CN101935439A - Method for preparing uniformly dispersed PET/nano-inorganic composite material - Google Patents
Method for preparing uniformly dispersed PET/nano-inorganic composite material Download PDFInfo
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- CN101935439A CN101935439A CN 201010271286 CN201010271286A CN101935439A CN 101935439 A CN101935439 A CN 101935439A CN 201010271286 CN201010271286 CN 201010271286 CN 201010271286 A CN201010271286 A CN 201010271286A CN 101935439 A CN101935439 A CN 101935439A
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Abstract
The invention relates to a method for preparing a uniformly dispersed polyethylene terephthalate (PET)/nano-inorganic composite material. The method comprises the following steps of: adding terephthalic acid, glycol, a polycondensation catalyst and a stabilizer into a reaction kettle according to a proportion; esterifying the mixture at the temperature of between 198 and 245 DEG C and under the pressure of between 0.40 and 0.45MPa for 3 to 4 hours; relieving the pressure to normal pressure and reducing the temperature to 150 DEG C and heating the mixture to 245 DEG C after the esterification is finished; adding an inorganic filler and a dispersing agent into the system; and vacuuming the system until the pressure is less than 300Pa, raising the temperature to 265 to 275 DEG C and reacting the mixture for 3 to 5 hours to obtain the composite material which is formed by uniformly dispersing the inorganic filler in PET. The inorganic filler adopted by the invention has the advantages of wide source, easy processing and low cost of modification process; and the method has the advantages of simple process, safety and no pollution and is applicable to industrial development of the PET/nano-inorganic composite material.
Description
Technical field
The present invention relates to polymer/inorganic Composite Preparation technical field, be specifically related to dispersion agent preparation, nano inorganic material surface modification, the preparation of original position esterifying polycondensation has the novel method of the PET/nano-inorganic matrix material of good dispersion.
Background technology
In the modifying process of polyester and fiber, adding various inorganic particles is a kind of common methods.Add different inorganic particles, polyester that modification obtains or fiber can produce different functions.The characteristics that interpolation nano-inorganic makes polyester are: the source of inorganic materials is wide, easily processing, and the modifying process cost is low, has reduced the production cost of polyester; The polymer particle surface property improves, and is convenient to process film forming; The crystal property and the mechanical property of polymkeric substance improve.But, because the absorption of nano inoganic particle self is reunited and the bad dispersibility in PET, caused the downgrade of product, limited the industrialized development of PET/nano-inorganic matrix material.
Patent CN1663977A discloses a kind of calcium carbonate microparticle and has been evenly distributed, the preparation method of the poor calcium carbonate modified polyester of aggregated particle.Preparation earlier contains the estrodur performed polymer of lime carbonate, and the polycondensation system that again this performed polymer is joined in the main technical process participates in reaction, makes calcium carbonate modified polyester.Prepare nano-kaoline, montmorillonite clay-polyester mixed polymer among the patent CN1414033, be used for slowly/controlled releasing fertilizer coating cementing agent, organic-inorganic complex fertilizer binding agent, dryland soil water-holding agent and liquid ground film, sand texture modifier.A kind of method for preparing polyester/phyllosilicate nano-composite material is provided among the patent CN1396204, be to adopt melt intercalated method, make layered silicate material and polyester matrix compound and be dispersed in the polyester matrix, thereby prepare high performance nanometer composite polyester material with nanoscale.Patent JP04183717A2 discloses a kind of way of alcoholysis that adopts and has prepared calcium carbonate modified polyester, and concrete grammar is: earlier PTA and EG are carried out esterification and precondensation, obtain the polymerization degree and be about 8.3 oligopolymer; Then at pressure 0.03Kg/cm
2Condition under add CaCO
3/ EG slurry, The catalytic antimony trioxide, stablizer phosphoric acid ester add back alcoholysis 1h; Under 280 ℃, vacuum condition, carry out polycondensation at last, obtain viscosity and be about 0.37 low-viscosity polyester section, carrying out solid-phase polymerization again under 230 ℃, 4mmHg vacuum degree condition, is about 0.65 calcium carbonate modified polyester section thereby obtain limiting viscosity.
Mainly there is the deficiency of following several respects in aforesaid method: what have can only obtain the lower product of limiting viscosity in the melt phase polycondensation stage, and reach the desired viscosity of conventional PET product must be at the process solid state polymerization; The a plurality of reactors of use in reaction process that have have increased production cost; The addition of the mineral filler that has is less, does not demonstrate fully the effect of adding inorganic materials; The needs that have heat polyester once more, and polyester is easy to thermolysis in heat-processed, are difficult to obtain high-quality polyester/inorganic composite materials.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of nano-inorganic homodisperse matrix material in PET.
