CN1253499C - Polyethylene glycol terephthalate/inorganic nanometer partical composite material and preparing method thereof - Google Patents
Polyethylene glycol terephthalate/inorganic nanometer partical composite material and preparing method thereof Download PDFInfo
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- CN1253499C CN1253499C CN 03152832 CN03152832A CN1253499C CN 1253499 C CN1253499 C CN 1253499C CN 03152832 CN03152832 CN 03152832 CN 03152832 A CN03152832 A CN 03152832A CN 1253499 C CN1253499 C CN 1253499C
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Abstract
The present invention discloses a polyethylene glycol terephthalate / inorganic nanometer particle composite material and a preparation method thereof. The composite material is composed of polyethylene glycol terephthalate and spherical inorganic nanometer particles evenly distributed in the polyethylene glycol terephthalate, wherein the particle diameter of the nanometer particle is from 1 to 100 nm, particularly, the mass ratio of the polyethylene glycol terephthalate to the nanometer particle is 70 to 99.999: 0.001 to 30, the difference between the particle diameters of the nanometer particles is less than 2 nm, and the particle presents a single particle dispersed state. The preparation method comprises the following steps: firstly, nanometer particle dispersed solutions of calcium carbonate or zirconia or zinc oxide or titanium oxide are respectively prepared; then the solution and ethylene glycol are mixed in a stirring state, the mass ratio of the solutions to the ethylene glycol is 1 to 60: 40 to 99, and the mixture is stirred to produce a stable solution; finally, the stable solution, terephthalic acid and catalyst are mixed and stirred, the mass ratio of the stable solution to the terephthalic acid to the catalyst is 1300 to 1500: 2000 to 2200: 0.4 to 0.6, and the polyethylene glycol terephthalate/ inorganic nanometer particle composite material is prepared according to the conventional mode for synthesizing polyethylene glycol terephthalate. The present invention can be widely used for the food packing industry which needs high temperature disinfection, and the field of engineering plastics and electric materials.
Description
Technical field the present invention relates to a kind of matrix material and preparation method thereof, especially polyethylene terephthalate/inorganic nanometer particle compesite and preparation method thereof.
Background technology is present, and people improve the application performance of polyester material in different field in order further to improve the applicability of polyethylene terephthalate (PET).The existing report that utilizes inorganic nano-particle to improve its thermodynamic property.As in October 4 calendar year 2001, a kind of polyester based matrix material with better thermodynamic property and preparation method thereof (International Publication Number:WO 01/72881A1.Title:Polyester-based compositions having improved thermalmechanical properties andprocess to produce said compositions.) is disclosed among WO 01/72881 A1, wherein, the polyester based matrix material comprises the spherical mineral particle of polyester matrix and nano-scale, and the weight content of mineral particle is 0.01～25% of a polyester based matrix material; The preparation method is for earlier being less than or equal to water and dibasic alcohol and dicarboxylic acid or dicarboxylic ester and particle diameter the SiO of 200nm
2Colloidal sol is mixed and made into the water-sol mutually, again acid or acid esters and glycol is carried out esterification or transesterification reaction, under vacuum carboxylate is carried out polyreaction and obtains the polyester based matrix material afterwards.But this polyester based performance of composites as second-order transition temperature, Tc, melt temperature etc., is compared with PET, does not see substantial raising; Also because of not containing the preparation technology of inorganic nano-particle, the homogeneity of its particle diameter and shape-dependent constant are all uncontrollable, have influenced performance of composites for the preparation method.
The summary of the invention the technical problem to be solved in the present invention provides a kind of thermal characteristics to improve polyethylene terephthalate/inorganic nanometer particle compesite easy to prepare and preparation method for overcoming weak point of the prior art.
Polyethylene terephthalate/inorganic nanometer particle compesite comprises polyethylene terephthalate and uniform distribution inorganic nano-particle therein, said inorganic nano-particle is spherical, its particle diameter is 1～100nm, mass ratio between particularly said polyethylene terephthalate and inorganic nano-particle is 70～99.999 to 0.001～30, poor＜the 2nm of the particle diameter that said spherical inorganic nano-particle is mutual, and spherical inorganic nano-particle is the single particle dispersion state.
As the further improvement of polyethylene terephthalate/inorganic nanometer particle compesite, described inorganic nano-particle is lime carbonate or zirconium white or zinc oxide or titanium oxide.
