CN103205091A - Inorganic nanoparticle dispersion for high-transparency high-barrier polyester material, and preparation method thereof - Google Patents
Inorganic nanoparticle dispersion for high-transparency high-barrier polyester material, and preparation method thereof Download PDFInfo
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- CN103205091A CN103205091A CN201210007033XA CN201210007033A CN103205091A CN 103205091 A CN103205091 A CN 103205091A CN 201210007033X A CN201210007033X A CN 201210007033XA CN 201210007033 A CN201210007033 A CN 201210007033A CN 103205091 A CN103205091 A CN 103205091A
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Abstract
The invention relates to a single-particle inorganic nanoparticle dispersion for a high-transparency high-barrier polyester material, and a preparation method thereof. The dispersion includes 2-60% of a single-particle inorganic nanoparticle, a modifier having an amount being 0.01-30% of the amount of the inorganic nanoparticle, and the balance dihydric alcohol. The preparation method of the dispersion comprises the following steps: modifying the colloid or dispersion of water or low-boiling-point alcohol of the single-particle inorganic nanoparticle through the modifier, mixing with high-boiling-point dihydric alcohol, and distilling for replacing and removing water or the low-boiling-point alcohol to obtain the dispersion for the in-situ polymerizing preparation of the high-transparency high-barrier polyester material.
Description
Technical field:
The invention belongs to field of nanometer material technology, relate to the technology of preparing of single particle inorganic nano-particle, further relate to single particle inorganic nano-particle molecular dispersion that is applied to the high transparency high separation polyester material and preparation method thereof.
Background technology:
Polyethylene terephthalate (PET) is a kind of polymkeric substance of excellent property, because advantages such as its transparency, wear resistance, plasticity-and mechanical property are good are widely used in the 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.Keeping under original high transparent condition, improving its barrier property is the hot fields of researching and developing at present, and the polyester material of high transparency high separation is at thin-film material such as packing film, sun power backboard film etc.; Bottle level material such as beverage pack bottling, Beer Bottle etc. have wide application market.The technology that improves at present barrier property under the transparent condition of height has coating, MULTILAYER COMPOSITE co-extrusion, blend (with barrier resins) etc., and these methods exist the cost height, the Technology difficulty is big, equipment requirements is high and reclaim defective such as difficulty.
Along with the development of nanotechnology, use nano-material modified PET, with the research of the barrier, crystal property and other performance that improve PET also more and more widely.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 because poor stability and application cost are crossed high factor, limited its application; Be in the patent of CN1504510 at publication number, directly with nanoparticulate dispersed in solvent, form suspensoid, with intermediate co-blended in reactor of the pretreated mixture of this process and poly terephthalic acid ethylene glycol vinegar (P ET), 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; The Liaoyang petrochemical industry adopts the inorganic sol modified PET polyester through macromolecular compound polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), polyoxyethylene (PEO), polystyrene modifications such as (PS), obtain nanometer PET polyester composite, its barrier property improves 3～5 times, but because polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG) the properties-correcting agent heatproof of etc.ing are low, unavoidably can xanthochromia in the PET polyreaction degrade and influence the transparent and color characteristics of product; The colloidal sol size distribution of Shi Yonging is wide simultaneously, scope is big, has also influenced the transparency of product.
The contriver recognizes and disperses to be grafted on the PET molecular chain and homogeneous phase is distributed in the polyester material by specific inorganic nano-particle (particle diameter and shape) single particle, it is feasible keeping high-clarity, the inorganic nano-particle homogeneous phase is distributed in and forms " labyrinth " effect on the polyester molecule chain simultaneously, can under the transparent condition of height, solve the high-barrier problem, modification owing to inorganic materials simultaneously can increase substantially heat resistance and mechanical property, thereby satisfies the needs of process for processing when satisfying the barrier property of polyester material.
Further, if the particle diameter of the inorganic nano-particle that uses is lower than 30nm, this inorganic nano-particle just can not influence the transparency of thin slice, bottle sheet or film, if the particle diameter of nano inoganic particle greater than 100nm, optical transmittance is lowered.Therefore, need to use particle diameter less than the inorganic nano-particle of 30nm, preferably use the nano inoganic particle of particle diameter 10～30nm, more preferably use particle diameter less than the inorganic nano-particle of 10nm.
Summary of the invention
The purpose of this invention is to provide the single particle nano inorganic composite particles (SiO that a kind of high density (2～60%) participates in the specified particle diameter of synthetic dibasic alcohol (ethylene glycol) system of polyester
2, AL
2O
3, ZrO
2, CaO, BaSO
4Deng) dispersion, the PET polyester is carried out the in-situ polymerization modification not changing under the synthetic technology condition of polyester then, prepare for the high transparency high separation polyester with direct concentration material or high density master batch, directly the concentration material is directly used in the production of high transparency high separation polyester product, master batch adopts directly to add in high transparency high separation polyester product production process and uses, and finally all obtains high performance high transparency high separation polyester product.
