CN103059519A - Preparation method for white polyester master batches - Google Patents
Preparation method for white polyester master batches Download PDFInfo
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- CN103059519A CN103059519A CN2012105272323A CN201210527232A CN103059519A CN 103059519 A CN103059519 A CN 103059519A CN 2012105272323 A CN2012105272323 A CN 2012105272323A CN 201210527232 A CN201210527232 A CN 201210527232A CN 103059519 A CN103059519 A CN 103059519A
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- pigment
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- coupling agent
- inorganic
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- 229920000728 polyester Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000049 pigment Substances 0.000 claims abstract description 66
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- 238000004381 surface treatment Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 21
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 15
- 239000011247 coating layer Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000032050 esterification Effects 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- -1 boric acid ester Chemical class 0.000 claims description 7
- 150000007520 diprotic acids Chemical class 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 239000012756 surface treatment agent Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000001038 titanium pigment Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000004595 color masterbatch Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000012463 white pigment Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Abstract
The invention relates to a preparation method for white polyester master batches. The preparation method comprises the following steps of (1) performing surface treatment on a pigment; a, performing inorganic surface treatment on the pigment; and b, performing coupling agent surface treatment on the pigment; (2) esterifying; (3) performing polycondensation; and (4) pelleting. According to the preparation method, resin is not required to be subjected to secondary smelting; the process is simple, and the production cost is low; and the dispersion uniformity of the pigment in polyester is improved, and the final viscosity of the color master batches can be more convenient to control by performing the inorganic surface treatment and the coupling agent surface treatment on the pigment and controlling system viscosity during adding the pigment and the system viscosity during terminating the polycondensation.
Description
Technical field
The present invention relates to a kind of preparation method of polyester masterbatch, particularly a kind of preparation method of white polyester masterbatch.
Background technology
As a kind of important method of producing white polyester film, add directly that the white master material method is compared to coating method and staining has its unique advantage, not only can reduce operation, reduce production costs; Minimizing is because using dyestuff to cause pollution to environment; Substantially need not consider coating method or staining must pay close attention to dye (face) material and the viscosity fastness situation of counterdie.
Colour batch mainly forms by pigment with as the resin of carrier, at present, the preparation of masterbatch usually adopt melting again comminution granulation be prepared, be about to pigment, auxiliary agent and mix under melt temperature as the resin of carrier, through extruding, granulation and making.There is following defective in this method: (1) need to be to again melting of vector resin, and production process is complicated, and production cost is high; (2) owing to higher as the resin viscosity of carrier, cause the dispersion of pigment in resin inhomogeneous, cause the colour batch streaking even, and then affect the homogeneity of white polyester film colourity; (3) vector resin viscosity after carrying out melting can descend, and the final viscosity of colour batch also can be different along with the difference of pigment add-on, caused colour batch final viscosity be difficult to control.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the above-mentioned technical problem that prior art exists, and a kind of preparation method of white polyester masterbatch is provided.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of preparation method of white polyester masterbatch, described preparation method comprises following operation:
1. the surface treatment procedure of pigment:
A. the inorganic surfaces of pigment is processed:
Be that the pigment of 10～5000nm carries out surface treatment with inorganic surface treatment agent to particle diameter, coating thickness in surface of pigments is the inorganic coating layer of 3～15nm;
B. the coupling agent surface treatment of pigment:
The pigment that above-mentioned inorganic surfaces is processed carries out the coupling agent surface treatment;
2. esterification step:
In conversion unit, add diprotic acid and dibasic alcohol, be filled with nitrogen, 230～250 ℃ of esterifications 2～3 hours;
3. polycondensation step:
After above-mentioned esterification finishes, conversion unit is vacuumized, make the pressure in the equipment be lower than 60pa, keep simultaneously the interior temperature of conversion unit at 270～285 ℃, the beginning polycondensation, when the viscosity of system reaches 0.20dl/g～0.65dl/g, add the surface-treated pigment of operation (1), when system viscosity reaches 0.50dl/g～0.70dl/g, stop polycondensation;
4. granulating working procedure
Polycondensation through making silk, cooling, granulation, obtains the white polyester masterbatch after stopping.
In the aforesaid method, described inorganic surface treatment agent can be one or more in silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide, the ferric oxide.
In the aforesaid method, described pigment is one or more in titanium pigment, plumbous matter pigment, zinc matter pigment, weisspiessglanz, barium sulfate, the calcium carbonate.
In the aforesaid method, the particle diameter of described pigment is 10～5000nm.
In the aforesaid method, described inorganic coating layer can be the individual layer coating layer, also can be the multilayer coating structure layer.
