CN102250401B - Preparation method of high whiteness and high density polyethylene - Google Patents
Preparation method of high whiteness and high density polyethylene Download PDFInfo
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Abstract
The invention provides a preparation method of high whiteness and high density polyethylene. The preparation method comprises the following steps: a, providing a premix of a high density polyethylene base material and an assistant system which accounts for 0.18-0.20 wt% of the high density polyethylene base material, wherein the assistant system comprises an antioxidant, a processing assistant, a metal ion passivant, and a fluorescent whitening agent, the antioxidant comprises a main antioxidant 1,3,5-tri(3,5-ditertiarybutyl-4-hydroxybenzyl)isocyanuric acid and an auxiliary antioxidant distearyl thiodipropionate, the processing assistant is a zinc calcium stearate with a weight ratio of zinc stearate to calcium stearate of 1:0.95-1:1.05, and the metal ion passivant is a polyhydroxy alcohol metal ion passivant; and b, carrying out twin screw extrusion on the premix to obtain the high whiteness and high density polyethylene.
Description
Technical field
The present invention relates to a kind of poly preparation method, relate more specifically to a kind of preparation method of high whiteness high density polyethylene(HDPE).Again particularly, the present invention relates to a kind of high chromium series high density polyethylene(HDPE) product priming color of carrying, improve its in extrusion process repeatedly colour stability so that the preparation method that can be repeatedly used.
Background technology
The easy flavescence of polyolefin products, reason is many-sided, both at home and abroad existing many bibliographical informations.
On the one hand, high density polyethylene(HDPE) (HDPE) product is at its synthetic, as to store and process and finally use stages, owing to be subjected to the effect of the environmental factorss such as light, heat, oxygen, produce the chemical reaction of hinge or degraded, make slowly flavescence of material color, serious meeting causes the mechanical properties such as shock strength, tensile strength and elongation significantly to descend, thereby affects the normal use of material.Add oxidation inhibitor and processing stabilizers etc. and can delay the oxidation of polymkeric substance in the course of processing, help to control the color of polymkeric substance.Yet, kind, especially some hindered phenol antioxygens of adding oxidation inhibitor, the interaction between its oxidation inhibitor and their oxidation products, such as quinones etc., normally coloured material, the flavescence of the polymer materials that can cause equally.
On the other hand, residual metal ions such as Cr, Ti in the polyolefin products, usually can make polymkeric substance store or the course of processing in variable color more serious.Usually, the more polyolefine of residual Cr metal ion is the high density polyethylene(HDPE) product for the chromium with vapor phase process production.The metal ions such as Cr, Ti residual in hindered phenol antioxygen meeting and the resin react, and form coloured inner complex, make the product colour jaundice.Although the development along with the polyolefin polymerization process technology, the residual quantity that the minimizing gold in resin belongs to material has become possibility, and still, the activity of metal residue is eliminated in the agent of choice for use metallic ion passivation, thereby improve the color (whiteness) of resin, remain at present general method.
And white dyes is because its superior fluorescent brightening effect, good thermostability, and addition characteristics seldom have been widely used in polyolefin field.After it absorbs sightless UV-light, be converted to the long blueness of wavelength or the visible light of purple, thereby can compensate undesired yellow in the matrix, thereby make the whiter, brighter of plastics change.For this reason, can improve by white dyes the whiteness of resin.
At present existing patent documentation has openly been described by collaborative Hinered phenols primary antioxidant, the agent of phosphorous acid salt auxiliary antioxidant, processing aid Zinic stearas, metallic ion passivation agent and the white dyes etc. of using, and improves the method for polyethylene product priming color.But the amplitude that its whiteness improves still has certain limitation, and also being difficult to be applicable to chromium is the high density polyethylene(HDPE) product that vapor phase process is produced.
In sum, this area lacks a kind of preparation method of high whiteness high density polyethylene(HDPE).Therefore, high chromium series high density polyethylene(HDPE) product priming color can be carried in the urgent need to developing a kind of preparation method of high whiteness high density polyethylene(HDPE) in this area, improve its in extrusion process repeatedly colour stability in order to can be repeatedly used.
