CN100386359C - Preparation method of polyethylene glycol terephthalate composite material possessing high separating performance - Google Patents
Preparation method of polyethylene glycol terephthalate composite material possessing high separating performance Download PDFInfo
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- CN100386359C CN100386359C CNB2005101279624A CN200510127962A CN100386359C CN 100386359 C CN100386359 C CN 100386359C CN B2005101279624 A CNB2005101279624 A CN B2005101279624A CN 200510127962 A CN200510127962 A CN 200510127962A CN 100386359 C CN100386359 C CN 100386359C
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Abstract
The present invention relates to a method for preparing polyethylene terephthalate (PET) composite material, particularly to a method for preparing PET composite material which is formed by the composition of PET and nanometer oxide and has high barrier properties. The composite material of PET and inorganic nanometer oxide is prepared by that inorganic nanometer oxide sol or a mixture of inorganic nanometer oxide particles and inorganic nanometer oxide sol is added in the esterification step or the polycondensation step in the PET synthesizing process, and the inorganic nanometer oxide sol is composed of inorganic nanometer oxide and ethylene glycol, wherein the inorganic nanometer oxide accounts for 5 to 30 wt% of the total weight of the inorganic nanometer oxide sol. The PET composite material is synthesized in the presence of the inorganic nanometer oxide.
Description
Technical field
The present invention relates to the preparation method of a kind of polyethylene terephthalate (PET) matrix material, particularly a kind of preparation method of the PET matrix material that is composited by PET and nano inorganic oxide with high obstructing performance.
Background technology
PET is the good polymkeric substance of a kind of character.Because advantages such as its wear resistance, plasticity-and mechanical property are good are widely used in the engineering plastics, but because its melt strength is poor, crystallization rate slowly, poor dimensional stability, barrier and poor heat resistance etc. have limited it and have used widely.Along with the development of nanotechnology, use nano-material modified PET, also more and more widely with the research of the barrier, crystal property and other performance that improve PET.Existing filler mainly is nano powder or particle, nano powder or particulate suspension, nanometer laminated structure material etc., and colloidal sol of no use improves the research of PET.Such as Chinese Academy of Sciences chemistry etc. unit prepared PET/MMT (polynite) laminated nm-silicate composite material; In being the patent of CN1587316, publication number related to a kind of polyethylene terephthalate/nano hydrotalcite (double-metal hydroxide) mixture, the advantage of this invention is because nano hydrotalcite has and the similar nanometer laminated structure of polynite, can directly carry out organic intercalation in terephthalic acid/ethylene glycol mixture handles, guaranteed the good distribution of nano hydrotalcite in PET, obtain mechanics, the pet material of excellent propertys such as fire-retardant and obstruct, but, limited its application because poor stability and application cost are crossed high factor; At publication number is in the patent of CN1504510, directly with nanoparticulate dispersed in solvent, form suspensoid, with intermediate co-blended in reactor of pretreated mixture of this process and polyethylene terephthalate (PET), obtain nano composite material then.This matrix material further with polymkeric substance polymer Application of composite, can obtain high heat-resisting, high-modulus, processibility, the nano composite material of high barrier and functional novel polyethylene terephthalate (PET) and inorganics.Yet the pretreated mixture that this method obtains is very easily reunited, and influences the dispersion effect of nanoparticle, and then has influence on whole performance of composites.
A purpose of the present invention provides the preparation method of polyethylene terephthalate (PET) matrix material.
Another object of the present invention provides the preparation method of the polyethylene terephthalate matrix material with high barrier.
Matrix material with polyethylene terephthalate of high obstructing performance of the present invention, be to add the inorganic nanometer oxide colloidal sol or the mixture of inorganic nanometer oxide particle and inorganic nanometer oxide colloidal sol in esterification in the PET building-up process or the polycondensation phase.
Matrix material with polyethylene terephthalate of high obstructing performance of the present invention is made up of polyethylene terephthalate and inorganic nanometer oxide, and wherein inorganic nanometer oxide accounts for the 0.1wt%～20wt% of matrix material gross weight.
