4 hour, be warmed up to 250～280 ℃ of air distillation polymerizations 1～10 hour again, after pelletizing, extract, be drying to obtain polymeric amide clay nano master batch;
(5) 100 parts of ethylene glycol terephthalates (BHET) and 5～40 parts of polymeric amide clay nano master batches are added reactor, being warming up to 180～240 ℃ stirred 0.5～3 hour, adopt ordinary method, add 0.01～1 part of polyester polycondensation catalyst and 0.05～2 part of additive, be warming up to 240～280 ℃, be decompressed to 1～50Pa aftercondensated 1～5 hour through twice, promptly get PET copolyesters/clay nanocomposites.Gained polynite disperse phase is scattered in the PET matrix with 10～100nm yardstick.
The used clay of the present invention is that a class mineral main component is for containing the layered silicate of 85～95% polynites (MMT).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.The montmorillonite clay internal surface has negative charge, the Na of interlayer absorption
+, Ca
2+, Mg
2+Deng positively charged ion is the interchangeability positively charged ion, can exchange with other metallic cation or the organic cation outside the layer.Clay cation total exchange capacity (CEC) is 50～200meq/100g, is preferably 90～110meq/100g.Clay content is 0.1～20 part, is preferably 1～5 part.
Dispersion medium of the present invention can be water, lower alcohols such as methyl alcohol, ethanol, ethylene glycol etc.
The organic intercalation agent that the present invention uses is monomer of polyamide or acid amides polymerizing catalyst, organic phosphonium salt, pyridinium salt or water-soluble polymers, as hexanolactam, butyrolactam, spicy inner formyl amine, ω oenantholactam, 11 lactan, laurolactam and their open-loop products amino acid (as hexosamine, aminobutyric acid, aminocaprylic acid, ten monoamino-acids, ten diamino acid etc.), hexadecyl triphenyl bromide phosphine, hexadecyl pyridinium bromide, polyvinyl alcohol, polyvinylpyrrolidone etc.
Dispersion aids of the present invention is to make clay disperse better phosphoric acid ester material in monomer of polyamide, can be trimethyl phosphite 99, triethyl phosphate, triphenylphosphate and analogue thereof.
Ionization auxiliary agent of the present invention can be phosphoric acid, hydrochloric acid, sulfuric acid or acetic acid etc.
Acid amides polymerizing catalyst of the present invention can be water, hexosamine, aminobutyric acid, aminocaprylic acid, ten monoamino-acids, ten diamino acid etc.
Additive of the present invention can be molecular weight stabilizer, as acetic acid, hexanodioic acid, dicarboxylic acid, dicarboxylic ester etc., can be stablizer, as phosphoric acid salt, phosphite etc., can also be lubricant, nucleator, tinting material etc.Additive can separately or be used.
The polyester polycondensation catalyst that the present invention uses is antimony acetate, antimonous oxide, butyl (tetra) titanate, titanium potassium oxalate(T.P.O.) etc.
The present invention introduces the acid amides segment in the PET macromolecular chain, improves the consistency of itself and clay, has prepared strippable PET copolyesters/clay nanocomposites, has improved the polynite dispersing uniformity greatly.
Description of drawings
Fig. 1 is PET copolyesters/clay nanocomposites x-ray diffraction pattern
Fig. 2 is PET copolyesters/clay nanocomposites DSC heating curve
Fig. 3 is PET copolyesters/clay nanocomposites DMA curve
Embodiment
Embodiment 1
(1) be that 100meq/100g, particle diameter 200 purpose montmorillonite 50.0g and trimethyl phosphite 99 4g join in the 2000g deionized water with cation exchange capacity, high-speed stirring 0.5 hour obtains the aqeous suspension A of montmorillonite.(2) 10.0g hexosamine, 10.2g phosphoric acid are dissolved in and obtain organising liquid B in the 500g deionized water.(3) under agitation B is added dropwise among the A, temperature maintenance kept 4 hours at 80 ℃, naturally cool to room temperature after, centrifugal, the washing, obtain filter cake 110g (solid content 48%).(4) then, 110g filter cake, 435g hexanolactam, 43.5g hexosamine, 0.44g hexanodioic acid are blended in 90 ℃ to be stirred 3 hours, continue to be warmed up to 260 ℃ and begin distillation continuation reaction 4 hours, the pressurization discharging, the Cast Strip pelletizing, the water hot extraction, vacuum-drying obtains the nylon 6/ clay master batch of clay content 10%.