The preparation method of polyethylene terephthalate/inorganic nanometer particle compesite comprises with ordinary method and obtains ethylene glycol, particularly earlier calcium oxide is mixed with water, mass ratio between the two is 5～25 to 75～95, make it hydrolysis, feeding carbonic acid gas adjusting pH value again is 8～10,5～10 ℃ of following stirring in water bath to generating nanoparticle dispersive solution, or earlier zirconium oxychloride or zinc sulfate are mixed with water, mass ratio between the two is 5～25 to 75～95, make it dissolving, after regulating pH value and be 8～10 with ammoniacal liquor again, be washed with water to wherein chlorion or concentration＜10 of sulfate ion
-5The mol/ liter, be stirred to after again its aqueous ethanolic solution with 10% being mixed and generate nanoparticle dispersive solution, or earlier tetrabutyl titanate is mixed mutually with water, ethanol, triangular mass ratio is 5～15 to 5～20 to 60～75, make it hydrolysis, regulating its pH value with acid or ammoniacal liquor again is 2～3 or 8～10, and in 60～80 ℃ of following stirring in water bath to generating nanoparticle dispersive solution; Nano-particle solution is sneaked in the ethylene glycol under whipped state, the mass ratio between nano-particle solution and ethylene glycol is 1～60 to 40～99 again, mixes liquid to generating stabilizing solution; At last stabilizing solution and terephthalic acid, catalyst mix are stirred, triangular mass ratio is 1300～1500 to 2000～2200 to 0.4～0.6, and the mode of synthetic polyethylene terephthalate makes polyethylene terephthalate/inorganic nanometer particle compesite routinely.
As the preparation method's of polyethylene terephthalate/inorganic nanometer particle compesite further improvement, described water is deionized water or distilled water; Described acid is hydrochloric acid or nitric acid or sulfuric acid; Described catalyzer is the mixture of antimony acetate or zinc acetate and antimony acetate.
Beneficial effect with respect to prior art is, one places observation under the electron microscope with freezing little section of matrix material, and the size that is distributed in the spherical inorganic nano-particle among the PET as can be known equably is consistent, and be the single particle dispersion state, no agglomeration exists; They are two years old, after the matrix material that makes tested with difference formula scanning calorimeter, learn: 1. second-order transition temperature has improved 8～20 ℃, and increase along with inorganic nano-particle content, second-order transition temperature is in rising trend, and this greatly helps its use in the food product pack industry that needs high-temperature sterilization; 2. improved Tc significantly, improvement value reaches 17～26 ℃, and raise along with the increase of inorganic nano-particle content, crystallization velocity also obtains to significantly improve, this point shows also fairly obvious in cold crystallization, cold crystallization peak temperature value has reduced by 6～26 ℃, the raising of this crystallization velocity is highly advantageous to its use as engineering plastics, when being the demoulding, bigger distortion and contraction can not appear, 3. melt temperature also is improved, and has improved 13～15 ℃, and this will help its use as electrical material; Its three, in the process of preparation, used inorganic nano-particle easily makes, and the consistence of the particle diameter of particle and shape-dependent constant all can be controlled effectively, inorganic nano-particle can be directly and reactant add together, make integrated artistic easy.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 be to the matrix material freezing microtome section take the photograph after with Japanese JOEL100CX II type transmission electron microscopy observation photo, wherein, (a) figure is the photo of pure PET material; (b) figure is the matrix material photo when containing 0.05% inorganic nano-particle weight; (c) figure is the matrix material photo when containing 0.5% inorganic nano-particle weight; (d) figure is the matrix material photo when containing 2% inorganic nano-particle weight; (e) figure is the matrix material photo when containing 10% inorganic nano-particle weight.