The present invention includes following three steps:
(1) preparation of BHEM
Under nitrogen protection, earlier maleic anhydride is warming up to 60 ℃ of fusions, add ethylene glycol and catalyzer tosic acid more in proportion, isothermal reaction 1～3h, discharging is standby; Wherein the mol ratio of maleic anhydride and ethylene glycol is 1: 2～2.5, and the amount of tosic acid accounts for 0.5～2% of the total mass that feeds intake;
(2) surface modification of nano-inorganic
With quality is that 1～5% properties-correcting agent of inorganic materials quality joins in 10～20wt% inorganic materials slurries after water-soluble, is to react 1h under 20～80 ℃ of conditions in temperature, filters, and drying obtains the modified Nano inorganic materials;
(3) preparation of PET/nano-inorganic matrix material
With terephthalic acid (PTA), ethylene glycol (EG), polycondensation catalyst antimonous oxide (Sb
2O
3) or antimony acetate and stablizer trimethyl phosphite 99 (TMP) adding reactor, 1. stir forms slurry, and wherein the mol ratio of PTA and EG is 1: 1.1～1.5, and the amount of catalyzer and stablizer all accounts for 0.1% of PTA quality; Add nano-inorganic and BHEM in EG, 2. ultra-sonic dispersion 30min forms slurry, and wherein the weight ratio of BHEM and nano-inorganic is 1: 5～20, and the weight ratio of nano-inorganic and EG is 1: 1.3～2.5; 1. slurry in the reactor is warming up to 198～245 ℃, esterification 3～4h under 0.40～0.45MPa condition, after esterification finishes, the system pressure release to normal pressure, be cooled to 150 ℃ after reheat to 245 ℃, then 2. slurry is added in the reactor and stir, be evacuated to pressure, be warming up to 265～275 ℃ less than 300Pa, reaction 3～5h obtains nano-inorganic homodisperse matrix material in PET.
Among the above-mentioned preparation method, the properties-correcting agent of nano inorganic material is one or more the mixture in polyoxyethylene glycol phosphoric acid ester (molecular weight of polyoxyethylene glycol is 200～20000), trimethyl-glycine phosphoric acid ester, stearic acid, the oleic acid, be to obtain wetting ability or hydrophobic nano inorganic material after the modification, described nano inorganic material is CaCO
3, SiO
2, ZnO or BaSO
4
Advance of the present invention is:
1. in position in the polymerization process, add a spot of BHEM, improved the compatibility between polyester and the nano inorganic material, prepare homodisperse PET/nano-inorganic matrix material; And when being increased to the 2wt% of PET theoretical yield along with the content of BHEM, the nano-inorganic content that is dispersed among the PET also is increased to 20% of PET quality thereupon, obtain the PET/nano-inorganic matrix material of limiting viscosity about 0.65, this invention has solved nano-inorganic and disperseed a uneven difficult problem in PET.
2. the source of mineral filler of the present invention is wide, easily processing, and the modifying process cost is low; Technology is simple, safety non-pollution, is applicable to the industrialized development of PET/nano-inorganic matrix material.
Description of drawings
Fig. 1 is the structure iron of used dispersion agent among the present invention;
Fig. 2 is experiment flow figure of the present invention;
Fig. 3 is that filler is 5wt%S-CaCO
3, dispersion agent is the PET/nano-CaCO of 1wt%
3The stereoscan photograph of matrix material;
Fig. 4 is that filler is 5wt%P-CaCO
3, dispersion agent is the PET/nano-CaCO of 1wt%
3The stereoscan photograph of matrix material;
Fig. 5 is that filler is 5wt%S-BaSO
4, dispersion agent is the PET/PET/nano-BaSO of 0.5wt%
4The stereoscan photograph of matrix material;
Fig. 6 is that filler is that 5wt%S-ZnO, dispersion agent are the stereoscan photograph of the PET/nano-ZnO matrix material of 0.5wt%.
Fig. 7 is that filler is 5wt%P-SiO
2, dispersion agent is the PET/nano-SiO of 0.5wt%
2The stereoscan photograph of matrix material.
Embodiment
Embodiment one:
Get 520g PTA, 0.52g Sb
2O
3Join among the 194ml EG with 0.52g TMP, 1. stir forms slurry; In 200ml EG, add 151g polyoxyethylene glycol phosphoric acid ester (molecular weight polyethylene glycol is 1000) modified calcium carbonate (P-CaCO
3) and 22.65g BHEM, 2. ultra-sonic dispersion 30min forms slurry.1. join slurry in the reactor, under 235 ℃, 0.40MPa condition behind the esterification 3.5h, the system pressure release to normal pressure, be cooled to reheat to 245 ℃ (for ethylene glycol unnecessary in the removing system) after 150 ℃, 2. slurry joins in the reactor then, be evacuated to pressure 200Pa, react 4h under 275 ℃ of conditions, the amount that obtains being dispersed in the lime carbonate among the PET accounts for 19.97% of PET quality, and limiting viscosity is 0.66 PET/nano-CaCO
3Matrix material.
