CN1143872C - Composite nanometer polyester/layered silicate material and its prpen. - Google Patents
Composite nanometer polyester/layered silicate material and its prpen. Download PDFInfo
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- CN1143872C CN1143872C CNB011137541A CN01113754A CN1143872C CN 1143872 C CN1143872 C CN 1143872C CN B011137541 A CNB011137541 A CN B011137541A CN 01113754 A CN01113754 A CN 01113754A CN 1143872 C CN1143872 C CN 1143872C
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- layered silicate
- phyllosilicate
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- 229920000728 polyester Polymers 0.000 title claims description 41
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims description 40
- 239000000463 material Substances 0.000 title claims description 38
- 239000002131 composite material Substances 0.000 title abstract description 7
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 39
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001634 Copolyester Polymers 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 230000002687 intercalation Effects 0.000 claims abstract description 7
- 238000009830 intercalation Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 58
- 239000002114 nanocomposite Substances 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 13
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 4
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 150000007520 diprotic acids Chemical class 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 235000013405 beer Nutrition 0.000 abstract description 4
- -1 aromatic dicarboxylic acid ester Chemical class 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 3
- 235000014171 carbonated beverage Nutrition 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 125000003275 alpha amino acid group Chemical group 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000138 intercalating agent Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 206010025482 malaise Diseases 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a polyester-phyllosilicate nanometer composite material and a preparation method thereof, wherein the polyester-phyllosilicate nanometer composite material is especially suitable for producing packaging containers for carbonated drink, beer, etc., hot canned bottles and repeated canned bottles. The polyester-phyllosilicate nanometer composite material comprises aromatic dicarboxylic acid and/or aromatic dicarboxylic acid ester, and dibasic alcohol. The polyester-phyllosilicate nanometer composite material is prepared by two production methods, a direct esterification method and/or an ester interchange polycondensation method in an esterify stage or a polycondensation stage for producing copolyester by directly esterifying and polycondensing the aromatic dicarboxylic acid. 0.01 to 11.0 wt% of phyllosilicate relative to the copolyester is added in an ester interchange stage or a polycondensation stage for producing the copolyester by interchanging ester and polycondensing the aromatic dicarboxylic acid after being treated by a special intercalation treated agent. In this way, the polyester-phyllosilicate nanometer composite material is obtained.
Description
The nano composite material of copolyester that the present invention relates to a kind of preparation that is applicable to packaging vessel (soda pop, beer etc.), hot canned bottle, repetitive canned bottle etc. is manufacture method extremely, is in particular polyester/phyllosilicate nano-composite material and preparation method thereof.
Polyethylene terephthalate (PET) is a kind of of many uses, macromolecular material that output is very big, all has great production application to be worth in fields such as fiber, film, engineering plastics.Particularly the chemical reagent stability of PET, good mechanical performance, processing characteristics make it in packaging vessel (bottle) manufacturing field significant progress arranged in recent years.But still there is deficiency in the gas barrier property of PET own, has limited the application in food container (bottle) or the demanding packaging vessel of other gas barrier property (bottle) field.
Use laminar silicic acid salt pair polyester through intercalation modifying to carry out the composite study that the modification preparation has a property many reports are arranged.CN97122065.4 has reported a kind of with the lamella silicate modified PET matrix material through intercalation processing and Silante terminated processing, and its intercalator is amino acid or contains hydramine than short carbon chain; CN1187506A has reported a kind of with through the lamella silicate modified PBT matrix material of intercalation processing, and its intercalator is amino acid or contains hydramine or alkyl ammonia salt than short carbon chain.Because treatment agent can not possess long carbochain and oh group simultaneously, make and to take into account preferably that cause the barrier poor effect of matrix material, transparency is also influenced to the intercalation effect of layered silicate with to the consistency of polyester material.Therefore the material of these two kinds of method preparations more is applicable to the application in fields such as fiber, engineering plastics, and is unwell to the Application Areas of packaging vessel.
Purpose of the present invention be exactly provide for the above-mentioned deficiency that solves prior art a kind of can be used for producing have high-clarity, the polyester/phyllosilicate nano-composite material and the manufacture method thereof of the preparation that is specially adapted to packaging vessel (soda pop, beer etc.), hot canned bottle, repetitive canned bottle etc. of good gas barrier, good blowing processing characteristics.