Summary of the invention
The first purpose of the present invention is to obtain a kind of preparation method of high whiteness high density polyethylene(HDPE), can carry high chromium series high density polyethylene(HDPE) product priming color, improve its in extrusion process repeatedly colour stability in order to can be repeatedly used.
The second purpose of the present invention is to obtain a kind of high whiteness high density polyethylene(HDPE), can carry high chromium series high density polyethylene(HDPE) product priming color, improve its in extrusion process repeatedly colour stability in order to can be repeatedly used.
The 3rd purpose of the present invention is to obtain adjuvant system in the application of the whiteness that improves the high density polyethylene(HDPE) base-material.
In a first aspect of the present invention, a kind of preparation method of high whiteness high density polyethylene(HDPE) is provided, said method comprising the steps of:
(a) degree of providing high density polyethylene(HDPE) base-material and the Preblend that accounts for described polyethylene base-material 0.18-0.20 % by weight adjuvant system, described adjuvant system comprises oxidation inhibitor, processing aid, metallic ion passivation agent and white dyes;
Described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is 1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, and molecular formula is: C
48H
69N
3O
6, structural formula is:;
Described auxiliary antioxidant is the two stearyl alcohol esters of thio-2 acid, and molecular formula is: C
42H
82O
4S, structural formula is:
Described processing aid is that the part by weight of Zinic stearas and calcium stearate is 1: 0.95～1: 1.05 in zinc calcium stearate processing aid and the described processing aid;
Described metallic ion passivation agent is polyhydroxy-alcohol metalloid ion passivator,
(b) twin-screw extrusion is carried out in described Preblend, obtain described polyethylene.
In a specific embodiment of the present invention, in the described oxidation inhibitor, the part by weight of primary antioxidant and auxiliary antioxidant is 1: 1.67 ± 0.167.
In a preference, the consumption of described primary antioxidant is 300 ± 30ppm; Auxiliary antioxidant 500 ± 50ppm, described processing aid 1000 ± 100ppm; Metallic ion passivation agent 50 ± 5ppm; Fluorescent whitening agent OB 5 ± 2ppm.
In a specific embodiment of the present invention, the proportioning of described oxidation inhibitor and processing aid is: 1: (1.25 ± 0.125).
In a specific embodiment of the present invention, described polyhydroxy-alcohol metalloid ion passivator is glycerol.
In a specific embodiment of the present invention, described white dyes is benzoxazoles thiophene-based white dyes (for example Ciba company produces OB).
In a preference, described white dyes is selected from the OB product that vapour Bagong department (Ciba), BASF AG (Basf), Bayer AG (Bayer), Jin Hai Albemarle Corporation (Alblend) and Nanjing Ge Ruiluo Science and Technology Ltd. produce.
In a specific embodiment of the present invention, the twin-screw extrusion processing temperature of described step (b) is that 210 ± 5 ℃, screw speed are 300 ± 5rpm/min.
In a specific embodiment of the present invention, described step (b) adopts rotating Vortex meshed double screw extrusion equipment to carry out twin-screw extrusion.
In a preference, adopt high speed rotating Vortex extruding machine with two screw rods engaging.
In a specific embodiment of the present invention, the rate of feeding of twin screw extruder is 0.75 ± (0.01) Hz (hertz).
The high whiteness high density polyethylene(HDPE) that a second aspect of the present invention provides a kind of method of the present invention to make, its initial yellowness index is-12～-14, and the b value is-5～-6; Extrude rear yellowness index for 5 times-9～-11, the b value is-4～-5; (bioassay standard ASTM E313-00); Density is at 949kg/m
3-953kg/m
3(bioassay standard GB/T 1033.2-2010).
A third aspect of the present invention provides the application of a kind of adjuvant system in the whiteness that improves the high density polyethylene(HDPE) base-material,
Described adjuvant system comprises oxidation inhibitor, processing aid, metallic ion passivation agent and white dyes;
Described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is 1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, and molecular formula is: C
48H
69N
3O
6, structural formula is:
Described auxiliary antioxidant is the two stearyl alcohol esters of thio-2 acid, and molecular formula is: C
42H
82O
4S, structural formula is:
Described processing aid is that the part by weight of Zinic stearas and calcium stearate is 1: 0.95～1: 1.05 in zinc calcium stearate processing aid and the described processing aid;
Described metallic ion passivation agent is polyhydroxy-alcohol metalloid ion passivator.