Described inorganic nanometer oxide is selected from one or more the mixture in aluminum oxide, zirconium white, silicon-dioxide, calcium oxide, antimony peroxide, cerium dioxide, yttrium oxide, zinc oxide, nickel oxide, chromic oxide, the titanium oxide.The particle diameter of described inorganic nanometer oxide is 1nm～10 μ m.
The preparation method of the matrix material of the polyethylene terephthalate with high obstructing performance of the present invention is: be to add inorganic nanometer oxide colloidal sol in esterification in the PET building-up process or the polycondensation phase, or the mixture of inorganic nanometer oxide particle and inorganic nanometer oxide colloidal sol, obtain having the matrix material of the polyethylene terephthalate of high obstructing performance; Wherein:
Esterification stage, rough vacuum polycondensation or high vacuum polycondensation stage at polyethylene terephthalate add the inorganic nanometer oxide colloidal sol that accounts for reaction mixture gross weight 1wt%～50wt%; Or the inorganic nanometer oxide particle of adding 1wt%～70wt% and the mixture of inorganic nanometer oxide colloidal sol;
The temperature of reaction in esterification stage is 200～290 ℃, and reaction pressure is 0.1～0.6MPa, and the reaction times is 1～4 hour; Rough vacuum stage polycondensation temperature is 200～290 ℃, and reaction pressure is 100000～500Pa, and the reaction times is 10～90 minutes; High vacuum stage of Fig polycondensation temperature is 250～300 ℃, and reaction pressure is 500～50Pa, and the reaction times is 1～4 hour.
Described inorganic nanometer oxide colloidal sol is made up of inorganic nanometer oxide and ethylene glycol, and wherein inorganic nanometer oxide accounts for the 5wt%～30wt% of inorganic nanometer oxide colloidal sol total amount.
In the mixture of described inorganic nanometer oxide particle and inorganic nanometer oxide colloidal sol, inorganic nanometer oxide colloidal sol accounts for the 10wt%～90wt% of this mixture total weight amount.
Described inorganic nanometer oxide (comprising nano particle and colloidal sol) is selected from one or more the mixture in aluminum oxide, zirconium white, silicon-dioxide, calcium oxide, antimony peroxide, cerium dioxide, yttrium oxide, zinc oxide, nickel oxide, chromic oxide, the titanium oxide etc.; Grain diameter is between 1nm～10 μ m.
In the building-up process of the matrix material of polyethylene terephthalate, to contain the colloidal sol of metal oxide, inorganic non-metallic oxide compound or the mixture of nano particle and colloidal sol, join in the polymerization system of PET, obtain the matrix material of forming by PET and inorganic nano material.This matrix material has good barrier performance to water, oxygen and carbonic acid gas etc., and processing characteristics is good simultaneously; Inorganic materials in this matrix material is not reunited, good dispersity.
Embodiment
Embodiment 1
Adding the weight percent that accounts for reaction mixture in the esterification technique stage of producing PET is 50% titanium oxide sol, and wherein, the weight percent that titanium oxide accounts for colloidal sol is 5%, and particle diameter is similar normal state and distributes between 1nm～50nm, and solvent is an ethylene glycol.Esterification reaction temperature is 200～220 ℃, and reaction pressure is 0.1～0.25MPa, and the reaction times is 1～2 hour.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 200～240 ℃, and reaction pressure is 100000～500Pa, reaction times is 10～30 minutes, high vacuum stage of Fig polycondensation temperature is 250～275 ℃, and reaction pressure is 500～50Pa, and the reaction times is 1～1.5 hour.
Embodiment 2
Adding the weight percent that accounts for reaction mixture in the esterification technique stage of producing PET is 70% the silicon dioxide gel and the mixture of nanometer silicon dioxide particle, wherein, silicon dioxide gel accounts for the 10wt% of additive total amount, the weight percent that inorganic nanometer oxide in the colloidal sol accounts for colloidal sol is 30%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 5nm～10 μ m, solvent is an ethylene glycol.Wherein esterification reaction temperature is 220～240 ℃, and reaction pressure is 0.2～0.6MPa, and the reaction times is 1.5～2 hours.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 230～250 ℃, and reaction pressure is 100000～500Pa, reaction times is 20～30 minutes, high vacuum stage of Fig polycondensation temperature is 250～275 ℃, and reaction pressure is 500～50Pa, and the reaction times is 2～2.5 hours.