The objective of the invention is to realize by following technical solution:
A kind of polyester/phyllosilicate nano-composite material, it includes following component, and the weight percent of each component is:
Aromatic binary carboxylic acid and/or aromatic binary carboxylic acid ester 50%-70%
Dibasic alcohol 25%-45%
Organic layered silicate 0.01%-10%
Wherein said organic layered silicate is the product after layered silicate is handled through the intercalation processing agent, and described treatment agent is the quaternary ammonium salts organism that possesses long carbochain and oh group simultaneously, and its molecular formula is:
N=7-18 in the formula, x=1-3, y=0-2.
The preparation method of aforesaid a kind of polyester/phyllosilicate nano-composite material, it can adopt the transesterify route, also can adopt the direct esterification path of preparing, and organic layered silicate adds with the form of ethylene glycol suspension liquid; The treatment process of its layered silicate is to learn from else's experience to be ground to the above-mentioned layered silicate 100-500 order of certain fineness, adds the suspension liquid that water is made 0.1-10wt%, under the violent stirring, is warming up to 50-90 ℃, adds treatment agent, and add-on is controlled at 1: 0.8-3.0; In 30 minutes, be warming up to 100 ℃ gradually, kept 1 hour, naturally cool to room temperature; Filter, and with deionized water wash until can not detecting the free treatment agent; In vacuum, 25-110 ℃ following drying; Regrinding is to required fineness 100-500 order.
Purpose of the present invention also can further realize by following technical measures:
Aforesaid a kind of polyester/phyllosilicate nano-composite material, wherein said polyester is to be formed by direct esterification and/or transesterify, polycondensation by aromatic binary carboxylic acid and/or aromatic binary carboxylic acid ester, dibasic alcohol and layered silicate, aromatic binary carboxylic acid can be terephthalic acid, m-phthalic acid, 2, a kind of in 6-naphthalic acid, the 1,4 cyclohexanedicarboxylic acid; The aromatic binary carboxylic acid ester of described copolyesters is terephthalic acid, m-phthalic acid, 2, a kind of in the corresponding ester such as 6-naphthalic acid, 1,4 cyclohexanedicarboxylic acid; The dibasic alcohol of described copolyesters is ethylene glycol, butyleneglycol, 1, ammediol, pentanediol, Resorcinol, 1, a kind of in the 4-cyclohexanedimethanol, diprotic acid in the described copolyesters and dibasic alcohol can be single components, also can be the mixed compositions of above-mentioned diacid, glycol.
Aforesaid a kind of polyester/phyllosilicate nano-composite material, wherein said layered silicate are the polynite of sodium base, or are the polynite of calcium base, and its cationic exchange total volume is 40-200meq/100g.
Aforesaid a kind of polyester/phyllosilicate nano-composite material, the n in the wherein said treatment agent molecular formula is 7-18, organic stratiform silicate content is 1.0-3.0wt%.
Aforesaid a kind of polyester/phyllosilicate nano-composite material, it also includes other additive component, and other additive component is to contain promotor, matting agent, white dyes, the thermo-stabilizer that is lower than 15wt%.
The preparation method of aforesaid a kind of polyester/phyllosilicate nano-composite material, the treatment process of wherein said its layered silicate is to learn from else's experience to be ground to the above-mentioned layered silicate 200-300 order of certain fineness, add the suspension liquid that water is made for 1-5wt%, under the violent stirring, be warming up to 50-90 ℃, add treatment agent, it is 1 that add-on is controlled at: 1.0-1.5; In 30 minutes, be warming up to 100 ℃ gradually, kept 1 hour, naturally cool to room temperature; Filter, and with deionized water wash until can not detecting the free treatment agent; In vacuum, 25-110 ℃ following drying; Regrinding is to required fineness 200-300 order.
