CN1324890A - 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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- CN1324890A CN1324890A CN 01113754 CN01113754A CN1324890A CN 1324890 A CN1324890 A CN 1324890A CN 01113754 CN01113754 CN 01113754 CN 01113754 A CN01113754 A CN 01113754A CN 1324890 A CN1324890 A CN 1324890A
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Abstract
The present invention relates to a polyester/layered silicate nanometer composite material suitable for producing packing containers and its preparation method. It is characterized by that it includes aromatic binary carboxylic acid and/or aromatic binary carboxylic ester and dihydric alcohol, and utilizes two production methods of direct esterification and/or ester exchange condensation, and adds 0.01-11.0 wt% of layered silicate treated by special intercalation treatment agent in the above-mentioned direct esterification stage or polycondensation stage and ester exchange stage or polycondensation stage so as to obtain the invented polyester/layered silicate nanometer composite material.
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, the profit in the corresponding ester such as 6-naphthalic acid, 1,4 cyclohexanedicarboxylic acid; The dibasic alcohol of described copolyesters is a kind of in ethylene glycol, butyleneglycol, 1, ammediol, pentanediol, Resorcinol, 1, 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, 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 method prepares above-mentioned polyester/nano matrix 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/nano matrix 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 the layered silicate of handling through I 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:
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 I 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): 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 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.
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, it is characterized in that to adopt the transesterify route, also can adopt the direct esterification path of preparing, 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 method to prepare above-mentioned polyester/nano matrix 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 above-mentioned polyester/nano matrix 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 true CN1324890A (en) | 2001-12-05 |
| CN1143872C CN1143872C (en) | 2004-03-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011137541A Expired - Lifetime CN1143872C (en) | 2001-07-06 | 2001-07-06 | Composite nanometer polyester/layered silicate material and its prpen. |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 method for production thereof |
| CN100436547C (en) * | 2002-12-17 | 2008-11-26 | 希尔蒂股份公司 | Laminar silicate intercalation compound with increased expanding volume, its preparing method and use |
| 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 |
| CN110724369A (en) * | 2019-10-15 | 2020-01-24 | 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 |
| CN111019100A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Montmorillonite-modified barrier polyester and preparation method thereof |
Families Citing this family (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 |
-
2001
- 2001-07-06 CN CNB011137541A patent/CN1143872C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436547C (en) * | 2002-12-17 | 2008-11-26 | 希尔蒂股份公司 | Laminar silicate intercalation compound with increased expanding volume, its preparing method and use |
| 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 method for production 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 |
| CN111019100A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Montmorillonite-modified barrier polyester and preparation method thereof |
| CN110724369A (en) * | 2019-10-15 | 2020-01-24 | 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 |
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| Publication number | Publication date |
|---|---|
| CN1143872C (en) | 2004-03-31 |
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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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