Embodiment 3
Adding the weight percent that accounts for reaction mixture in the esterification technique stage of producing PET is 1% zirconia sol and nano zirconium dioxide particulate mixture, wherein, zirconia sol accounts for the 90wt% of additive total amount, the weight percent that inorganic nanometer oxide in the colloidal sol accounts for colloidal sol is 15%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 5nm～10 μ m, solvent is an ethylene glycol.Wherein esterification reaction temperature is 220～240 ℃, and reaction pressure is 0.2～0.25MPa, and the reaction times is 1.5～2 hours.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 230～250 ℃, and reaction pressure is 100000～500Pa, reaction times is 20～30 minutes, high vacuum stage of Fig polycondensation temperature is 250～275 ℃, and reaction pressure is 500～50Pa, and the reaction times is 2～2.5 hours.
Embodiment 4
Adding the weight percent that accounts for reaction mixture respectively in the esterification technique stage of producing PET is 1% titanium oxide sol and zirconia sol, wherein, titanium oxide and the zirconium dioxide weight percent in colloidal sol is respectively 10% and 15%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 5nm～10 μ m, solvent is respectively ethylene glycol.Esterification reaction temperature is 230～250 ℃, and reaction pressure is 0.25～0.35MPa, and the reaction times is 1.5～2.5 hours.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 240～260 ℃, and reaction pressure is 100000～500Pa, reaction times is 30～40 minutes, high vacuum stage of Fig polycondensation temperature is 275～285 ℃, and reaction pressure is 500～50Pa, and the reaction times is 2～2.5 hours minutes.
Embodiment 5
Add the mixture that the weight percent that accounts for reaction mixture is 15% titanium oxide sol, zirconia sol and zirconium dioxide nanoparticles in the esterification technique stage of producing PET.Wherein, colloidal sol accounts for the 40wt% of additive total amount, and titanium oxide and the zirconium dioxide weight percent in colloidal sol is respectively 10% and 15%, and the inorganic nanometer oxide grain diameter is similar normal state and distributes between 5nm～10 μ m, and solvent is respectively ethylene glycol.Esterification reaction temperature is 250～260 ℃, and reaction pressure is 0.25～0.35MPa, and the reaction times is 2.5～3 hours.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 250～260 ℃, and reaction pressure is 100000～500Pa, reaction times is 20～30 minutes, high vacuum stage of Fig polycondensation temperature is 275～280 ℃, and reaction pressure is 500～50Pa, and the reaction times is 3～3.5 hours.
Embodiment 6
Add the mixture that the weight percent that accounts for reaction mixture is 40% silicon dioxide gel, calcium oxide colloidal sol and nanometer silicon dioxide particle in the esterification technique stage of producing PET, wherein, colloidal sol accounts for the 50wt% of additive total amount, silicon-dioxide and the calcium oxide weight percent in colloidal sol is respectively 25% and 5%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 1nm～10 μ m, solvent is respectively ethylene glycol.Esterification reaction temperature is 250～290 ℃, and reaction pressure is 0.25～0.5MPa, and the reaction times is 3～4 hours.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 250～290 ℃, and reaction pressure is 100000～500Pa, reaction times is 40～70 minutes, high vacuum stage of Fig polycondensation temperature is 275～300 ℃, and reaction pressure is 500～50Pa, and the reaction times is 3～3.5 hours.
Embodiment 7
Adding the weight percent that accounts for reaction mixture in the esterification technique stage of producing PET is 25% silicon-dioxide, aluminum oxide and titanium oxide sol system, wherein, silicon-dioxide, aluminum oxide and the titanium oxide weight percent in colloidal sol is respectively 15%, 10% and 5%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 1nm～10 μ m, solvent is respectively ethylene glycol.Esterification reaction temperature is 240～260 ℃, and reaction pressure is 0.25～0.4MPa, and the reaction times is 2～3 hours.The product of above-mentioned esterification technique obtains the PET matrix material of high-barrier again through polycondensating process.Wherein, rough vacuum stage polycondensation temperature is 250～270 ℃, and reaction pressure is 100000～500Pa, reaction times is 60～90 minutes, high vacuum stage of Fig polycondensation temperature is 275～290 ℃, and reaction pressure is 500～50Pa, and the reaction times is 2.5～3 hours.