The detailed technical scheme of the present invention is:
A kind of single particle inorganic nano-particle molecular dispersion for high transparency high separation polyester film material is characterized in that: comprise 2 ~ 60% single particle inorganic nano-particle, with respect to the properties-correcting agent of inorganic particulate 0.01 ~ 30% and the dibasic alcohol of surplus.
According to above-described inorganic particulate, it is characterized in that: described inorganic particulate is a kind of in silicon oxide, aluminum oxide, zirconium white, calcium oxide, magnesium oxide, calcium carbonate, the barium sulfate etc. or the mixture more than two kinds wherein.A kind of in preferred silicon oxide, aluminum oxide, the barium sulfate or the mixture more than two kinds wherein.
According to above-described single particle inorganic nano-particle, it is characterized in that: described inorganic particulate single particle is shaped as sphere, ellipse and clavate etc., and is preferred spherical.
According to above-described single particle inorganic nano-particle, it is characterized in that: its particle diameter is for greater than less than 100nm; Preferably less than 30nm; More preferably select less than 10nm.
Content according to above-described inorganic particulate is characterized in that: content (weight percent) is 2 ~ 60%, preferred 20～40%.
According to above-described properties-correcting agent, it is characterized in that: properties-correcting agent is a kind of in silane coupling agent, titante coupling agent, aluminium esters of gallic acid coupling agent, the Borate Ester as Coupling or the mixture more than two kinds wherein.
Content according to above-described properties-correcting agent is characterized in that: the weight percent with respect to inorganic particulate is 0.01 ~ 30%, preferred 2～20%.
According to above-described dibasic alcohol, it is characterized in that: dibasic alcohol is a kind of in the high boiling point dibasic alcohol such as ethylene glycol, propylene glycol, butyleneglycol or the mixture more than two kinds wherein, preferred ethylene glycol.
A kind of preparation method of the single particle inorganic nano-particle molecular dispersion for high transparency high separation polyester film material, it is characterized in that: by water or low-boiling point alcohol colloid or the dispersion of modifier modification single particle inorganic nano-particle, then by mixing back distillation displacement with the high boiling point dibasic alcohol except anhydrating or low-boiling point alcohol obtains preparing high transparency high separation polyester material dispersion for in-situ polymerization.
According to above-described preparation method, it is characterized in that: be in the water or low-boiling point alcohol colloid or dispersion of the single particle inorganic nano-particle under the whipped state adding under the certain temperature condition after the direct adding of a certain amount of properties-correcting agent or the prehydrolysis, through obtaining inorganic nano-particle water or low-boiling point alcohol colloid or the dispersion of modification after the reaction of certain hour.
According to above-described method of modifying, it is characterized in that: the pre-hydrolysis method of properties-correcting agent is: properties-correcting agent is added dropwise in the mixture that PH is 4～11 water or water and alcohol (methyl alcohol or Virahol), is stirred under normal temperature, the normal pressure that mixture is transparent to be hydrolysis and to finish.
According to above-described method of modifying, it is characterized in that: modified condition is: 20～80 ℃ of normal pressure, temperature; The time of modification is 10 minutes to 24 hours.
According to above-described water or low-boiling point alcohol colloid or dispersion, it is characterized in that: low-boiling point alcohol is colloid or the dispersion of methyl alcohol, ethanol, Virahol etc. or its mixture more than two kinds.Preferably water and methyl alcohol.
According to above-described preparation method, it is characterized in that: the inorganic nano-particle water of high-boiling point alcohol and modification or low-boiling point alcohol colloid or dispersion is even according to 3:1～1:3 mixed.
According to above-described preparation method, it is characterized in that: the mixture that claim 14 is obtained distills, and distills to be normal pressure or underpressure distillation.
According to above-described preparation method, it is characterized in that: the temperature condition of distillation is: 60～160 ℃, and preferred 100～120 ℃.The preferred vacuum tightness of underpressure distillation is: greater than 0.04MPa.The time conditions of distillation is: 1～6 hour, and preferred 1.5～2 hours.
According to above-described preparation method, it is characterized in that: the water of system or low-boiling point alcohol content are preparation and finish less than 0.3% behind displacement water outlet or low-boiling point alcohol.
Description of drawings:
The transmission electron microscope picture of Fig. 1 products obtained therefrom (TEM) 10～20nm
The transmission electron microscope picture of Fig. 2 products obtained therefrom (TEM) is less than 10nm
The particle size distribution figure of Fig. 3 products obtained therefrom (laser particle analyzer)
Embodiment:
The present invention is described further below in conjunction with specific embodiment.But the present invention is not limited to following examples.