The preparation method of aforesaid a kind of polyester/phyllosilicate nano-composite material, when wherein said employing ester exchange polycondensation legal system is equipped with polyester/phyllosilicate nano-composite material, earlier aromatic binary carboxylic acid ester and dibasic alcohol are pressed 1: the mixed of 1.1-1: 2.0mol, Zn, Mn, Mg, Ca, one or more make transesterification catalyst the Co compound, 180-260 ℃ of following normal pressure transesterify, the ethylene glycol suspension liquid 0.01-5.0wt% that adds organic layered silicate again, add Sb simultaneously, Ti, Ge, one or more make polycondensation catalyst the Sn compound, the reaction system intensification of reducing pressure gradually, until high temperature 255-295 ℃, high vacuum, prepare above-mentioned polyester/phyllosilicate nano-composite material, the ethylene glycol suspension liquid of treated layered silicate also can add in precondensation stage, can also add in polycondensation phase.
The preparation method of aforesaid a kind of polyester/phyllosilicate nano-composite material, when wherein said direct esterification-polycondensation process prepares above-mentioned polyester/phyllosilicate nano-composite material, earlier aromatic acid and dibasic alcohol are pressed 1: the mixed of 1.1-1: 2.0mol, the ethylene glycol suspension liquid that adds treated layered silicate again, add Sb simultaneously, Ti, Ge, one or more of Sn compound are made catalyzer, at 200-290 ℃, pressure esterification under 0.0-0.5MPa, reaction system is through precondensation 0.1-0.01MPa, after 220-270 ℃, decompression heats up gradually, until high temperature 255-295 ℃, high vacuum, prepare above-mentioned polyester/phyllosilicate nano-composite material, the ethylene glycol suspension liquid of treated layered silicate also can add in precondensation stage, also can add in polycondensation phase.
The invention has the advantages that the polyester/phyllosilicate nano-composite material that adopts the method for the invention preparation, have high-clarity, good barrier properties for gases, good blowing processing characteristics, can be applicable to the preparation of packaging vessel (soda pop, beer etc.), hot canned bottle, repetitive canned bottle etc.
The present invention will be further described below in conjunction with embodiment, but the present invention is not limited to following example.
Embodiment one:
Produce polyester/phyllosilicate nano-composite material with the DMT method:
Dimethyl terephthalate (DMT) and ethylene glycol are pressed 1: the mixed of 1.9mol, use Zn
2+, Mn
2+Deng making transesterification catalyst, 180-260 ℃ of following normal pressure transesterify, add the ethylene glycol suspension liquid (2.0wt% of the reasonable opinion of layered silicate PET output) of treated layered silicate again, add Sb (Ac) simultaneously
3Deng making polycondensation catalyst, the reaction system intensification of reducing pressure gradually, until high temperature (275-285 ℃), high vacuum (≤133Pa), produce limiting viscosity and be 0.65 polyester/phyllosilicate nano-composite material.O
2Transmitance (25 ℃, 50%RH): 1.50 * 10
-15Cm
3Cm/ (cm
2SPa), conventional relatively PET value is 8.50 * 10
-15Cm
3Cm/ (cm
2SPa); Light transmission rate 92%, mist degree 1.5, conventional PET light transmission rate 91%, mist degree 5.1.
Embodiment two:
Produce polyester/phyllosilicate nano-composite material with the PTA method:
With terephthalic acid and ethylene glycol by 1: the mixed of 1.9mol adds the ethylene glycol suspension liquid (2.0wt% of the reasonable opinion of layered silicate PET output) of treated layered silicate, adding Sb (Ac)
3Make catalyzer, under 180-260 ℃, pressure esterification under 0.2-0.5Mpa, reaction system through precondensation (0.1-0.01MPa, 220-270 ℃) after, decompression heats up gradually, until high temperature (275-285 ℃), high vacuum (≤133Pa), producing limiting viscosity is 0.64 polyester slice.O
2Transmitance (25 ℃, 50%RH): 1.62 * 10
-15Cm
3Cm/ (cm
2SPa) conventional relatively PET value is 8.50 * 10
-15Cm
3Cm/ (cm
2SPa); Light transmission rate 92%, mist degree 1.5, conventional PET light transmission rate 91%, mist degree 5.1.