Description of drawings
Fig. 1 is the performance map of embodiments of the invention 1～4.YI refers to the yellowness index of product among the figure, is obtained by the HunterLab instrument test.YI or b* value are less, show that product colour is whiter.
Embodiment
The inventor in order to improve whiteness, by improving preparation technology, has obtained a kind of adjuvant system of high density polyethylene(HDPE) through extensive and deep research, and it is excellent especially to be surprised to find that its whiteness when adopting twin-screw extrusion improves.Finished on this basis the present invention.
Herein, " high whiteness " refers to have lower yellowness index.For example the yellowness index of product reduces more than 200% than high density polyethylene(HDPE) product traditional on the market; After extruding for 5 times on the twin screw extruder product yellowness index than market on the priming color of traditional high density polyethylene(HDPE) product also low more than 100%.Described yellowness index can be measured by this area standard method.Concrete example as, on the HunterLab testing tool, be worth (yellowness index) and b value based on color measurenent L (lightness) value, YI (Yellow Index) in the three-dimensional rectangle space of opposition color theory.
Herein, " high density polyethylene(HDPE) " refers to that a kind of high-crystallinity by the ethylene copolymer generation, density are at 0.940g/cm
3More than, nonpolar thermoplastic polyolefin resin.
Herein, " ppm " refers to weight percent.
Below describe in detail to various aspects of the present invention: unless otherwise defined or explanation, same meanings that all specialties used herein and scientific words and those skilled in the art are familiar with.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Adjuvant system
The invention provides a kind of preparation method and prepared high whiteness high density polyethylene(HDPE) thereof of high whiteness high density polyethylene(HDPE), said method comprising the steps of:
Described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is 1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, and molecular formula is: C
48H
69N
3O
6, structural formula is:
Described auxiliary antioxidant is the two stearyl alcohol esters of thio-2 acid, and molecular formula is: C
42H
82O
4S, structural formula is:
Described processing aid is that the part by weight of Zinic stearas and calcium stearate is 1: 0.95～1: 1.05 in zinc calcium stearate processing aid and the described processing aid;
Described metallic ion passivation agent is polyhydroxy-alcohol metalloid ion passivator.
Oxidation inhibitor
Described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant, and wherein primary antioxidant is selected from Irganox3114, chemistry is by name: 1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, molecular formula is: C
48H
69N
3O
6, structural formula is:
Described auxiliary antioxidant is DSTDP, and chemistry is by name: the two stearyl alcohol esters of thio-2 acid, molecular formula is: C
42H
82O
4S, structural formula is:
Preferably, primary antioxidant is selected from Irganox3114, and auxiliary antioxidant is selected from DSTDP, and the two part by weight is 1: 1.67 ± 0.167.
Preferably, the proportioning of described oxidation inhibitor and processing aid is: 1: 1.25 ± 0.125.
Processing aid
Described processing aid is that the part by weight of Zinic stearas and calcium stearate is 1: 0.95～1: 1.05 in zinc calcium stearate processing aid and the described processing aid.
Hinered phenols primary antioxidant Irganox1010 and Irganox10103114, phosphorous acid salt auxiliary antioxidant class Irgaphos168, Ultranox626, Doverphos9228 etc. are main and auxiliary oxidation inhibitor relatively more commonly used in the polyolefin industry.In fact; another kind of oxidation inhibitor; monothioester kind antioxidant DSTDP or DSTP (stearic bicine diester base thiobis propionic acid fat); because it has good decompose hydroperoxide function; in polyethylene when being subjected to that the phenols primary antioxidant is collaborative to be used; the long-acting thermal-oxidative aging property of better thermo-oxidative stability can be provided in resin treatment and storage process, make the polyvinyl resin color more inhibited from yellowing.Metallic stearates has been widely used in the high density polyethylene(HDPE) product as acid neutralizing agent and inside and outside lubricant owing to having excellent performance.And it also helps the stable of polyethylene product and improves the color of polyethylene product.The selection of acid neutralizing agent can determine the color that polyvinyl resin is final, thereby has affected the reaction of many organic compositions in the system because acid neutralizing agent has changed the acidity in the polymkeric substance.Therefore other materials are evaded or impurity and the stabilization of polymer of these polymkeric substance the insides that neutralize are very important by adding.Different stearate or its are collaborative, are different to the contribution of polyethylene product color, so, select suitable processing aid also extremely important to the color of improving high-density polyethylene resin.