(zirconium dioxide accounts for the 20wt % of colloidal sol total amount to embodiment 1 in the zirconia sol system, solvent is water, the particle diameter of zirconium dioxide is that 10nm～30nm) middle adding accounts for the titanate coupling agent of colloidal sol product population 12wt %, under normal pressure, 60 ℃, carry out heated and stirred, reflux, 1.5 add the ethylene glycol with weight after hour, carry out air distillation content of water in system at 120 ℃ and be lower than 0.3%, cooling is taken out, obtain stable modification zirconium dioxide/ethylene glycol dispersion, viscosity 25 mPa S.This dispersion is enclosed within the glass container, keeps measuring viscosity after 1 month in 50 ℃ thermostatic bath, the result is 30mPa S, is stable.
Embodiment 2 is at silicon-dioxide and aluminum oxide mixed sols system (25 wt % of silica comprises colloidal sol total amount, aluminum oxide accounts for 5 wt % of colloidal sol total amount, solvent is methyl alcohol, the inorganic particulate particle diameter is that 10nm～20nm) middle adding accounts for the silane coupling agent of colloidal sol product population 12 wt %, at normal pressure, carry out heated and stirred under 60 ℃, reflux, 1.5 add the ethylene glycol with weight after hour, carry out air distillation till not having methyl alcohol to steam at 120 ℃, cooling is taken out, obtain stable improved silica and aluminum oxide mixing/ethylene glycol dispersion, viscosity 30mPa S.This dispersion is enclosed within the glass container, keeps measuring viscosity after 1 month in 50 ℃ thermostatic bath, the result is 30mPa S, is stable.
Embodiment 3 is at silicon dioxide gel system (the 40wt % of silica comprises colloidal sol total amount, solvent is water, particle diameter is to add the silane coupling agent that accounts for colloidal sol product population 12wt % in 10～20nm), under normal pressure, 60 ℃, carry out heated and stirred, reflux, add the ethylene glycol with weight after 2 hours, (vacuum tightness 0.04～0.06MPa) is not till having water to steam to carry out underpressure distillation at 100 ℃, cooling is taken out, obtain stable improved silica/ethylene glycol dispersion, viscosity 24mPa S.This dispersion is enclosed within the glass container, keeps measuring viscosity after 1 month in 50 ℃ thermostatic bath, the result is 24mPa S, is stable.
Claims (18)
1. single particle inorganic nano-particle molecular dispersion that is used for high transparency high separation polyester film material is characterized in that: comprise 2 ~ 60% single particle inorganic nano-particle, with respect to the properties-correcting agent of inorganic particulate 0.01 ~ 30% and the dibasic alcohol of surplus.
2. inorganic particulate according to claim 1 is characterized in that: described inorganic particulate is a kind of in silicon oxide, aluminum oxide, zirconium white, calcium oxide, magnesium oxide, calcium carbonate, the barium sulfate etc. or the mixture more than two kinds wherein.
3. a kind of in preferred silicon oxide, aluminum oxide, the barium sulfate or the wherein mixture more than two kinds.
4. single particle inorganic nano-particle according to claim 1, it is characterized in that: described inorganic particulate single particle is shaped as sphere, ellipse and clavate etc., and is preferred spherical.
5. single particle inorganic nano-particle according to claim 1 is characterized in that: its particle diameter is for greater than less than 100nm; Preferably less than 30nm; More preferably select less than 10nm.
6. the content of inorganic particulate according to claim 1, it is characterized in that: content (weight percent) is 2 ~ 60%, preferred 20～40%.
7. properties-correcting agent according to claim 1 is characterized in that: properties-correcting agent is a kind of in silane coupling agent, titante coupling agent, aluminium esters of gallic acid coupling agent, the Borate Ester as Coupling or the mixture more than two kinds wherein.
8. the content of properties-correcting agent according to claim 1, it is characterized in that: the weight percent with respect to inorganic particulate is 0.01 ~ 30%, preferred 2～20%.
9. dibasic alcohol according to claim 1 is characterized in that: dibasic alcohol is a kind of in the high boiling point dibasic alcohol such as ethylene glycol, propylene glycol, butyleneglycol or the mixture more than two kinds wherein, preferred ethylene glycol.
10. preparation method who is used for the single particle inorganic nano-particle molecular dispersion of high transparency high separation polyester film material, it is characterized in that: by water or low-boiling point alcohol colloid or the dispersion of modifier modification single particle inorganic nano-particle, then by mixing back distillation displacement with the high boiling point dibasic alcohol except anhydrating or low-boiling point alcohol obtains preparing high transparency high separation polyester material dispersion for in-situ polymerization.