Fig. 2 is a second-order transition temperature of measuring matrix material, the heating and cooling time-scale of Tc and melt temperature, wherein, ordinate zou is a temperature, X-coordinate is the time, curve 1 among the figure is warmed up to 280 ℃ for the temperature rise rate with 50 ℃/minute from room temperature, curve 2 is to be incubated 5 minutes down at 280 ℃, to remove thermal history, curve 3 is to room temperature with 200 ℃/minute rate of temperature fall fast cooling, curve 4 is at room temperature being incubated 2 minutes, curve 5 is warmed up to 280 ℃ for the temperature rise rate with 10 ℃/minute from room temperature, and curve 6 is to be incubated 5 minutes down at 280 ℃, and curve 7 cools to room temperature for the rate of temperature fall with 10 ℃/minute from 280 ℃;
Fig. 3 records with the Pyris-1 type difference formula of U.S. PE company scanning calorimeter, the second-order transition temperature graphic representation that contains the matrix material of Different Weight inorganic nano-particle per-cent, wherein, ordinate zou is the unit heat flux, X-coordinate is a temperature, curve 8 among the figure is pure PET (second-order transition temperature is 73.88 ℃), curve 9 among the figure is for containing (second-order transition temperature is 81.588 ℃) at 0.05% o'clock, curve 10 is for containing (second-order transition temperature is 85.441 ℃) at 0.5% o'clock, curve 11 is for containing (second-order transition temperature is 88.965 ℃) at 2% o'clock, and curve 12 is for containing (second-order transition temperature is 92.098 ℃) at 10% o'clock;
Fig. 4 records with the Pyris-1 type difference formula of U.S. PE company scanning calorimeter, the graphic representation that contains the matrix material of Different Weight inorganic nano-particle per-cent, wherein, ordinate zou is the unit heat flux, X-coordinate is a temperature, curve 13 among the figure be pure PET's (193.76 ℃ of decrease temperature crystalline peak temperatures), curve 14 among the figure is for containing (210.34 ℃ of decrease temperature crystalline peak temperatures) at 0.05% o'clock, curve 15 is for containing (213.35 ℃ of decrease temperature crystalline peak temperatures) at 0.5% o'clock, curve 16 is for containing (216.83 ℃ of decrease temperature crystalline peak temperatures) at 2% o'clock, and curve 17 is for containing (218.29 ℃ of decrease temperature crystalline peak temperatures) at 10% o'clock;
Fig. 5 records with the Pyris-1 type difference formula of U.S. PE company scanning calorimeter, the cold crystallization graphic representation that contains the matrix material of Different Weight inorganic nano-particle per-cent, wherein, ordinate zou is the unit heat flux, X-coordinate is a temperature, curve 18 among the figure be pure PET's (153.81 ℃ of cold crystallization peak temperatures), curve 19 among the figure is for containing (147.35 ℃ of cold crystallization peak temperatures) at 0.05% o'clock, curve 20 is for containing (142.53 ℃ of cold crystallization peak temperatures) at 0.5% o'clock, curve 21 is for containing (136.52 ℃ of cold crystallization peak temperatures) at 2% o'clock, and curve 22 is for containing (127.63 ℃ of cold crystallization peak temperatures) at 10% o'clock;
Fig. 6 records with the Pyris-1 type difference formula of U.S. PE company scanning calorimeter, the melting curve figure that contains the matrix material of Different Weight inorganic nano-particle per-cent, wherein, ordinate zou is the unit heat flux, X-coordinate is a temperature, curve 23 among the figure be pure PET's (242.13 ℃ of fusion peak temperatures), curve 24 among the figure is for containing (254.33 ℃ of fusion peak temperatures) at 0.05% o'clock, curve 25 is for containing (255.45 ℃ of fusion peak temperatures) at 0.5% o'clock, curve 26 is for containing (255.87 ℃ of fusion peak temperatures) at 2% o'clock, and curve 27 is for containing (255.63 ℃ of fusion peak temperatures) at 10% o'clock.
Embodiment at first makes or buys from market ethylene glycol, terephthalic acid with ordinary method.
Embodiment 1:
Earlier calcium oxide is mixed with water, mass ratio between the two is 5 to 95, make it hydrolysis, feeding carbonic acid gas again, to regulate pH value be 8,, or earlier zirconium oxychloride or zinc sulfate mixed with water to generating nanoparticle dispersive solution 5 ℃ of following stirring in water bath, mass ratio between the two is 5 to 95, make it dissolving, after regulating pH value and be 8 with ammoniacal liquor again, be washed with water to wherein chlorion or concentration＜10 of sulfate ion
-5The mol/ liter, be stirred to after again its aqueous ethanolic solution with 10% being mixed and generate nanoparticle dispersive solution, or earlier tetrabutyl titanate, water, ethanol are mixed mutually, triangular mass ratio is 5 to 20 to 75, make it hydrolysis, regulating its pH value with hydrochloric acid or ammoniacal liquor again is 2 or 8, and in 60 ℃ of following stirring in water bath to generating nanoparticle dispersive solution; Nano-particle solution is sneaked in the ethylene glycol under whipped state, the mass ratio between nano-particle solution and ethylene glycol is 2 to 98 again, mixes liquid to generating settled solution; At last settled solution is mixed stirring with terephthalic acid, catalyst acetic acid antimony, triangular mass ratio is 1300 to 2200 to 0.6, and the mode of synthetic polyethylene terephthalate makes polyethylene terephthalate/lime carbonate or zirconium white or zinc oxide or TiOx nano matrix material routinely.After the test of this nano composite material, its result is as follows: shown in the curve 9 among (b) among Fig. 1, Fig. 3 of recording by the corresponding means of testing among Fig. 2, the curve 14 among Fig. 4, the curve 19 among Fig. 5, the curve 24 among Fig. 6.