Embodiment 8
The mixed reaction solution of ethylene glycol and terephthalic acid etc. is 220～240 ℃ in temperature earlier, and reaction pressure is to carry out esterification under the processing condition of 0.2～0.3MPa.Afterwards, adding the weight percent that accounts for final PET matrix material in the rough vacuum polycondensating process stage of producing PET is 1% titanium oxide sol, and wherein, the weight percent that inorganic nanometer oxide accounts for colloidal sol is 10%, particle diameter is similar normal state and distributes between 1nm～50nm, solvent is an ethylene glycol.Rough vacuum stage polycondensation temperature is 220～250 ℃, reaction pressure is 100000～500MPa, reaction times is 20～30 minutes, high vacuum stage of Fig polycondensation temperature is 250～275 ℃, reaction pressure is 500～50Pa, reaction times is 2.5～3 hours, obtains the PET matrix material of high-barrier.
Embodiment 9
The mixed reaction solution of ethylene glycol and terephthalic acid etc. is 220～240 ℃ in temperature earlier, and reaction pressure is to carry out esterification under the processing condition of 0.2～0.3MPa.Afterwards, add the mixture that the weight percent that accounts for reaction mixture is 10% titanium oxide sol, zirconia sol and zirconium dioxide nanoparticles in the rough vacuum polycondensating process stage of producing PET, wherein, colloidal sol accounts for the 60wt% of additive total amount, titanium oxide and the zirconium dioxide weight percent in colloidal sol is respectively 10% and 15%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 1nm～10 μ m, solvent is respectively ethylene glycol.Rough vacuum stage polycondensation temperature is 260～270 ℃, reaction pressure is 100000～500Pa, reaction times is 30～50 minutes, high vacuum stage of Fig polycondensation temperature is 270～280 ℃, reaction pressure is 500～50Pa, reaction times is 2.5～3 hours, obtains the PET matrix material of high-barrier.
Embodiment 10
The mixed reaction solution of ethylene glycol and terephthalic acid etc. is 220～240 ℃ in temperature earlier, and reaction pressure is to carry out esterification under the processing condition of 0.25～0.4MPa.Afterwards, through the rough vacuum polycondensating process stage of PET, adding the weight percent that accounts for reaction mixture in the high vacuum polycondensating process stage of producing PET is 20% the silicon-dioxide and the mixture of calcium oxide colloidal sol and nanometer silicon dioxide particle, wherein, colloidal sol accounts for the 40wt% of additive total amount, silicon-dioxide and the calcium oxide weight percent in colloidal sol is respectively 20% and 1 0%, the inorganic nanometer oxide grain diameter is similar normal state and distributes between 1nm～10 μ m, solvent is respectively ethylene glycol.Rough vacuum stage polycondensation temperature is 265～280 ℃, reaction pressure is 100000～500Pa, reaction times is 40～50 minutes, high vacuum stage of Fig polycondensation temperature is 275～300 ℃, reaction pressure is 500～50Pa, reaction times is 3.5～4 hours, obtains the PET matrix material of high-barrier.
Embodiment 11
The mixed reaction solution of ethylene glycol and terephthalic acid etc. is 220～240 ℃ in temperature earlier, and reaction pressure is to carry out esterification under the processing condition of 0.25～0.4MPa.Afterwards, through the rough vacuum polycondensating process stage of PET, adding the weight percent that accounts for reaction mixture in the high vacuum polycondensating process stage of producing PET is 20% silicon-dioxide, aluminum oxide and titanium oxide sol, wherein, the 10wt% of silica comprises colloidal sol total amount, aluminum oxide accounts for the 5wt% of colloidal sol total amount, and titanium oxide accounts for the 5wt% of colloidal sol total amount.The inorganic nanometer oxide grain diameter is similar normal state and distributes between 1nm～10 μ m, solvent is respectively ethylene glycol.Rough vacuum stage polycondensation temperature is 270～280 ℃, reaction pressure is 100000～500Pa, reaction times is 30～40 minutes, high vacuum stage of Fig polycondensation temperature is 280～300 ℃, reaction pressure is 500～50Pa, reaction times is 2.5～3 hours, obtains the PET matrix material of high-barrier.