In the aforesaid method, described coupling agent is titanate coupling agent, silane coupling agent, phosphate coupling agent, boric acid ester coupler, organic complex or aluminic acid compound.
Compared with prior art, the present invention has following advantage:
1. the inventive method does not need resin is carried out second melting, and technique is simple, and production cost is low.
2. the present invention processes and the coupling agent surface treatment by pigment being carried out inorganic surfaces, and the system viscosity during by the adding fashionable system viscosity and stop polycondensation of control pigment, improved pigment polyester dispersing uniformity, can control comparatively expediently the final viscosity of colour batch, make things convenient for the granulation of masterbatch.
Embodiment
Color and luster homogeneity for the white polyester that guarantees to adopt white master material preparation provided by the invention needs the colo(u)rant dispersion in the masterbatch even.For guarantee that pigment is uniformly dispersed in masterbatch, the size of particles of selected pigment should be as much as possible little, but along with reducing of pigment particle size, powder pigment has very high surfactivity under the effect of surface effects, small-size effect and quantum tunneling effect, very easily reunite between granules of pigments, it is inhomogeneous to cause pigment particles to disperse in vector resin.Moreover, because pigment itself just is difficult for disperseing in organic medium, so that be uniformly dispersed the very difficulty of pigment in vector resin; Therefore, before adding in the vector resin, must carry out surface treatment to it to pigment, to improve the dispersing property of pigment in vector resin.
Surface treatment to pigment has following several method usually: inorganic surfaces processing, coupling agent surface treatment, tensio-active agent surface treatment, hyper-dispersant surface treatment and rosined soap surface treatment etc.The present invention selects inorganic surfaces to process and coupling agent surface-treated method is carried out surface treatment to pigment.
Inorganic surfaces is processed and with inorganic surface treatment agent pigment is carried out surface treatment exactly, form the inorganic coating layer in surface of pigments, reduce the reunion between pigment, improve the dispersing property of pigment particles in vector resin, improve the physicals of the white film of producing with the made white master material of the present invention.But because its water-wet behavior, dispersing property is relatively poor in organic medium, wants to make the white polyester masterbatch of superior performance, must carry out the coupling agent surface treatment to the white pigment of processing through inorganic surfaces again.
Be used for white pigment is carried out one or more that inorganic surface treatment agent that inorganic surfaces processes can be selected from silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide, ferric oxide.Process by the inorganic surfaces to white pigment, having formed thickness on the white pigment surface is the inorganic coating layer of 3～15nm, inorganic integument can coat for the individual layer of silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide etc., also can be their multilayer coating structure, the total thickness of coating layer is 3～15nm.
The coupling agent surface treatment is exactly first selected coupling agent to be dissolved in the suitable solvent, adds and has carried out the pigment that inorganic surfaces is processed, and is controlled under the suitable condition and stirring, carries out coupling agent and coats.Coupling agent among the present invention can be selected from titanate coupling agent, silane coupling agent, phosphate coupling agent, boric acid ester coupler, organic complex or aluminic acid compound.
White pigment among the present invention can be selected from one or more in the titanium pigment that particle diameter is 10～5000nm, plumbous matter pigment, zinc matter pigment, weisspiessglanz, barium sulfate, the calcium carbonate.
Polyester among the present invention be by diprotic acid and dibasic alcohol by the polymkeric substance that polycondensation gets, comprise as diprotic acid: terephthalic acid, m-phthalic acid, phthalic acid, naphthalic acid, hexanodioic acid, SA etc.; Comprise as dibasic alcohol in addition: ethylene glycol, 1,3-PD, BDO, cyclohexanedimethanol etc.Can be by a kind of diprotic acid and a kind of dibasic alcohol polycondensation as the polyester of product and get, can be a kind of diprotic acid and several dibasic alcohol polycondensation and get, can also be by several diprotic acid and a kind of dibasic alcohol polycondensation and get.In the present invention, preferred polyethylene terephthalate.
Among the present invention, white pigment adds at polycondensation step, can improve the dispersing uniformity of pigment in polyester on the one hand, can control more expediently the final viscosity of colour batch on the other hand, is convenient to the granulation of masterbatch.White pigment adds fashionable, because polycondensation is also being carried out, the viscosity of system is in continuous variation, the viscosity of system is less, shows that the flowability of system is better, and it is easier that pigment disperses in system, but, the reduction of system viscosity, the shearing action decline to pigment, polymkeric substance is unfavorable for the refinement of pigment.Therefore, require white pigment add the viscosity of fashionable system can not be too high can not be too low, the present invention is selected from and adds the surface-treated pigment of operation (1) when system viscosity reaches 0.20dl/g～0.65dl/g, stops polycondensation when system viscosity reaches 0.50dl/g～0.70dl/g.