Embodiment 2:
Earlier calcium oxide is mixed with water, mass ratio between the two is 10 to 90, make it hydrolysis, feeding carbonic acid gas again, to regulate pH value be 8.5,, or earlier zirconium oxychloride or zinc sulfate mixed with water to generating nanoparticle dispersive solution 7 ℃ of following stirring in water bath, mass ratio between the two is 10 to 90, make it dissolving, after regulating pH value and be 8.5 with ammoniacal liquor again, be washed with water to wherein chlorion or concentration＜10 of sulfate ion
-5The mol/ liter, be stirred to after again its aqueous ethanolic solution with 10% being mixed and generate nanoparticle dispersive solution, or earlier tetrabutyl titanate, water, ethanol are mixed mutually, triangular mass ratio is 8 to 10 to 65, make it hydrolysis, regulating its pH value with nitric acid or ammoniacal liquor again is 2.3 or 8.5, and in 68 ℃ of following stirring in water bath to generating nanoparticle dispersive solution; Nano-particle solution is sneaked in the ethylene glycol under whipped state, the mass ratio between nano-particle solution and ethylene glycol is 10 to 90 again, mixes liquid to generating settled solution; At last settled solution is mixed stirring with terephthalic acid, catalyst acetic acid zinc with the mixture of antimony acetate, triangular mass ratio is 1380 to 2080 to 0.5, and the mode of synthetic polyethylene terephthalate makes polyethylene terephthalate/lime carbonate or zirconium white or zinc oxide or TiOx nano matrix material routinely.After the test of this nano composite material, its result is as follows: shown in the curve 10 among (c) among Fig. 1, Fig. 3 of recording by the corresponding means of testing among Fig. 2, the curve 15 among Fig. 4, the curve 20 among Fig. 5, the curve 25 among Fig. 6.
Embodiment 3:
Earlier calcium oxide is mixed with water, mass ratio between the two is 20 to 80, make it hydrolysis, feeding carbonic acid gas again, to regulate pH value be 9,, or earlier zirconium oxychloride or zinc sulfate mixed with water to generating nanoparticle dispersive solution 9 ℃ of following stirring in water bath, mass ratio between the two is 20 to 80, make it dissolving, after regulating pH value and be 9 with ammoniacal liquor again, be washed with water to wherein chlorion or concentration＜10 of sulfate ion
-5The mol/ liter, be stirred to after again its aqueous ethanolic solution with 10% being mixed and generate nanoparticle dispersive solution, or earlier tetrabutyl titanate, water, ethanol are mixed mutually, triangular mass ratio is 13 to 16 to 70, make it hydrolysis, regulating its pH value with sulfuric acid or ammoniacal liquor again is 2.7 or 9.6, and in 75 ℃ of following stirring in water bath to generating nanoparticle dispersive solution; Nano-particle solution is sneaked in the ethylene glycol under whipped state, the mass ratio between nano-particle solution and ethylene glycol is 30 to 70 again, mixes liquid to generating settled solution; At last settled solution is mixed stirring with terephthalic acid, catalyst acetic acid antimony, triangular mass ratio is 1460 to 2150 to 0.5, and the mode of synthetic polyethylene terephthalate makes polyethylene terephthalate/lime carbonate or zirconium white or zinc oxide or TiOx nano matrix material routinely.After the test of this nano composite material, its result is as follows: shown in the curve 11 among (d) among Fig. 1, Fig. 3 of recording by the corresponding means of testing among Fig. 2, the curve 16 among Fig. 4, the curve 21 among Fig. 5, the curve 26 among Fig. 6.
Embodiment 4:
Earlier calcium oxide is mixed with water, mass ratio between the two is 25 to 75, make it hydrolysis, feeding carbonic acid gas again, to regulate pH value be 10,, or earlier zirconium oxychloride or zinc sulfate mixed with water to generating nanoparticle dispersive solution 10 ℃ of following stirring in water bath, mass ratio between the two is 25 to 75, make it dissolving, after regulating pH value and be 10 with ammoniacal liquor again, be washed with water to wherein chlorion or concentration＜10 of sulfate ion
-5The mol/ liter, be stirred to after again its aqueous ethanolic solution with 10% being mixed and generate nanoparticle dispersive solution, or earlier tetrabutyl titanate, water, ethanol are mixed mutually, triangular mass ratio is 15 to 5 to 60, make it hydrolysis, regulating its pH value with hydrochloric acid or ammoniacal liquor again is 3 or 10, and in 80 ℃ of following stirring in water bath to generating nanoparticle dispersive solution; Nano-particle solution is sneaked in the ethylene glycol under whipped state, the mass ratio between nano-particle solution and ethylene glycol is 60 to 40 again, mixes liquid to generating settled solution; At last settled solution is mixed stirring with terephthalic acid, catalyst acetic acid zinc with the mixture of antimony acetate, triangular mass ratio is 1500 to 2000 to 0.4, and the mode of synthetic polyethylene terephthalate makes polyethylene terephthalate/lime carbonate or zirconium white or zinc oxide or TiOx nano matrix material routinely.After the test of this nano composite material, its result is as follows: shown in the curve 12 among (e) among Fig. 1, Fig. 3 of recording by the corresponding means of testing among Fig. 2, the curve 17 among Fig. 4, the curve 22 among Fig. 5, the curve 27 among Fig. 6.