Claims (3)
1. preparation method with polyethylene terephthalate matrix material of high obstructing performance, it is characterized in that: be to add inorganic nanometer oxide colloidal sol in esterification in the building-up process of polyethylene terephthalate or the polycondensation phase, or the mixture of inorganic nanometer oxide particle and inorganic nanometer oxide colloidal sol, obtain having the matrix material of the polyethylene terephthalate of high obstructing performance; Wherein:
Esterification stage, rough vacuum polycondensation or high vacuum polycondensation stage at polyethylene terephthalate add the inorganic nanometer oxide colloidal sol that accounts for reaction mixture gross weight 1wt%～50wt%; Or the inorganic nanometer oxide particle of adding 1wt%～70wt% and the mixture of inorganic nanometer oxide colloidal sol;
The temperature of reaction in esterification stage is 200～290 ℃, and reaction pressure is 0.1～0.6MPa; Rough vacuum stage polycondensation temperature is 200～290 ℃, and reaction pressure is 100000～500Pa; High vacuum stage of Fig polycondensation temperature is 250～300 ℃, and reaction pressure is 500～50Pa;
Described inorganic nanometer oxide colloidal sol is made up of inorganic nanometer oxide and ethylene glycol, and wherein inorganic nanometer oxide accounts for the 5wt%～30wt% of inorganic nanometer oxide colloidal sol total amount;
In the mixture of described inorganic nanometer oxide particle and inorganic nanometer oxide colloidal sol, inorganic nanometer oxide colloidal sol accounts for the 10wt%～90wt% of this mixture total weight amount;
The reaction times in described esterification stage is 1～4 hour;
The reaction times of described rough vacuum stage polycondensation is 10～90 minutes;
The reaction times of described high vacuum stage of Fig polycondensation is 1～4 hour.
2. method according to claim 1 is characterized in that: described inorganic nanometer oxide particle grain size is between 1nm～10 μ m.
3. method according to claim 1 is characterized in that: described inorganic nanometer oxide particle is selected from one or more the mixture in aluminum oxide, zirconium white, silicon-dioxide, calcium oxide, antimony peroxide, cerium dioxide, yttrium oxide, zinc oxide, nickel oxide, chromic oxide, the titanium oxide.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391449B1 (en) * | 1998-12-07 | 2002-05-21 | Amcol International Corporation | Polymer/clay intercalates, exfoliates, and nanocomposites comprising a clay mixture and a process for making same |
| US6486253B1 (en) * | 1999-12-01 | 2002-11-26 | University Of South Carolina Research Foundation | Polymer/clay nanocomposite having improved gas barrier comprising a clay material with a mixture of two or more organic cations and a process for preparing same |
| CN1504510A (en) * | 2002-11-28 | 2004-06-16 | 柯扬船 | Nanometer composite material of polyester and inorganic matter and preparing method thereof |
| CN1587316A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing polyethylene glycol terephthalate/nano hydrotalcite composite |
| CN1638953A (en) * | 2002-02-28 | 2005-07-13 | 三菱树脂株式会社 | Gas barrier material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6391449B1 (en) * | 1998-12-07 | 2002-05-21 | Amcol International Corporation | Polymer/clay intercalates, exfoliates, and nanocomposites comprising a clay mixture and a process for making same |
| US6486253B1 (en) * | 1999-12-01 | 2002-11-26 | University Of South Carolina Research Foundation | Polymer/clay nanocomposite having improved gas barrier comprising a clay material with a mixture of two or more organic cations and a process for preparing same |
| CN1638953A (en) * | 2002-02-28 | 2005-07-13 | 三菱树脂株式会社 | Gas barrier material |
| CN1504510A (en) * | 2002-11-28 | 2004-06-16 | 柯扬船 | Nanometer composite material of polyester and inorganic matter and preparing method thereof |
| CN1587316A (en) * | 2004-07-09 | 2005-03-02 | 浙江大学 | Process for preparing polyethylene glycol terephthalate/nano hydrotalcite composite |
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