CN103059519B - A kind of preparation method of white polyester masterbatch - Google Patents
A kind of preparation method of white polyester masterbatch Download PDFInfo
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- CN103059519B CN103059519B CN201210527232.3A CN201210527232A CN103059519B CN 103059519 B CN103059519 B CN 103059519B CN 201210527232 A CN201210527232 A CN 201210527232A CN 103059519 B CN103059519 B CN 103059519B
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 23
- 229920000728 polyester Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000049 pigment Substances 0.000 claims abstract description 66
- 238000004381 surface treatment Methods 0.000 claims abstract description 39
- 239000007822 coupling agent Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 21
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 239000012756 surface treatment agent Substances 0.000 claims abstract description 10
- 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
- 239000012463 white pigment Substances 0.000 claims description 10
- 238000006243 chemical 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
- 238000000576 coating method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 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
- 239000011248 coating agent Substances 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
- -1 boric acid ester Chemical class 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
- 150000001875 compounds Chemical class 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
- 238000012423 maintenance Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 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
- 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
- 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
- 239000006185 dispersion Substances 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
- 238000003756 stirring Methods 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
- 230000000052 comparative effect 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
- 230000009467 reduction Effects 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
- 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect 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
- 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
- 230000008569 process 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
- 230000005641 tunneling Effects 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A preparation method for white polyester masterbatch, described method comprises the surface treatment procedure of (1) pigment: the inorganic surface treatment of a. pigment; B. the coupling agent surface treatment of pigment; (2) esterification step; (3) polycondensation step; (4) granulating working procedure.The inventive method does not need to carry out second melting to resin, and technique is simple, and production cost is low; By carrying out inorganic surface treatment and coupling agent surface treatment to pigment, and by control pigment add fashionable system viscosity and stop polycondensation time system viscosity, improve the dispersing uniformity of pigment at polyester, the final viscosity of colour batch can be controlled comparatively expediently.
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 producing a kind of important method of white polyester film, directly adding white master material method and being compared to the advantage that coating method and staining have its uniqueness, not only can reduce operation, reduce production cost; Reduce and cause the pollution to environment because using dyestuff; Substantially the viscosity fastness situation of dye (face) material that coating method or staining must be paid close attention to and counterdie need not be considered.
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, mix under melt temperature by pigment, auxiliary agent and the resin as carrier, through extruding, granulation and obtaining.There is following defect in this method: (1) needs vector resin melting again, and production process is complicated, and production cost is high; (2) because the resin viscosity as carrier is higher, cause the dispersion of pigment in resin uneven, cause colour batch streaking even, and then affect the homogeneity of white polyester film colourity; (3) vector resin viscosity after carrying out melting can decline, and the final viscosity of colour batch also can be different along with the difference of pigment add-on, and what cause the final viscosity of colour batch is difficult to control.
Summary of the invention
The technical problem to be solved in the present invention is the above-mentioned technical problem overcoming prior art existence, provides a kind of preparation method of white polyester masterbatch.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A preparation method for white polyester masterbatch, described preparation method comprises following operation:
1. the surface treatment procedure of pigment:
A. the inorganic surface treatment of pigment:
Carrying out surface treatment with inorganic surface treatment agent to the pigment that particle diameter is 10 ~ 5000nm, is the inorganic coating layer of 3 ~ 15nm at the coated thickness of surface of pigments;
B. the coupling agent surface treatment of pigment:
Coupling agent surface treatment is carried out to the pigment of above-mentioned inorganic surface treatment;
2. esterification step:
In conversion unit, add diprotic acid and dibasic alcohol, be filled with nitrogen, 230 ~ 250 DEG C of esterifications 2 ~ 3 hours;
3. polycondensation step:
After above-mentioned esterification terminates, conversion unit is vacuumized, make pressure in equipment lower than 60pa, temperature simultaneously in maintenance conversion unit is at 270 ~ 285 DEG C, start polycondensation, add the pigment that operation (1) is surface-treated when the viscosity of system reaches 0.20dl/g ~ 0.65dl/g, stop polycondensation when system viscosity reaches 0.50dl/g ~ 0.70dl/g;
4. granulating working procedure
Polycondensation through making silk, cooling, granulation, obtains white polyester masterbatch after stopping.
In aforesaid method, described inorganic surface treatment agent can be one or more in silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide, ferric oxide.
In aforesaid method, described pigment is one or more in titanium pigment, plumbous matter pigment, zinc matter pigment, weisspiessglanz, barium sulfate, calcium carbonate.
In aforesaid method, the particle diameter of described pigment is 10 ~ 5000nm.
In aforesaid method, described inorganic coating layer can be individual layer coating layer, also can be multilayer coating structure layer.
In aforesaid method, described coupling agent is titanate coupling agent, silane coupling agent, phosphate coupling agent, boric acid ester coupler, organic complex or aluminated compound.
Compared with prior art, tool of the present invention has the following advantages:
1. the inventive method does not need to carry out second melting to resin, and technique is simple, and production cost is low.