Obviously, those skilled in the art can carry out various changes and modification to polyethylene terephthalate/inorganic nanometer particle compesite of the present invention and preparation method and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (6)
1, a kind of polyethylene terephthalate/inorganic nanometer particle compesite, comprise polyethylene terephthalate and uniform distribution inorganic nano-particle therein, said inorganic nano-particle is spherical, its particle diameter is 1～100nm, mass ratio between said polyethylene terephthalate and inorganic nano-particle is 70～99.999 to 0.001～30, poor＜the 2nm that it is characterized in that the particle diameter that said spherical inorganic nano-particle is mutual, and spherical inorganic nano-particle is the single particle dispersion state.
2, polyethylene terephthalate/inorganic nanometer particle compesite according to claim 1 is characterized in that said inorganic nano-particle is lime carbonate or zirconium white or zinc oxide or titanium oxide.
3, the preparation method of the described polyethylene terephthalate/inorganic nanometer particle compesite of claim 1 comprises with ordinary method obtaining ethylene glycol, it is characterized in that:
(1), calcium oxide is mixed with water, mass ratio between the two is 5～25 to 75～95, make it hydrolysis, feeding carbonic acid gas again, to regulate pH value be 8～10,, or zirconium oxychloride or zinc sulfate mixed with water to generating nanoparticle dispersive solution 5～10 ℃ of following stirring in water bath, mass ratio between the two is 5～25 to 75～95, make it dissolving, after regulating pH value and be 8～10 with ammoniacal liquor again, be washed with water to wherein chlorion or concentration＜10 of sulfate ion
-5The mol/ liter, be stirred to after again its aqueous ethanolic solution with 10% being mixed and generate nanoparticle dispersive solution, or tetrabutyl titanate mixed mutually with water, ethanol, triangular mass ratio is 5～15 to 5～20 to 60～75, make it hydrolysis, regulating its pH value with acid or ammoniacal liquor again is 2～3 or 8～10, and in 60～80 ℃ of following stirring in water bath to generating nanoparticle dispersive solution;
(2), nano-particle solution is sneaked in the ethylene glycol under whipped state, the mass ratio between nano-particle solution and ethylene glycol is 1～60 to 40～99, mixes liquid to generating stabilizing solution;
(3), stabilizing solution and terephthalic acid, catalyst mix are stirred, triangular mass ratio is 1300～1500 to 2000～2200 to 0.4～0.6, and the mode of synthetic polyethylene terephthalate makes polyethylene terephthalate/inorganic nanometer particle compesite routinely.
4, the preparation method of polyethylene terephthalate/inorganic nanometer particle compesite according to claim 3 is characterized in that water is deionized water or distilled water.
5, the preparation method of polyethylene terephthalate/inorganic nanometer particle compesite according to claim 3 is characterized in that acid is hydrochloric acid or nitric acid or sulfuric acid.
6, the preparation method of polyethylene terephthalate/inorganic nanometer particle compesite according to claim 3 is characterized in that catalyzer is the mixture of antimony acetate or zinc acetate and antimony acetate.
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| 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 |
| US8475921B2 (en) * | 2005-07-21 | 2013-07-02 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Composite material, composite material substrate, composite material dispersed fluid, and manufacturing methods thereof |
| CN100425652C (en) * | 2005-12-13 | 2008-10-15 | 苏州市凯米克新材料有限公司 | High-performance reinforced fire-retardant polyster engineering plastic |
| CA2787584A1 (en) | 2012-08-22 | 2014-02-22 | Hy-Power Nano Inc. | Method for continuous preparation of indium-tin coprecipitates and indium-tin-oxide nanopowders with substantially homogeneous indium/tin composition, controllable shape and particle size |
| CN103709689B (en) * | 2013-12-30 | 2015-11-11 | 上海紫东薄膜材料股份有限公司 | The preparation method of the homodisperse PET film of a kind of vanadium dioxide |
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