11. preparation method according to claim 9, it is characterized in that: be in the water or low-boiling point alcohol colloid or dispersion of the single particle inorganic nano-particle under the whipped state adding under the certain temperature condition after the direct adding of a certain amount of properties-correcting agent or the prehydrolysis, through obtaining inorganic nano-particle water or low-boiling point alcohol colloid or the dispersion of modification after the reaction of certain hour.
12. the method for modifying according to claim 9, it is characterized in that: the pre-hydrolysis method of properties-correcting agent is: properties-correcting agent is added dropwise in the mixture that PH is 4～11 water or water and alcohol (methyl alcohol or Virahol), is stirred under normal temperature, the normal pressure that mixture is transparent to be hydrolysis and to finish.
13. the method for modifying according to claim 9 is characterized in that: modified condition is: 20～80 ℃ of normal pressure, temperature; The time of modification is 10 minutes to 24 hours.
14. water according to claim 9 or low-boiling point alcohol colloid or dispersion is characterized in that: low-boiling point alcohol is colloid or the dispersion of methyl alcohol, ethanol, Virahol etc. or its mixture more than two kinds; Preferably water and methyl alcohol.
15. preparation method according to claim 9 is characterized in that: the inorganic nano-particle water of high-boiling point alcohol and modification or low-boiling point alcohol colloid or dispersion is even according to 3:1～1:3 mixed.
16. preparation method according to claim 9 is characterized in that: the mixture that claim 14 is obtained distills, and distills to be normal pressure or underpressure distillation.
17. preparation method according to claim 15 is characterized in that: the temperature condition of distillation is: 60～160 ℃, and preferred 100～120 ℃; The preferred vacuum tightness of underpressure distillation is: greater than 0.04MPa; The time conditions of distillation is: 1～6 hour, and preferred 1.5～2 hours.
18. preparation method according to claim 9 is characterized in that: the water of system or low-boiling point alcohol content are preparation and finish less than 0.3% behind displacement water outlet or low-boiling point alcohol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893259A (en) * | 2015-03-26 | 2015-09-09 | 苏州市德莱尔建材科技有限公司 | PET beer bottle and preparation method therefor |
| CN105037754A (en) * | 2015-06-26 | 2015-11-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for preparing functional polyester master batch by adopting slurry method |
| CN107674186A (en) * | 2017-10-31 | 2018-02-09 | 上海航天设备制造总厂 | A kind of method that in-situ polymerization prepares PEPA/nano hydrotalcite |
| CN111019217A (en) * | 2019-12-23 | 2020-04-17 | 浙江大学 | Nano composite polymer material |
| CN111849131A (en) * | 2020-07-01 | 2020-10-30 | 湖南翰墨新材料有限公司 | Inorganic nano polymer modified photovoltaic back panel film and preparation method thereof |
| CN111959075A (en) * | 2020-08-26 | 2020-11-20 | 安徽省恳思惠新型材料有限责任公司 | Multi-layer co-extrusion high-barrier film applied to vacuum insulation panel packaging |
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| CN1699166A (en) * | 2005-05-23 | 2005-11-23 | 电子科技大学 | Nano organic solvent silicasol and preparation method thereof |
| CN101092506A (en) * | 2007-06-26 | 2007-12-26 | 上海大学 | Nano composite material of copolyester, and preparation method |
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2012
- 2012-01-11 CN CN201210007033XA patent/CN103205091A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1699166A (en) * | 2005-05-23 | 2005-11-23 | 电子科技大学 | Nano organic solvent silicasol and preparation method thereof |
| CN101092506A (en) * | 2007-06-26 | 2007-12-26 | 上海大学 | Nano composite material of copolyester, and preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104893259A (en) * | 2015-03-26 | 2015-09-09 | 苏州市德莱尔建材科技有限公司 | PET beer bottle and preparation method therefor |
| CN105037754A (en) * | 2015-06-26 | 2015-11-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Process for preparing functional polyester master batch by adopting slurry method |
| CN105037754B (en) * | 2015-06-26 | 2017-12-08 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of technique that functional polyester master batch is prepared using slurry method |
| CN107674186A (en) * | 2017-10-31 | 2018-02-09 | 上海航天设备制造总厂 | A kind of method that in-situ polymerization prepares PEPA/nano hydrotalcite |
| CN111019217A (en) * | 2019-12-23 | 2020-04-17 | 浙江大学 | Nano composite polymer material |
| CN111019217B (en) * | 2019-12-23 | 2021-01-19 | 浙江大学 | Nano composite polymer material |
| CN111849131A (en) * | 2020-07-01 | 2020-10-30 | 湖南翰墨新材料有限公司 | Inorganic nano polymer modified photovoltaic back panel film and preparation method thereof |
| CN111959075A (en) * | 2020-08-26 | 2020-11-20 | 安徽省恳思惠新型材料有限责任公司 | Multi-layer co-extrusion high-barrier film applied to vacuum insulation panel packaging |
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Application publication date: 20130717 |