The metallic ion passivation agent
Described metallic ion passivation agent is polyhydroxy-alcohol metalloid ion passivator.
Preferably, described polyhydroxy-alcohol metalloid ion passivator is glycerol.
Can described polyhydroxy-alcohol metalloid ion passivator be 2?-6? the C3 of individual hydroxyl?-C10? alkyl alcohol.
White dyes
Preferably, described white dyes is benzoxazoles thiophene-based white dyes.
More preferably, described white dyes is selected from the OB product that vapour Bagong department (Ciba), BASF AG (Basf), Bayer AG (Bayer), Jin Hai Albemarle Corporation (Alblend) and Nanjing Ge Ruiluo Science and Technology Ltd. produce.OB (Ciba) most preferably.
Twin-screw extrusion
Preferably, the twin-screw extrusion processing temperature of described step (b) is that 210 ± 5 ℃, screw speed are 300 ± 5rpm/min.
Preferably, described step (b) adopts rotating Vortex meshed double screw extrusion equipment to carry out twin-screw extrusion.
In a preference, adopt high speed rotating Vortex extruding machine with two screw rods engaging.
Preferably, is rate of feeding 0.75 ± 0.01Hz (hertz)?
In addition, the machined parameters of twin screw extruder, especially processing temperature, screw speed and repeatedly rate of feeding in the extrusion etc., directly affect the states such as conveying, melting and mixing of material (solid and melt) in twin screw, thereby affect shear viscosity, shearing rate and the shear-stress etc. of material in screw rod and machine barrel, the color of resin is produced very large impact.So, in selected twin screw screw combinations situation, obtain the high-density polyethylene resin of high whiteness, the extrusion parameter of control twin screw extruder is extremely important.
The high density polyethylene(HDPE) base-material
High density polyethylene(HDPE) base-material among the present invention is commercially available.For example can adopt the chromium-based catalysts based on metal A l improvement, as comonomer, adopt pentane and nitrogen to prepare as the vapor phase process reaction process of inert component with hexene-1.In the reaction process, satisfy the index request of polymerization product by the relative proportion of adjusting reactant: the temperature by the control gas-phase fluidized-bed reactor obtains desirable melting index, by adjusting comonomer the dividing potential drop of ethene is recently controlled the density of polyethylene product, control suitable output by the rate of injection of regulating catalyzer.Simultaneously, activity by the control catalyzer, conditioned reaction device pressure, discharging speed and the reactor fluidisation bed bed height of control polymkeric substance, the parameters such as the mass rate of the Pressure Drop of grid distributor, fluidizing agent and subsequent reactor fluidisation speed in the adjustment reactor, control the speed of polyreaction, control the state of aggregation of polymkeric substance, in reactor, produce the polyethylene product of specific product structure.
The high whiteness high density polyethylene(HDPE) that method of the present invention makes, its initial yellowness index be-12～-14, and the b value is-5～-6, extrudes rear yellowness index-9～-11 5 times, and the b value is-4～-5; Density is at 949kg/m3-953kg/m3.
The present invention is by further optimizing the collaborative of major and minor oxidation inhibitor, select more suitably processing aid and metallic ion passivation agent, by with the combination of white dyes, under specific twin screw processing conditions, obtain the high-density polyethylene resin product of higher whiteness, overcome the defective of prior art.
In a specific embodiment of the present invention, the oxidation inhibitor Preblend system that contains auxiliary antioxidant DSTDP, 1000ppm zinc calcium stearate processing aid (zinc calcium ratio is 1: 1), 50ppm metallic ion passivation agent glycerol and the 5ppm fluorescent whitening agent OB of 300ppm primary antioxidant Irganox3114,500ppm by use, select high speed rotating Vortex extruding machine with two screw rods engaging, control twin-screw extrusion processing temperature be 210 ℃, when screw speed is 300rpm/min, chromium is that the high density polyethylene(HDPE) product has best priming color; The control rate of feeding is when being 0.75Hz, and system is through having best colour stability behind the compound extruded several times, and the hold facility of color is greatly improved.
