CN100537659C - Preparation method of PET copolyester/clay nanocomposite - Google Patents
Preparation method of PET copolyester/clay nanocomposite 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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- 239000004927 clay Substances 0.000 title claims abstract description 67
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 15
- 150000001408 amides Chemical class 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000004952 Polyamide Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000002612 dispersion medium Substances 0.000 claims abstract description 8
- 229920002647 polyamide Polymers 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000009830 intercalation Methods 0.000 claims abstract description 6
- 230000002687 intercalation Effects 0.000 claims abstract description 6
- 238000005453 pelletization Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MSWZFWKMSRAUBD-UHFFFAOYSA-N 2-Amino-2-Deoxy-Hexose Chemical compound NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- AKVBCGQVQXPRLD-UHFFFAOYSA-N 2-aminooctanoic acid Chemical compound CCCCCCC(N)C(O)=O AKVBCGQVQXPRLD-UHFFFAOYSA-N 0.000 claims description 3
- 229940124277 aminobutyric acid Drugs 0.000 claims description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical group [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical class OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 11
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000002685 polymerization catalyst Substances 0.000 abstract 1
- 229920002292 Nylon 6 Polymers 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000004927 fusion Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005341 cation exchange Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 101100232929 Caenorhabditis elegans pat-4 gene Proteins 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- DVBJBNKEBPCGSY-UHFFFAOYSA-M cetylpyridinium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 DVBJBNKEBPCGSY-UHFFFAOYSA-M 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- -1 formyl amine Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了PET共聚酯/粘土纳米复合材料的制备方法，以重量份计，按下述步骤进行：(1)将粘土分散在分散介质中，与助分散剂形成稳定的悬浮体系；(2)将有机插层剂、离子化助剂和分散介质混合均匀；(3)在搅拌下将步骤(2)制得的溶液滴加至步骤(1)制得的粘土悬浮液中，搅拌反应，离心、洗涤；(4)将步骤(3)制得的滤饼、酰胺聚合催化剂和添加剂加入到聚酰胺单体中，搅拌，常压蒸馏聚合，切粒、萃取、干燥即得到聚酰胺粘土母粒；(5)BHET和聚酰胺粘土纳米母粒缩聚。本发明将大大提高了蒙脱土分散均匀性。The invention discloses a preparation method of a PET copolyester/clay nanocomposite material, which is carried out according to the following steps in parts by weight: (1) dispersing the clay in a dispersion medium to form a stable suspension system with an auxiliary dispersant; ( 2) Mix the organic intercalation agent, ionization aid and dispersion medium evenly; (3) add the solution prepared in step (2) dropwise to the clay suspension prepared in step (1) under stirring, and stir to react , centrifugation, washing; (4) the filter cake, amide polymerization catalyst and additives prepared in step (3) are added to the polyamide monomer, stirred, atmospheric distillation polymerization, pelletizing, extraction, drying to obtain polyamide clay Masterbatch; (5) Polycondensation of BHET and polyamide clay nanometer masterbatch. The invention greatly improves the dispersion uniformity 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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| CN101775126B (en) * | 2009-01-09 | 2011-09-07 | 中国石油天然气股份有限公司 | A kind of polyester polycondensation catalyst and its preparation method and application |
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