Among the present invention, the add-on of white pigment is preferably 20%～60% by with respect to 1%～70% of the theoretical output gross weight of synthetic masterbatch.
In order to detect the dispersing uniformity of pigment in masterbatch and the performance of the masterbatch that obtains of the inventive method, the masterbatch that the present invention is obtained and PET polyester slice are according to the 80:20(weight ratio) ratio mix, then melting, slab, membrane, the performance of test membrane.
The invention will be further described below in conjunction with specific embodiment.
Every 10L ethylene glycol is equivalent to about 180mol ethylene glycol in following examples, and every 10kg terephthalic acid is equivalent to the 60mol terephthalic acid.
Embodiment 1
(1) inorganic surfaces is processed: be that to coat thickness be 10nm left and right sides silicon-aluminium binary coating for titanium dioxide surface about 350nm at particle diameter.
Be to add sodium hexametaphosphate dispersant in 20%～30% the titanium dioxide slurries to massfraction, with pH be adjusted to about 9.5 carry out pre-dispersed. under 85～90 ℃ of conditions, the mass ratio of control silicon-dioxide and pigment is 1%～5%, transfer the pH=8.5 of solution with water glass, ageing 2 h finish the bag silicon fiml; On this basis, holding temperature is about 70 ℃, and pH value about 8.5 adds Tai-Ace S 150 and dilute sodium hydroxide, and the mass ratio that the stoichiometry of Tai-Ace S 150 is controlled at aluminium sesquioxide and titanium dioxide is 3%～7%.Regulate the pH to 7.0 of slurries with Tai-Ace S 150, ageing 4 h are washed to the sulfate radical-free ion, filter, and 100 ℃ of dryings obtain the titanium dioxide of silicon-aluminium binary coating.
(2) coupling agent surface treatment: the titanate coupling agent that will account for particle weight 3% is dissolved in the Virahol, the titanium dioxide granule behind the adding inorganic coating, and the mass ratio that adds the aqueous isopropanol of titanium dioxide amount and titanate coupling agent is about 1:4.Stir the 1.5h filtration drying, carry out 9～10h Soxhlet extraction, then drying for standby with isopropanol solvent again.
(3) 4.5L ethylene glycol is added in the reactor, then add the terephthalic acid that 10kg is mixed with antimony glycol, wherein the content of antimony glycol is about 0.03% of terephthalic acid weight; , be replaced and fill 170kPa nitrogen in the backward still air displacement in the reactor with nitrogen, then be heated to 230～250 ℃, carry out esterification under the condition that stirs, reacted 2～3 hours, esterification finishes;
(4) after esterification finishes, reactor is vacuumized, make the pressure in the reactor be lower than 60pa, keep simultaneously reactor temperature at 270～285 ℃, carry out polycondensation, when reaction system viscosity reaches the 0.45dl/g left and right sides, add in the reaction system the theoretical output gross weight 45% that is equivalent to product P ET, pass through the titanium dioxide that step (1) (2) is processed, proceed polycondensation.
(5) when reaction system viscosity reaches 0.60dl/g, stop polycondensation, through making silk, cooling, granulation, obtain the white polyester masterbatch.
Embodiment 2～12
With the method that is similar to embodiment 1, according to the pigment type described in the table 1, pigment particle size, pigment add-on, inorganic coating layer kind, inorganic coating layer thickness, coupling agent surface treatment agent kind, to add pigment be system viscosity, prepares the white master material of different viscosity.
Table 1: the material usage data table of each embodiment
Comparative Examples
(1) be that melting is carried out in 0.70dl/g left and right sides PET section with viscosity about 260 ℃, then add the particle diameter that is equivalent to melting PET gross weight 1% and be about 350nm and through with embodiment 1 in the titanium dioxide of step (1) (2) same treatment.Stir, disperse, then make silk, pelletizing.
The masterbatch that each embodiment and Comparative Examples are obtained and PET section are according to the 80:20(weight ratio) ratio mix then melting, slab, membrane, test performance.
Table 2: each embodiment performance test data
| Embodiment | The close value of light |
| 1 | 0.852 |
| 2 | 0.135 |
| 3 | 1.043 |
| 4 | 0.509 |
| 5 | 0.793 |
| 6 | 0.916 |
| 7 | 0.499 |
| 8 | 0.863 |
| 9 | 0.799 |
| 10 | 0.833 |
| 11 | 0.947 |
| 12 | 0.811 |
| Comparative Examples | 0.122 |
。When a beam intensity is I
0Illumination on film the time, except reflection, part light is stopped by wherein pigment particles and absorbs the remainder transmission.If transmitted light intensity is I
1, definition transmissivity (T) is:
T=I
1/I
0×100% (1)
The transmittancy of transmissivity reflection film, its inverse have then represented the ability that film stops light, are called light resistance rate (O):
O=1/T=I
0/I
1 (2)
The close value of the light of film (D) is defined as follows:
D=lgO=lgI
0/I
1 (3)
The close value of light is larger, and colo(u)rant dispersion is more even in the surface film, and finer particles is little.