Embodiment two:
The replacing slurry 2. volume of middle EG is 100ml, P-CaCO
3Add-on 75.5g, the add-on of BHEM is other condition of 7.55g such as embodiment one.The amount that obtains being dispersed in the lime carbonate among the PET accounts for 9.98% of PET quality, and limiting viscosity is 0.66 PET/nano-CaCO
3Matrix material.
Embodiment three:
The replacing slurry 2. volume of middle EG is 55ml, P-CaCO
3Add-on be 37.75g, the add-on of BHEM is 7.55g, other condition such as embodiment one.The amount that obtains being dispersed in the lime carbonate among the PET accounts for 5.00% of PET quality, and limiting viscosity is 0.68 PET/nano-CaCO
3Matrix material.
Embodiment four:
P-CaCO in the replacing system
3Be stearic acid modified CaCO
3(S-CaCO
3), the slurry 2. volume of middle EG is 50ml, S-CaCO
3Add-on be 37.75g, the add-on of BHEM is 7.55g, other condition such as embodiment one.The amount that obtains being dispersed in the lime carbonate among the PET accounts for 4.99% of PET quality, and limiting viscosity is 0.67 PET/nano-CaCO
3Matrix material.
Embodiment five:
Mineral filler in the replacing system is stearic acid modified BaSO
4(S-BaSO
4), the slurry 2. volume of middle EG is 50ml, S-BaSO
4Add-on 37.75g, the add-on of BHEM is 3.775g, other condition such as embodiment one.The amount that obtains being dispersed in the barium sulfate among the PET accounts for 4.98% of PET quality, and limiting viscosity is 0.70 PET/nano-BaSO
4Matrix material.
Embodiment six:
Mineral filler in the replacing system is stearic acid modified ZnO (S-ZnO), and the slurry 2. volume of middle EG is 50ml, the add-on 37.75g of S-ZnO, and the add-on of BHEM is 3.775g, other condition such as embodiment one.The amount that obtains being dispersed in the zinc oxide among the PET accounts for 4.99% of PET quality, and limiting viscosity is 0.66 PET/nano-ZnO matrix material.
Embodiment seven:
Mineral filler in the replacing system is polyoxyethylene glycol phosphoric acid ester (molecular weight polyethylene glycol is 1000) improved silica (P-SiO
2), the slurry 2. volume of middle EG is 50ml, P-SiO
2Add-on 37.75g, the add-on of BHEM is 3.775g, other condition such as embodiment one.The amount that obtains being dispersed in the silicon-dioxide among the PET accounts for 4.97% of PET quality, and limiting viscosity is 0.67 PET/nano-SiO
2Matrix material.
Embodiment eight:
The catalyzer of changing reaction system is an antimony acetate, other condition such as embodiment one.The amount that obtains being dispersed in the lime carbonate among the PET accounts for 19.97% of PET quality, and limiting viscosity is 0.64 PET/nano-CaCO
3Matrix material.
Claims (3)
1. the preparation method of a homodisperse polyethylene terephthalate/nano-inorganic substance (PET/nano-inorganic) matrix material the steps include:
(1) preparation of dispersion agent toxilic acid binaryglycol ester (BHEM)
Under nitrogen protection, earlier maleic anhydride is warming up to 60 ℃ of fusions, add ethylene glycol and catalyzer tosic acid more in proportion, isothermal reaction 1～3h, discharging is standby; Wherein the mol ratio of maleic anhydride and ethylene glycol is 1: 2～2.5, and the amount of tosic acid accounts for 0.5～2% of the total mass that feeds intake;
(2) surface modification of nano-inorganic
With quality is that 1～5% properties-correcting agent of inorganic materials quality joins in 10～20wt% inorganic materials slurries after water-soluble, is to react 1h under 20～80 ℃ of conditions in temperature, filters, and drying obtains the modified Nano inorganic materials;
(3) preparation of PET/nano-inorganic matrix material
With terephthalic acid (PTA), ethylene glycol (EG), polycondensation catalyst antimonous oxide (Sb
2O
3) or antimony acetate and stablizer trimethyl phosphite 99 (TMP) adding reactor, 1. stir forms slurry, and wherein the mol ratio of PTA and EG is 1: 1.1～1.5, and the amount of catalyzer and stablizer all accounts for 0.1% of PTA quality; Add nano-inorganic and BHEM in EG, 2. ultra-sonic dispersion 30min forms slurry, and wherein the weight ratio of BHEM and nano-inorganic is 1: 5～20, and the weight ratio of nano-inorganic and EG is 1: 1.3～2.5; 1. slurry in the reactor is warming up to 198～245 ℃, esterification 3～4h under 0.40～0.45MPa condition, after esterification finishes, the system pressure release to normal pressure, be cooled to 150 ℃ after reheat to 245 ℃, then 2. slurry is added in the reactor and stir, be evacuated to pressure, be warming up to 265～275 ℃ less than 300Pa, reaction 3～5h obtains nano-inorganic homodisperse matrix material in PET.