Technical scheme of the present invention has following advantage:
The present invention not only has novelty technically, and product performance are superior; Simultaneously, capable of reducing energy consumption in manufacturing process, economize in raw materials, have great environmental and social benefits.The product that the present invention is prepared compared with prior art, has following advantage:
(1) technological innovation:
Developed a kind of novel high-density polyethylene product improvement in performance technology, by conditioned reaction device parameter, the optimizing product molecular weight distribution has obtained a kind of polyethylene product with unique products structural form.
(2) product performance:
1. product has good whiteness, and yellowness index reduces more than 200% than high density polyethylene(HDPE) product traditional on the market.
2. product has good anti-yellowing effect in the course of processing, after extruding for 5 times on the twin screw extruder product yellowness index than market on the priming color of traditional high density polyethylene(HDPE) product also low more than 100%.
(3) economic benefit:
1. the effect of product high resistance xanthochromia in the course of processing can improve the ratio of using feed back, the about 100-300 RMB/ of unit of the cost that economizes in raw materials ton.
2. the product innovation cocoa reduces downstream client's process-cycle, enhances productivity.
(4) social benefit:
1. easily reuse, can increase the number of times that recycles, improve the energy utilising efficiency, reduce production costs and reduce to greatest extent the plastics pollution on the environment, have the significance of low-carbon (LC), Sustainable development and protection of the environment resource.
Specify such as nothing, various raw materials of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Other aspects of the present invention are because the disclosure of this paper is apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Embodiment
The oxidation inhibitor Preblend system that contains auxiliary antioxidant DSTDP, 1000ppm zinc calcium stearate processing aid (zinc calcium ratio is 1: 1), 50ppm metallic ion passivation agent glycerol and the 5ppm fluorescent whitening agent OB of 300ppm primary antioxidant Irganox3114,500ppm by use, select high speed rotating Vortex extruding machine with two screw rods engaging, control twin-screw extrusion processing temperature be 210 ℃, when screw speed is 300rpm/min, chromium is that the high density polyethylene(HDPE) product has best priming color; The control rate of feeding is when being 0.75Hz, and system is through having best colour stability behind the compound extruded several times, and the hold facility of color is greatly improved.
Press the ISO1133 method, 190 ℃ of temperature, under the pressure 21.6Kg condition, recording its melt flow rate (MFR) is 5-16.0g/10min, and the melt flow rate (MFR) of recommendation is 8-11g/10min, and the density of recommendation is 949-953kg/m3.
Add the component by following proportioning in the polyethylene matrix that more than makes, granulation is extruded under suitable twin screw extruder processing conditions, produces the finished product.The high-density polyethylene resin of anti-yellowing change in a kind of high whiteness of the present invention, the course of processing, component and weight comprise:
Said polyvinyl resin is for producing with gas-phase fluidized bed polymerization process, chromium-based catalysts, and density is 949-953kg/m3, and melting index is 8-11g/min, and hexene-1 is the high-density polyethylene resin of comonomer.
Said oxidation inhibitor A mainly refers to the oxidation inhibitor of hindered phenol.Be selected from four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, commodity are called Irganox1010, with 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, a kind of among the commodity Irganox3114 by name provided by Jin Hai Albemarle Corporation.The preferred Irganox3114 that uses is because it has than the better processing stability energy of Irganox1010 and long-acting thermal oxidation stability performance.Suitable interpolation concentration range is 300-600ppm, and the interpolation concentration range of recommendation is 300ppm.
Said oxidation inhibitor B comprises different types, mainly contain the phosphorous acid salt, be selected from three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, commodity Irganox168 by name and thiosulfates, be selected from thio-2 acid 2 stearyl ester, a kind of among commodity DSTDP by name or the DSTP provided by Jin Hai Albemarle Corporation.The preferred DSTDP that uses because it has good decompose hydroperoxide function, when being subjected to that the phenols primary antioxidant is collaborative to be used, can provide the long-acting thermal-oxidative aging property of better thermo-oxidative stability in resin treatment and storage process in polyethylene.Suitable interpolation concentration range is 300-800ppm, and the working concentration of recommendation is 500ppm.