Comparative Examples one:
Terephthalic acid and ethylene glycol are pressed 1: the mixed of 1.9mol, add ethylene glycol suspension liquid (2.0wt% of the reasonable opinion of layered silicate PET output) through the layered silicate of diethanolamine processing, add Sb (Ac)
3Make catalyzer, under 180-260 ℃, pressure esterification under 0.2-0.5MPa, reaction system through precondensation (0.1-0.01MPa, 220-270 ℃) after, decompression heats up gradually, until high temperature (275-285 ℃), high vacuum (≤133Pa), producing limiting viscosity is 0.64 polyester slice.O
2Transmitance (25 ℃, 50%RH): 3.21 * 10
-15Cm
3Cm/ (cm
2SPa); Polyester is sent out mist, poor transparency.
Claims (9)
1. polyester/phyllosilicate nano-composite material, it includes following component, and the weight percent of each component is:
Aromatic binary carboxylic acid and/or aromatic binary carboxylic acid ester 50%-70%
Dibasic alcohol 25%-45%
Organic layered silicate 0.01%-10%
Wherein said organic layered silicate is the product after layered silicate is handled through the intercalation processing agent, and described treatment agent is the quaternary ammonium salts organism that possesses long carbochain and oh group simultaneously, and its molecular formula is:
N=7-18 in the formula, x=1-3, y=0-2.
2. a kind of polyester/phyllosilicate nano-composite material according to claim 1, the polyester that it is characterized in that it is to be formed by direct esterification and/or transesterify, polycondensation by aromatic binary carboxylic acid and/or aromatic binary carboxylic acid ester, dibasic alcohol and layered silicate, aromatic binary carboxylic acid can be terephthalic acid, m-phthalic acid, 2, a kind of in 6-naphthalic acid, the 1,4 cyclohexanedicarboxylic acid; The aromatic binary carboxylic acid ester of described copolyesters is terephthalic acid, m-phthalic acid, 2, a kind of in 6-naphthalic acid, the 1,4 cyclohexanedicarboxylic acid in the corresponding ester; The dibasic alcohol of described copolyesters is ethylene glycol, butyleneglycol, 1, ammediol, pentanediol, Resorcinol, 1, a kind of in the 4-cyclohexanedimethanol, diprotic acid in the described copolyesters and dibasic alcohol can be single components, also can be the mixed compositions of above-mentioned diacid, glycol.
3. a kind of polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that described layered silicate is the polynite of sodium base, or is the polynite of calcium base that its cationic exchange total volume is 40-200meq/100g.
4. a kind of polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that the n in the treatment agent molecular formula is 7-18, and organic stratiform silicate content is 1.0-3.0wt%.
5. a kind of polyester/phyllosilicate nano-composite material according to claim 1, it is characterized in that it also includes other additive component, other additive component is to contain promotor, matting agent, white dyes, the thermo-stabilizer that is lower than 15wt%.
6. the preparation method of a kind of polyester/phyllosilicate nano-composite material according to claim 1 is characterized in that adopting the transesterify route, also can adopt the direct esterification path of preparing, and organic layered silicate adds with the form of ethylene glycol suspension liquid; The treatment process of its layered silicate is to learn from else's experience to be ground to the above-mentioned layered silicate 100-500 order of certain fineness, adds the suspension liquid that water is made 0.1-10wt%, under the violent stirring, is warming up to 50-90 ℃, adds treatment agent, and add-on is controlled at 1: 0.8-3.0; In 30 minutes, be warming up to 100 ℃ gradually, kept 1 hour, naturally cool to room temperature; Filter, and with deionized water wash until can not detecting the free treatment agent; In vacuum, 25-110 ℃ following drying; Regrinding is to required fineness 100-500 order.
7. the preparation method of a kind of polyester/phyllosilicate nano-composite material according to claim 6, the treatment process that it is characterized in that its layered silicate is to learn from else's experience to be ground to the above-mentioned layered silicate 200-300 order of certain fineness, add the suspension liquid that water is made for 1-5wt%, under the violent stirring, be warming up to 50-90 ℃, add treatment agent, it is 1 that add-on is controlled at: 1.0-1.5; In 30 minutes, be warming up to 100 ℃ gradually, kept 1 hour, naturally cool to room temperature; Filter, and with deionized water wash until can not detecting the free treatment agent; In vacuum, 25-110 ℃ following drying; Regrinding is to required fineness 200-300 order.