2. a kind of according to claim 1 preparation method of homodisperse PET/nano-inorganic matrix material, it is characterized in that: the properties-correcting agent of nano inorganic material is one or more the mixture in polyoxyethylene glycol phosphoric acid ester, trimethyl-glycine phosphoric acid ester, stearic acid, the oleic acid, be to obtain wetting ability or hydrophobic nano inorganic materials after the modification, wherein the molecular weight of polyoxyethylene glycol is 200～20000 in the polyoxyethylene glycol phosphoric acid ester.
3. a kind of according to claim 1 preparation method of homodisperse PET/nano-inorganic matrix material, it is characterized in that: described nano inorganic material is CaCO
3, SiO
2, ZnO or BaSO
4
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|---|---|---|---|
| CN2010102712869A CN101935439B (en) | 2010-09-03 | 2010-09-03 | Method for preparing uniformly dispersed PET/nano-inorganic composite material |
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|---|---|---|---|
| CN2010102712869A CN101935439B (en) | 2010-09-03 | 2010-09-03 | Method for preparing uniformly dispersed PET/nano-inorganic composite material |
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| CN101935439B CN101935439B (en) | 2012-05-16 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199330A (en) * | 2015-11-10 | 2015-12-30 | 聚威工程塑料(上海)有限公司 | Highly-filling polyester material and preparation method thereof |
| CN108409916A (en) * | 2018-04-18 | 2018-08-17 | 西北师范大学 | A kind of preparation method of LSOH anti-flaming unsaturated polyester resin composite material |
| CN110396181A (en) * | 2018-04-24 | 2019-11-01 | 中国石油化工股份有限公司 | A kind of preparation method of fast crystallizing polyester and its hot-filling polyester bottle piece |
| CN115286985A (en) * | 2022-01-24 | 2022-11-04 | 扬州工业职业技术学院 | Double-component water-based environment-friendly coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04183717A (en) * | 1990-11-19 | 1992-06-30 | Nippon Ester Co Ltd | Production of polyester |
| CN1663977A (en) * | 2005-02-06 | 2005-09-07 | 中国石化仪征化纤股份有限公司 | Method for preparing calcium carbonate modified polyester |
| CN101402722A (en) * | 2008-11-26 | 2009-04-08 | 吉林大学 | Method for preparing nano-calcium carbonate/polyester composite material |
-
2010
- 2010-09-03 CN CN2010102712869A patent/CN101935439B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04183717A (en) * | 1990-11-19 | 1992-06-30 | Nippon Ester Co Ltd | Production of polyester |
| CN1663977A (en) * | 2005-02-06 | 2005-09-07 | 中国石化仪征化纤股份有限公司 | Method for preparing calcium carbonate modified polyester |
| CN101402722A (en) * | 2008-11-26 | 2009-04-08 | 吉林大学 | Method for preparing nano-calcium carbonate/polyester composite material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199330A (en) * | 2015-11-10 | 2015-12-30 | 聚威工程塑料(上海)有限公司 | Highly-filling polyester material and preparation method thereof |
| CN108409916A (en) * | 2018-04-18 | 2018-08-17 | 西北师范大学 | A kind of preparation method of LSOH anti-flaming unsaturated polyester resin composite material |
| CN108409916B (en) * | 2018-04-18 | 2020-08-21 | 西北师范大学 | Preparation method of halogen-free low-smoke flame-retardant unsaturated polyester resin composite material |
| CN110396181A (en) * | 2018-04-24 | 2019-11-01 | 中国石油化工股份有限公司 | A kind of preparation method of fast crystallizing polyester and its hot-filling polyester bottle piece |
| CN110396181B (en) * | 2018-04-24 | 2021-12-07 | 中国石油化工股份有限公司 | Fast crystallization polyester and preparation method of hot-filling polyester bottle chip thereof |
| CN115286985A (en) * | 2022-01-24 | 2022-11-04 | 扬州工业职业技术学院 | Double-component water-based environment-friendly coating |
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| CN101935439B (en) | 2012-05-16 |
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