Said processing aid is selected from a kind of in calcium stearate and the Zinic stearas or two kinds, and (Ciba) company provides by the gas bar.Calcium stearate and Zinic stearas all are white in color Powdered.Calcium stearate also can improve the colour stability of system, but poor than Zinic stearas of successful.When adding the zinc calcium stearate combination, system can obtain more excellent hue preserving ability.Preferred Zinic stearas and the calcium stearate synergistic combination that cooperates at 1: 1 of using, suitable interpolation concentration range is 500ppm-1000ppm, the working concentration scope of recommendation is 1000ppm.
Said metallic ion passivation agent is selected from a kind of in polyoxyethylene glycol and the glycerol or two kinds.The molecular weight polyethylene glycol that the present invention uses is about 8000.Glycerol is commercially available analytical reagent.Because glycerol is thick liquid, for guaranteeing its dispersion effect, use after should making first master batch.Preferential recommendation glycerol is because the kish element in the more effective passivation polyethylene catalysts of more oh group energy in the glycerol.Suitable suitable interpolation concentration range is 50ppm-200ppm, and the working concentration of recommendation is 50ppm.
Said white dyes is two (the 5-tertiary butyl-2-benzoxazolyl) thiophene of 2,5-, and commodity are called OB, and department provides by the vapour Bagong.Because the white dyes add-on is few, should dilute rear use with the polyethylene matrix to it first, guarantee its in whole polyethylene and other additive system, thoroughly be uniformly dispersed (agglomeration can not be arranged).
The main and auxiliary oxidation inhibitor that more than uses in the invention can be one-component, also can be to mix composite component.For reaching more homodisperse purpose, preferentially use composite antioxidant component.
The twin screw extruder that uses among the present invention is TSE-24TC as high speed rotating Vortex extruding machine with two screw rods engaging, model, screw diameter 24cm, and length-to-diameter ratio (L/D) is 25: 1.For selected screw combinations, the temperature of twin screw extruder and rotating speed, repeatedly the rate of feeding in the extrusion etc. directly affects shear viscosity, shearing rate and the shear-stress of material in screw rod and machine barrel, and the color of product is produced very large impact.
Owing to add glycerol in the material, and the boiling point of glycerol is about 180 ℃, need in the course of processing needs the processing temperature of control material.Guaranteeing that material has in the situation of good plasticizing, lower processing temperature can cause product that whiter color is arranged.Find in the experiment, when processing temperature surpasses 230 ℃, die head at twin screw extruder finds to have the situation of smoldering, excess Temperature, the structure of glycerol in material changed, can weaken glycerol in the material to the passivation effect of residual Cr and Ti ion, finally cause polyethylene product color variation.
For specific twin screw extruder, after screw combinations is selected, for dispersing and mixing, there is the process of two competitions: 1, diffusion controlled process.Comprise: (1), screw speed reduce, and residence time of material is elongated, and it is even to be conducive to diffusive mixing; (2), temperature raises, rate of diffusion is accelerated, it is even to be conducive to equally diffusive mixing.2, shear control process.Shear-stress=melt viscosity * shearing rate comprises: (1), screw speed increase, and shearing rate increases thereupon, and shear-stress is increased, and it is even to be conducive to shear the control dispersing and mixing; (2), barrel zone temperature reduces, and causes that melt viscosity raises, and shear-stress is increased, it is even to be conducive to shear the control dispersing and mixing.So the selection of screw speed, barrel zone temperature and rate of feeding directly affects shearing rate, viscosity, output and material the residence time screw rod in of material in screw rod etc., the color of final product is also had a great impact.Because high-shear screw combinations or raising screw speed although shortened the residence time of material in screw rod, have aggravated frictional heat simultaneously, cause that temperature raises, reduced viscosity, cause shear-stress to reduce, namely shear shinning.Screw speed is excessively low, although frictional heat is little, temperature variation is little, and the residence time of material in screw rod lengthens, and makes the color variation of material.DSTDP is a kind of monothioester kind antioxidant, and crosslinked easily in the course of processing, too high rate of feeding can improve its crosslinking degree.For DSTDP oxidation inhibitor, when it and Hinered phenols antioxidant synergy, when twin screw was repeatedly extruded, low rate of feeding can reduce the fluctuation of forcing machine when work, is conducive to the stable of product colour, and also can improve to a certain extent the color of product.Said twin-screw extrusion condition among the present invention, such as processing temperature, screw speed and rate of feeding etc., suitable use range comprises: 180 ℃-230 ℃ of processing temperatures; Screw speed 100-400r/min; Rate of feeding 0.70Hz-0.80Hz, the working conditions of recommendation is: 210 ℃ of processing temperatures, screw speed 300r/min, rate of feeding 0.75Hz.
