CN1583878A - 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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- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 title abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 title 1
- 229920001223 polyethylene glycol Polymers 0.000 title 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 36
- -1 Alcohol ester Chemical class 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims description 57
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 39
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 39
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 235000011089 carbon dioxide Nutrition 0.000 claims description 6
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 6
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000009827 uniform distribution Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract 1
- CPGKMLVTFNUAHL-UHFFFAOYSA-N [Ca].[Ca] Chemical compound [Ca].[Ca] CPGKMLVTFNUAHL-UHFFFAOYSA-N 0.000 abstract 1
- HBBATKAUXPHIQN-UHFFFAOYSA-N [Cl].[Ti] Chemical compound [Cl].[Ti] HBBATKAUXPHIQN-UHFFFAOYSA-N 0.000 abstract 1
- ICGLOTCMOYCOTB-UHFFFAOYSA-N [Cl].[Zn] Chemical compound [Cl].[Zn] ICGLOTCMOYCOTB-UHFFFAOYSA-N 0.000 abstract 1
- NTBRLDWLSWZHSS-UHFFFAOYSA-N [Zr].[Cl] Chemical compound [Zr].[Cl] NTBRLDWLSWZHSS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- YXIDSOCDWLQVAZ-UHFFFAOYSA-N ethane-1,2-diol;formic acid Chemical compound OC=O.OCCO YXIDSOCDWLQVAZ-UHFFFAOYSA-N 0.000 abstract 1
- 235000019253 formic acid Nutrition 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 22
- 238000002425 crystallisation Methods 0.000 description 10
- 230000008025 crystallization Effects 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000004927 fusion Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 229910003087 TiOx Inorganic materials 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- FHUCUPVQDUPROK-UHFFFAOYSA-N acetic acid;antimony Chemical compound [Sb].CC(O)=O FHUCUPVQDUPROK-UHFFFAOYSA-N 0.000 description 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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Abstract
Second two of two formic acid of benzene that this invention has disclosed one kind and gathered correctly Alcohol ester/inorganic nanometer particle composite and method of preparing. The composite, in order to gather to two formic acid ethylene glycol ester and even of benzene the ones that are distributed the radius of particle among them for 1-100nm are too spherical to have The nanometer particle of the machine, especially the mass ratio between the two Whether. 70-99.999 is spherical among particles than 0.001-30 Difference of the radius of particle <2nm, and disperse the state while presenting single gram. It prepare it is first been in method what has been caused separately calcium calcium or chlorine zirconium not sour or Chlorine zinc or the scattered solution of nanometer particle of the chlorine titanium: In water this solution rain board sneak into ethylene glycol under the state, The mass ratio between the two is 1-60 to 40-90, mix it to growing Stabilize solution; Stabilize solution and to 2 first benzene finally Acid, the catalyst is mixed and mixed, the mass ratio among the three is 1300-1500 to 2000-2200 to 0.4-0.6, press the routine It formate by two office vs. benzene make the formic acid ethylene glycol ways of ester according to compound to two formic acid ethylene glycol ester of benzene/the inorganic nanometer particle Material.
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 thermalmechanieal 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 JOEL100CXII 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, it is characterized in that the mass ratio between 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.
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 polyethylene terephthalate/inorganic nanometer particle compesite according to claim 1 comprises with ordinary method obtaining ethylene glycol, it is characterized in that:
3.1, 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;
3.2, 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;
3.3, 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 preparation method 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 |
| CN101247912B (en) * | 2005-07-21 | 2010-08-04 | 株式会社丰田中央研究所 | Composite material, composite material substrate, composite material dispersion fluid, and method for producing same |
| CN103709689A (en) * | 2013-12-30 | 2014-04-09 | 上海紫东薄膜材料股份有限公司 | Preparation method of PET (polyester) film with uniformly dispersed vanadium dioxide |
| US9296622B2 (en) | 2012-08-22 | 2016-03-29 | Hy-Power Coatings Limited | Method for continuous preparation of indium-tin coprecipitates and indium-tin-oxide nanopowders with substantially homogeneous indium/tin composition, controllable shape and particle size |
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2003
- 2003-08-22 CN CN 03152832 patent/CN1253499C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412132C (en) * | 2005-03-04 | 2008-08-20 | 中国科学院合肥物质科学研究院 | Polyester bottle and preparation method thereof |
| CN101247912B (en) * | 2005-07-21 | 2010-08-04 | 株式会社丰田中央研究所 | Composite material, composite material substrate, composite material dispersion fluid, and method for producing same |
| 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 |
| US9296622B2 (en) | 2012-08-22 | 2016-03-29 | Hy-Power Coatings Limited | Method for continuous preparation of indium-tin coprecipitates and indium-tin-oxide nanopowders with substantially homogeneous indium/tin composition, controllable shape and particle size |
| CN103709689A (en) * | 2013-12-30 | 2014-04-09 | 上海紫东薄膜材料股份有限公司 | Preparation method of PET (polyester) film with uniformly dispersed vanadium dioxide |
| 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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