2. the present invention is by carrying out inorganic surface treatment and coupling agent surface treatment to pigment, and by control pigment add fashionable system viscosity and stop polycondensation time system viscosity, improve pigment polyester dispersing uniformity, the final viscosity of colour batch can be controlled comparatively expediently, facilitate the granulation of masterbatch.
Embodiment
In order to ensure the color evenness of the white polyester adopting white master material provided by the invention to prepare, need the colo(u)rant dispersion in masterbatch even.For ensureing that pigment is uniformly dispersed in masterbatch, the size of particles of selected pigment should be little as much as possible, but along with the reduction 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, cause pigment particles to disperse in vector resin uneven.Moreover, because pigment inherently not easily disperses in organic medium, make be uniformly dispersed the very difficulty of pigment in vector resin; Therefore, surface treatment must be carried out to it before pigment is added in vector resin, to improve the dispersing property of pigment in vector resin.
Usually following several method is had: inorganic surface treatment, coupling agent surface treatment, tensio-active agent surface treatment, hyper-dispersant surface treatment and rosined soap surface treatment etc. to the surface treatment of pigment.The present invention selects the method for inorganic surface treatment and coupling agent surface treatment to carry out surface treatment to pigment.
Inorganic surface treatment carries out surface treatment with inorganic surface treatment agent to pigment exactly, inorganic coating layer is formed in surface of pigments, reduce the reunion between pigment, improve the dispersing property of pigment particles in vector resin, the physicals of the white film that the made white master material of raising the present invention is produced.But due to its water-wet behavior, dispersing property is poor in organic medium, want the white polyester masterbatch of obtained superior performance, coupling agent surface treatment must be carried out again to the white pigment through inorganic surface treatment.
Inorganic surface treatment agent for carrying out inorganic surface treatment to white pigment can be selected from one or more in silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide, ferric oxide.By the inorganic surface treatment to white pigment, the inorganic coating layer that thickness is 3 ~ 15nm is defined on white pigment surface, inorganic integument can be that the individual layer of silicon-dioxide, aluminium sesquioxide, zirconium dioxide, zinc oxide etc. is coated, also can be their multilayer coating structure, the total thickness of coating layer be 3 ~ 15nm.
Coupling agent surface treatment is exactly first be dissolved in selected coupling agent in suitable solvent, then add the pigment carrying out inorganic surface treatment, controls under suitable conditions and stir, and it is coated to carry out coupling agent.Coupling agent in the present invention can be selected from titanate coupling agent, silane coupling agent, phosphate coupling agent, boric acid ester coupler, organic complex or aluminated compound.
White pigment in 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, calcium carbonate.
Polyester in the present invention is the polymkeric substance obtained by polycondensation by diprotic acid and dibasic alcohol, comprises 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.Polyester as product can be obtained by a kind of diprotic acid and a kind of dibasic alcohol polycondensation, can be a kind of diprotic acid and several dibasic alcohol polycondensation and obtain, can also be obtained by several diprotic acid and a kind of dibasic alcohol polycondensation.In the present invention, preferred polyethylene terephthalate.
In the present invention, white pigment adds at polycondensation step, can improve pigment dispersing uniformity in the polyester on the one hand, can control the final viscosity of colour batch more expediently on the other hand, be convenient to the granulation of masterbatch.White pigment adds fashionable, because polycondensation is also being carried out, the viscosity of system is in continuous change, the viscosity of system is less, and show that the mobility of system is better, it is easier that pigment disperses in system, but, the reduction of system viscosity, declines to the shearing action of pigment, polymkeric substance, is unfavorable for the refinement of pigment.Therefore, require white pigment add fashionable system viscosity can not 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.
In the present invention, the add-on of white pigment is relative to the theoretical output gross weight of synthesized masterbatch 1% ~ 70%, is preferably 20% ~ 60%.
In order to detect the performance of the masterbatch that the dispersing uniformity of pigment in masterbatch and the inventive method obtain, masterbatch the present invention obtained and PET polyester slice are according to 80:20(weight ratio) ratio mix, then melting, slab, membrane, the performance of test membrane.
Below in conjunction with specific embodiment, the invention will be further described.
In following examples, every 10L ethylene glycol is equivalent to about 180mol ethylene glycol, and every 10kg terephthalic acid is equivalent to 60mol terephthalic acid.
Embodiment 1
(1) inorganic surface treatment: particle diameter be the titanium dioxide surface of about 350nm coated on thickness be about 10nm silicon-aluminium binary coating.