The finished product of the present invention, form with pellet is directly tested with Hunter Lab tester, testing method is ASTM E313-00 with wherein yellowness index (YI) or b* value as the standard of estimating product colour Bai Yuhuang, and YI or b* value are less, show that product colour is whiter.
In following examples, prepare as follows first glycerol powder parent: at a high speed mixed sample device, add 3kg high density polyethylene(HDPE) powder matrix and 3g fluorescent whitening agent OB, cover tightly lid, with the speed high-speed mixing of 300rpm/mi n one minute, be dispersed in the polyethylene matrix with making the fluorescent whitening agent OB uniform and complete.Keep at a high speed mixed sample device not stop to stir, extract 25ml glycerol solvent with injection needle tube, slowly be injected on the filtering net at a high speed mixed sample device top, glycerol solvent on the filtering net enters in the compound sample of polyethylene powder and white dyes by strenuous vibration and the action of gravity of instrument, 25ml glycerol reagent is controlled to inject within one minute and finishes, keep at a high speed mixed sample device to continue to stir and reduce mixed sample device stirring velocity after 2 minutes to 50rpm/min, continue stirring and stop after 10 minutes, make glycerol powder parent.The glycerol that contains fluorescent whitening agent OB and the 10000ppm of 1000ppm in the powder parent of gained.
Preparation gathers hexylene glycol powder parent as follows: add 3kg high density polyethylene(HDPE) powder matrix and 3g fluorescent whitening agent OB at a high speed mixed sample device, cover tightly lid, with the speed high-speed mixing of 300rpm/min one minute, be dispersed in the polyethylene matrix with making the fluorescent whitening agent OB uniform and complete.And then the polyoxyethylene glycol of adding 3g, keep original mixing velocity to continue to stir after 2 minutes and stop, making polyoxyethylene glycol powder parent.Contain the fluorescent whitening agent OB of 1000ppm and the polyoxyethylene glycol of 1000ppm in the powder parent of gained.
Among following table 1 embodiment, produce with gas fluidized-bed process, employing chromium-based catalysts, 190 ℃ of temperature, under the pressure 21.6Kg condition, melt flow rate (MFR) is 5-16.0g/10min, and density is 949-953kg/m3, the high density polyethylene(HDPE) product of hexene-1 copolymerization is as base resin, add the powder parent of main and auxiliary oxidation inhibitor, processing aid, metallic ion passivation agent and white dyes after the metering, high-speed mixing is even, extruding pelletization under specific twin screw extruder condition.Commodity 1 have the industrial use similar with the present invention with commodity 2, and product is bought gained from general marketplace.Directly test sample of pellets with Hunter Lab tester, measure its yellowness index (YI) and b* value according to ASTM E313-00 method, YI and b* value are the smaller the better, and the outward appearance of illustrative material is more and more whiter.
Specific examples is seen such as following table 1:
Table 1
Table 1 is continuous
Table 1 is continuous
In example 1, example 2, example 3 and the example 4, fixedly the twin screw extruder condition is as follows: 300 ℃ of processing temperatures, and screw speed 150r/min, rate of feeding 0.75Hz has investigated processing aid Zinic stearas and calcium stearate to the impact of high density polyethylene(HDPE) color.Therefrom can find out, chromium is in the high density polyethylene(HDPE), use separately the anti-yellowing effect of processing aid Zinic stearas to be better than the calcium stearate that independent usage quantity equates, and the anti-yellowing effect of collaborative use Zinic stearas and calcium stearate (total amount is 0.1% weight unit) is better than using separately the anti-yellowing effect of Zinic stearas (total amount is 0.1% weight unit).