120gBHET and above-mentioned nylon 6/ clay master batch 10g join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, after treating the whole fusions of BHET, stir and dissolved fully until nylon 6/ clay nano master batch in 2 hours, add the 0.032g antimonous oxide, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 10～15Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get PET copolyesters/clay nanocomposites after 4 hours, intrinsic viscosity is 0.67dl/g, and through the XRD test, discovery has not had diffraction peak below 10 °, illustrates that montmorillonite layer peels off (seeing accompanying drawing 1b) fully.
By accompanying drawing 2 as can be known, the fusing point of PET copolyesters/clay nanocomposites is 250.6 ℃, between 257.2 ℃ of 219.4 ℃ of nylon 6 fusing points and PET fusing points, the melting peak that nylon 6 on the DSC of PET copolyesters/clay nanocomposites heating curve, do not occur, PET copolyesters/clay nanocomposites has been prepared in this explanation, rather than the simple mixtures of PET and nylon 6.
By accompanying drawing 3DMA curve as can be known, the second-order transition temperature of PET copolyesters is 79.3 temperature, between nylon 6 and PET second-order transition temperature, illustrates that equally the acid amides section introduced in the macromolecular chain of PET, has prepared the PET copolyesters.
Embodiment 2
The nylon 6/ clay nano master batch 20g of 106gBHET and embodiment 1 preparation joins in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, after treating the whole fusions of BHET, stir and dissolved fully until nylon 6/ clay master batch in 2 hours, add the 0.032g antimonous oxide, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 10～15Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get PET copolyesters/clay nanocomposites after 4 hours, intrinsic viscosity is 0.65dl/g, and through the XRD test, discovery has not had diffraction peak below 10 °, illustrates that montmorillonite layer peels off fully.
Embodiment 3
(1) be that 90meq/100g, particle diameter 200 purpose montmorillonite 50.0g and trimethyl phosphite 99 4g join in the 1000g deionized water with cation exchange capacity, high-speed stirring 0.5 hour obtains the aqeous suspension A of montmorillonite.(2) the 25.0g polyvinylpyrrolidone is dissolved in and obtains organising liquid B in the 500g deionized water.(3) under agitation B is added dropwise among the A, temperature maintenance kept 4 hours at 90 ℃, naturally cool to room temperature after, centrifugal, the washing, obtain filter cake 90g (solid content 51%).(4) then, 90g filter cake, 370g hexanolactam, 37.0g hexosamine are blended in 90 ℃ stirred 3 hours, be warmed up to 260 ℃ and begin distillation continuation reaction 6 hours, the pressurization discharging, the Cast Strip pelletizing, the water hot extraction, vacuum-drying obtains the nylon 6/ clay master batch of clay content 10%.
120gBHET and above-mentioned nylon 6/ clay nano master batch 10g join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, after treating the whole fusions of BHET, stir and dissolved fully until nylon 6/ clay nano master batch in 2 hours, add the 0.064g antimony acetate, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 10～15Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get PET copolyesters/clay nanocomposites after 4 hours, intrinsic viscosity is 0.68dl/g, and through the XRD test, discovery has not had diffraction peak below 10 °, illustrates that montmorillonite layer peels off (seeing accompanying drawing 1c) fully.
Embodiment 4
With cation exchange capacity is that 100meq/100g, particle diameter 200 purpose montmorillonite 50.0g and trimethyl phosphite 99 4g join in the 2000g deionized water, and high-speed stirring 0.5 hour obtains the aqeous suspension A of montmorillonite.(2) 10.0g hexosamine, 10.2g phosphoric acid are dissolved in and obtain organising liquid B in the 400g deionized water.(3) under agitation B is added dropwise among the A, temperature maintenance kept 4 hours at 80 ℃, naturally cool to room temperature after, centrifugal, the washing, obtain filter cake 110g (solid content 48%).(4) then, 110g filter cake, 195g hexanolactam, 19.5g hexosamine are blended in 90 ℃ stirred 3 hours, be warmed up to 260 ℃ and begin distillation continuation reaction 5 hours, the pressurization discharging, the Cast Strip pelletizing, the water hot extraction, vacuum-drying obtains the nylon 6/ clay master batch of clay content 20%.
120gBHET and above-mentioned nylon 6/ clay master batch 10g join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, after treating the whole fusions of BHET, stir and dissolved fully until nylon 6/ clay master batch in 2 hours, add the 0.032g antimonous oxide, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 10～15Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get PET copolyesters/clay nanocomposites after 4 hours, intrinsic viscosity is 0.67dl/g, and through the XRD test, discovery has not had diffraction peak below 10 °, illustrates that montmorillonite layer peels off fully.