8. the preparation method of a kind of polyester/phyllosilicate nano-composite material according to claim 6, when it is characterized in that adopting the ester exchange polycondensation legal system to be equipped with polyester/phyllosilicate nano-composite material, earlier aromatic binary carboxylic acid ester and dibasic alcohol are pressed 1: the mixed of 1.1-1: 2.0mol, Zn, Mn, Mg, Ca, one or more make transesterification catalyst the Co compound, 180-260 ℃ of following normal pressure transesterify, the ethylene glycol suspension liquid 0.01-5.0wt% that adds organic layered silicate again, add Sb simultaneously, Ti, Ge, one or more make polycondensation catalyst the Sn compound, the reaction system intensification of reducing pressure gradually, until high temperature 255-295 ℃, high vacuum, prepare above-mentioned polyester/phyllosilicate nano-composite material, the ethylene glycol suspension liquid of treated layered silicate also can add in precondensation stage, can also add in polycondensation phase.
9. the preparation method of a kind of polyester/phyllosilicate nano-composite material according to claim 7, when it is characterized in that direct esterification-polycondensation process prepares polyester/phyllosilicate nano-composite material, earlier aromatic acid and dibasic alcohol are pressed 1: the mixed of 1.1-1: 2.0mol, the ethylene glycol suspension liquid that adds treated layered silicate again, add Sb simultaneously, Ti, Ge, one or more of Sn compound are made catalyzer, at 200-290 ℃, pressure esterification under 0.0-0.5MPa, reaction system is through precondensation 0.1-0.01MPa, after 220-270 ℃, decompression heats up gradually, until high temperature 255-295 ℃, high vacuum, prepare above-mentioned polyester/phyllosilicate nano-composite material, the ethylene glycol suspension liquid of treated layered silicate also can add in precondensation stage, also can add in polycondensation phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011137541A CN1143872C (en) | 2001-07-06 | 2001-07-06 | Composite nanometer polyester/layered silicate material and its prpen. |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011137541A CN1143872C (en) | 2001-07-06 | 2001-07-06 | Composite nanometer polyester/layered silicate material and its prpen. |
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| Publication Number | Publication Date |
|---|---|
| CN1324890A CN1324890A (en) | 2001-12-05 |
| CN1143872C true CN1143872C (en) | 2004-03-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360611C (en) * | 2005-01-18 | 2008-01-09 | 中国科学院化学研究所 | Preparation method of nanometer montmorillonite organic phase intercalation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10259083B4 (en) * | 2002-12-17 | 2006-01-19 | Hilti Ag | Use of intumescent phyllosilicate intercalation compounds with increased rate of expansion and / or modified onset temperature |
| CN100412132C (en) * | 2005-03-04 | 2008-08-20 | 中国科学院合肥物质科学研究院 | Polyester bottle and preparation method thereof |
| CN101343405B (en) * | 2008-04-29 | 2011-01-12 | 常利红 | Preparation method for aliphatic polyester/phyllosilicate nano-composite material |
| CN105885361A (en) * | 2016-05-19 | 2016-08-24 | 苏州倍力特物流设备有限公司 | High-barrier nano composite packaging material and preparation method thereof |
| CN111019100B (en) * | 2018-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Montmorillonite-modified barrier polyester and preparation method thereof |
| CN110724369B (en) * | 2019-10-15 | 2021-12-10 | 界首市天鸿新材料股份有限公司 | Modified PET (polyethylene terephthalate) film for lithium battery flexible packaging film |
-
2001
- 2001-07-06 CN CNB011137541A patent/CN1143872C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100360611C (en) * | 2005-01-18 | 2008-01-09 | 中国科学院化学研究所 | Preparation method of nanometer montmorillonite organic phase intercalation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1324890A (en) | 2001-12-05 |
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Effective date of registration: 20160206 Address after: 211900 Yizheng Changjiang Road, Jiangsu, China, No. 1, No. Patentee after: CHINA SINOPEC YIZHENG CHEMICAL FIBER CO., LTD. Address before: 211900 Jiangsu city of Yizheng province Xupu Patentee before: Yizheng Chemical Fiber Co., Ltd., China Petrochemical Group Corp. |
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