Be add sodium hexametaphosphate dispersant in the titanium dioxide slurries of 20% ~ 30% to massfraction, solution ph is adjusted to about 9.5 carry out pre-dispersed. under 85 ~ 90 DEG C of conditions, the mass ratio controlling silicon-dioxide and pigment is 1% ~ 5%, the pH=8.5 of solution is adjusted with water glass, ageing 2 h, completes bag silicon fiml; On this basis, holding temperature is at about 70 DEG C, and pH value about 8.5, adds Tai-Ace S 150 and dilute sodium hydroxide, and it is 3% ~ 7% that the stoichiometry of Tai-Ace S 150 controls at the mass ratio of aluminium sesquioxide and titanium dioxide.Regulate the pH to 7.0 of slurries with Tai-Ace S 150, ageing 4 h, is washed to sulfate radical-free ion, and filter, 100 DEG C of dryings, obtain the titanium dioxide of silicon-aluminium binary coating.
(2) coupling agent surface treatment: be dissolved in Virahol by the titanate coupling agent accounting for particle weight 3%, adds the titanium dioxide granule after inorganic coating, and the mass ratio adding the aqueous isopropanol of titanium dioxide amount and titanate coupling agent is about 1:4.Stir 1.5h filtration drying, then carry out 9 ~ 10h Soxhlet extraction with isopropanol solvent, then drying for standby.
(3) add in reactor by 4.5L ethylene glycol, 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; With nitrogen by air displacement in reactor, be replaced in backward still and fill 170kPa nitrogen, be then heated to 230 ~ 250 DEG C, under the condition stirred, carry out esterification, react 2 ~ 3 hours, esterification terminates;
(4) after esterification terminates, reactor is vacuumized, make pressure in reactor lower than 60pa, keep reactor temperature at 270 ~ 285 DEG C simultaneously, carry out polycondensation, when reaction system viscosity reaches about 0.45dl/g, add in reaction system be equivalent to the theoretical output gross weight 45% of product P ET, through the titanium dioxide that step (1) (2) process, proceed polycondensation.
(5) when reaction system viscosity reaches 0.60dl/g, stopping polycondensation, through making silk, cooling, granulation, obtaining white polyester masterbatch.
Embodiment 2 ~ 12
By the method being similar to embodiment 1, according to the pigment type described in 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 amounts data sheet of each embodiment
Comparative example
(1) be that about 0.70dl/g PET section carries out melting at about 260 DEG C by viscosity, then add the particle diameter being equivalent to melting PET gross weight 1% and be about 350nm and pass through the titanium dioxide with step (1) (2) same treatment in embodiment 1.Stir, disperse, then make silk, pelletizing.
The masterbatch each embodiment and comparative example obtained is cut into slices according to 80:20(weight ratio with PET) ratio mix, then melting, slab, membrane, test performance.
Table 2: each embodiment performance test data
。When a beam intensity is I
0illumination on film time, except reflection except, some light by wherein pigment particles stop and absorb, 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 then represents the ability of film barrier light, is called light resistance rate (O):
O=1/T=I
0/I
1(2)
The close value of light (D) of film is defined as follows:
D=lgO=lgI
0/I
1(3)
The close value of light is larger, and in surface film, colo(u)rant dispersion is more even, and finer particles is little.
Claims (5)
1. a preparation method for white polyester masterbatch, is characterized in that, described preparation method comprises following operation:
(1) surface treatment procedure of pigment:
A. the inorganic surface treatment of pigment:
Carrying out surface treatment with inorganic surface treatment agent to the pigment that particle diameter is 10 ~ 5000nm, is the inorganic coating layer of 3 ~ 15nm at the coated thickness of surface of pigments;
B. the coupling agent surface treatment of pigment:
Coupling agent surface treatment is carried out to the pigment of above-mentioned inorganic surface treatment;
(2) esterification step:
In conversion unit, add diprotic acid and dibasic alcohol, be filled with nitrogen, 230 ~ 250 DEG C of esterifications 2 ~ 3 hours;
(3) polycondensation step:
After above-mentioned esterification terminates, conversion unit is vacuumized, make pressure in equipment lower than 60pa, temperature simultaneously in maintenance conversion unit is at 270 ~ 285 DEG C, start polycondensation, add the pigment that operation (1) is surface-treated when the viscosity of system reaches 0.20dl/g ~ 0.65dl/g, stop polycondensation when system viscosity reaches 0.50dl/g ~ 0.70dl/g;
(4) granulating working procedure
Polycondensation through making silk, cooling, granulation, obtains white polyester masterbatch after stopping;
Described pigment is one or more in titanium pigment, plumbous matter pigment, zinc matter pigment, weisspiessglanz, barium sulfate, calcium carbonate;
The add-on of described white pigment is relative to synthesized masterbatch output gross weight 1% ~ 70%.
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, ferric oxide.
3. preparation method according to claim 2, is characterized in that, the particle diameter of described pigment is 10 ~ 5000nm.
4. preparation method according to claim 3, is characterized in that, described inorganic coating layer is individual layer coating layer or multilayer coating structure layer.
5. preparation method according to claim 4, is characterized in that, described coupling agent is titanate coupling agent, silane coupling agent, phosphate coupling agent, boric acid ester coupler, organic complex or aluminated compound.
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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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2012
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| 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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| 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)》.2009,第35卷(第5期),第493-499页. * |
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