Claims (6)
1. the preparation method of a white polyester masterbatch is characterized in that, described preparation method comprises following operation:
(1) surface treatment procedure of pigment:
A. the inorganic surfaces of pigment is processed:
Be that the pigment of 10～5000nm carries out surface treatment with inorganic surface treatment agent to particle diameter, coating thickness in surface of pigments is the inorganic coating layer of 3～15nm;
B. the coupling agent surface treatment of pigment:
The pigment that above-mentioned inorganic surfaces is processed carries out the coupling agent surface treatment;
(2) esterification step:
In conversion unit, add diprotic acid and dibasic alcohol, be filled with nitrogen, 230～250 ℃ of esterifications 2～3 hours;
(3) polycondensation step:
After above-mentioned esterification finishes, conversion unit is vacuumized, make the pressure in the equipment be lower than 60pa, keep simultaneously the interior temperature of conversion unit at 270～285 ℃, the beginning polycondensation, when the viscosity of system reaches 0.20dl/g～0.65dl/g, add the surface-treated pigment of operation (1), when system viscosity reaches 0.50dl/g～0.70dl/g, stop polycondensation;
(4) granulating working procedure
Polycondensation through making silk, cooling, granulation, obtains the white polyester masterbatch after stopping.
2. preparation method according to claim 1 is characterized in that, described inorganic surface treatment agent is one or more in silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide, the ferric oxide.
3. preparation method according to claim 1 is characterized in that, described pigment is one or more in titanium pigment, plumbous matter pigment, zinc matter pigment, weisspiessglanz, barium sulfate, the calcium carbonate.
4. according to claim 1 or 3 described preparation methods, it is characterized in that the particle diameter of described pigment is 10～5000nm.
5. preparation method according to claim 1 is characterized in that, described inorganic coating layer is individual layer coating layer or multilayer coating structure layer.
6. preparation method according to claim 1 is characterized in that, described coupling agent is titanate coupling agent, silane coupling agent, phosphate coupling agent, boric acid ester coupler, organic complex or aluminic acid compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210527232.3A CN103059519B (en) | 2012-12-10 | 2012-12-10 | A kind of preparation method of white polyester masterbatch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210527232.3A CN103059519B (en) | 2012-12-10 | 2012-12-10 | A kind of preparation method of white polyester masterbatch |
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| Publication Number | Publication Date |
|---|---|
| CN103059519A true CN103059519A (en) | 2013-04-24 |
| CN103059519B CN103059519B (en) | 2015-09-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210527232.3A Active CN103059519B (en) | 2012-12-10 | 2012-12-10 | A kind of preparation method of white polyester masterbatch |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552764A (en) * | 2003-12-19 | 2004-12-08 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania in situ |
| CN1552765A (en) * | 2003-12-19 | 2004-12-08 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania generated in situ |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552764A (en) * | 2003-12-19 | 2004-12-08 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania in situ |
| CN1552765A (en) * | 2003-12-19 | 2004-12-08 | 上海交通大学 | Method for preparing uvioresistant polyester by nanometer titania generated in situ |
Non-Patent Citations (1)
| Title |
|---|
| 洪范 等: "超声分散原位聚合法制备纳米TiO2/聚酯复合材料", 《东华大学学报（自然科学版）》, vol. 35, no. 5, 31 October 2009 (2009-10-31), pages 493 - 499 * |
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Effective date of registration: 20240314 Address after: 230041 Lekai Industrial Park, zone a, Xinzhan Industrial Park, Xinzhan District, Hefei City, Anhui Province Patentee after: HEFEI LUCKY SCIENCE & TECHNOLOGY INDUSTRY Co.,Ltd. Country or region after: China Patentee after: LUCKY HEALTHCARE CO.,LTD. Patentee after: Tianjin Lekai Film Technology Co.,Ltd. Address before: 230041 Lekai Industrial Park, zone a, Xinzhan Industrial Park, Xinzhan District, Hefei City, Anhui Province Patentee before: HEFEI LUCKY SCIENCE & TECHNOLOGY INDUSTRY Co.,Ltd. Country or region before: China Patentee before: BAODING LUCKY FILM Co.,Ltd. Patentee before: Tianjin Lucky Film Co.,Ltd. |