Comparative Examples 1
With cation exchange capacity is that the polynite 8.0g of 100meq/100g is uniformly dispersed in 200g water, 2.2g dissolving the back in 100g water, cetyl trimethylammonium bromide adds in the polynite aqeous suspension, 80 ℃ are stirred centrifugation after 4 hours, clean repeatedly with distilled water, until detecting no bromide anion with the 0.1N silver nitrate solution, product is pulverized after drying, gets organic montmorillonoid powder cheating engaging layer spacing and further expands as 2.5nm.
132gBHET, 0.032g antimonous oxide and above-mentioned polynite powder 2.0g mix, join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, treat the whole fusions of BHET after, stirred 1 hour fast, add the 0.2g trimethyl phosphite 99, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 8～12Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get the PET/ clay nanocomposites after 4 hours, intrinsic viscosity is 0.64dl/g, and the cheating engaging layer spacing is 1.8nm (seeing accompanying drawing 1a).
Claims (2)
1.PET the preparation method of copolyesters/clay nanocomposites in weight part, is undertaken by following step:
(1) be that 0.1～20 part of the clay of 50～200meq/100g is dispersed in 1～400 part the dispersion medium with the cationic exchange total volume, the dispersion aids that adds 0.02～0.5 part simultaneously carries out high-speed stirring, forms stable suspension system;
(2) 0.02～10 part of organic intercalation agent, 0.01～1.0 part of ionization auxiliary agent and 1～400 part of dispersion medium are mixed, form the homogeneous system;
(3) drips of solution that under agitation step (2) is made adds in the slurry that step (1) makes, and in 50～150 ℃ of stirring reactions 0.5～8 hour, centrifugal then, washing, the filter cake solid content is 10～70%;
(4) 5～30 parts, 0.5～20 part acid amides polymerizing catalyst of the filter cake that step (3) is made and additive join in 100 parts of monomer of polyamide for 0～5 part, in ℃ scope of its melting temperature ± 20, stirred 1～4 hour, be warmed up to 250～280 ℃ of air distillation polymerizations 1～10 hour again, after pelletizing, extract, be drying to obtain polymeric amide clay nano master batch;
(5) 100 parts of ethylene glycol terephthalates and 5～40 parts of polymeric amide clay nano master batches are added reactor, being warming up to 180～240 ℃ stirred 0.5～3 hour, adopt ordinary method, add 0.01～1 part of polyester polycondensation catalyst and 0.05～2 part of additive, be warming up to 240～280 ℃, be decompressed to 1～50Pa aftercondensated 1～5 hour through twice, promptly get PET copolyesters/clay nanocomposites;
Described dispersion medium is water or lower alcohol;
Described organic intercalation agent is monomer of polyamide or acid amides polymerizing catalyst, organic phosphonium salt, pyridinium salt or water-soluble polymers;
Described dispersion aids is trimethyl phosphite 99, triethyl phosphate or triphenylphosphate;
Described ionization auxiliary agent is phosphoric acid, hydrochloric acid, sulfuric acid or acetic acid;
Described acid amides polymerizing catalyst is water, hexosamine, aminobutyric acid, aminocaprylic acid, ten monoamino-acids or ten diamino acid;
Described additive is molecular weight stabilizer, phosphoric acid salt, phosphite, lubricant, nucleator or tinting material, separately or be used;
Described polyester polycondensation catalyst is antimony acetate, antimonous oxide, butyl (tetra) titanate or titanium potassium oxalate(T.P.O.).
2. according to the preparation method of claim 1, it is characterized in that: described clay cation total exchange capacity is 90～110meq/100g, and clay content is 1～5 part.
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| CNB2004100740341A CN100537659C (en) | 2004-09-01 | 2004-09-01 | Method for preparing PET copolymer ester/clay nano composite material |
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| CN100537659C true CN100537659C (en) | 2009-09-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100402606C (en) * | 2006-03-30 | 2008-07-16 | 南京化工职业技术学院 | PET/clay nano composite materials and method for preparing same |
| CN101775126B (en) * | 2009-01-09 | 2011-09-07 | 中国石油天然气股份有限公司 | Polyester polycondensation catalyst, preparation method thereof and application thereof |
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Patent Citations (9)
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| CN1192444A (en) * | 1998-02-20 | 1998-09-09 | 华南理工大学 | Method for preparing polymer nanometre composite material |
| US6417262B1 (en) * | 1998-12-07 | 2002-07-09 | Eastman Chemical Company | High barrier amorphous polyamide-clay nanocomposite and a process for preparing same |
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