Example 4--example 6 has been investigated in the 3114/DSTDP antioxidant systems, and 3114 and DSTDP of different concns extrudes rear impact on product colour for many times.
Example 7--example 10 has been investigated 3114/DSTDP/ZnST/CaST=300: in 500: 500: 500 antioxidant systems, add the glycerol metallic ion passivation agent of different concns and repeatedly extrude rear impact on product colour.
Example 11--example 12 has been investigated 3114/DSTDP/ZnST/CaST=300: in 500: 500: 500 antioxidant systems, add the polyoxyethylene glycol metallic ion passivation agent of different concns and repeatedly extrude rear impact on product colour.
Example 13--example 20, investigated 3114/DSTDP/ZnST/CaST/ glycerol/OB=300: 500: 500: 500: in 50: 5 antioxidant systems, different twin-screw extrusion condition (processing temperature, screw speed and rate of feeding) is on the impact of product colour.
Example 21--example 23 is the comparative example of 1010/168/ZnST/CaST/ glycerol/OB system and invention formula for a product.
Example 24--example 27 is the comparative example of 3114/168/ZnST/CaST/ glycerol/OB system and invention formula for a product.
Example 28--example 31 is the comparative example of 1010/DSTDP/ZnST/CaST/ glycerol/OB system and invention formula for a product.
The above only is preferred embodiment of the present invention, be not to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (5)
1. the preparation method of a high whiteness high density polyethylene(HDPE) is characterized in that, said method comprising the steps of:
(a) provide the Preblend of high density polyethylene(HDPE) base-material and adjuvant system, described adjuvant system comprises oxidation inhibitor, processing aid, metallic ion passivation agent and white dyes; Described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant, and the parts by weight of each component are as follows:
Wherein primary antioxidant is 1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, and molecular formula is: C
48H
69N
3O
6, structural formula is:
Described auxiliary antioxidant is the two stearyl alcohol esters of thio-2 acid, and molecular formula is: C
42H
82O
4S, structural formula is:
Described processing aid is that the part by weight of Zinic stearas and calcium stearate is 1:0.95～1:1.05 in Zinic stearas and calcium stearate hybrid process auxiliary agent and the described processing aid;
Described metallic ion passivation agent is polyhydroxy-alcohol metalloid ion passivator, and described polyhydroxy-alcohol metalloid ion passivator is polyoxyethylene glycol and/or glycerol;
Described white dyes is two (the 5-tertiary butyl-2-benzoxazolyl) thiophene of 2,5-;
(b) twin-screw extrusion is carried out in described Preblend, obtain described high whiteness high density polyethylene(HDPE);
The twin-screw extrusion processing temperature of described step (b) is that 210 ± 5 ℃, screw speed are 300 ± 5rpm;
Described step (b) adopts rotating Vortex meshed double screw extrusion equipment to carry out twin-screw extrusion;
The rate of feeding of described extrusion equipment is 0.75 ± 0.01Hz (hertz).
2. the method for claim 1 is characterized in that, in the described oxidation inhibitor, the part by weight of primary antioxidant and auxiliary antioxidant is 1:1.67 ± 0.167.
3. the method for claim 1 is characterized in that, the weight proportion of described oxidation inhibitor and processing aid is: 1:(1.25 ± 0.125).
4. high whiteness high density polyethylene(HDPE) that makes such as the described method of claim 1～3 any one, its initial yellowness index is-12～-14, and the b value is-5～-6; Extrude rear yellowness index for 5 times-9～-11, the b value is measured with ASTM E313-00 bioassay standard-4～-5; Density is at 949kg/m
3-953kg/m
3, measure with the GB/T1033.2-2010 bioassay standard.
5. an adjuvant system is characterized in that in the application of the whiteness that improves the high density polyethylene(HDPE) base-material described adjuvant system comprises oxidation inhibitor, processing aid, metallic ion passivation agent and white dyes; Described oxidation inhibitor comprises primary antioxidant and auxiliary antioxidant, and the parts by weight of each component are as follows:
Wherein primary antioxidant is 1,3,5-three (3,5-di-tert-butyl-4-hydroxyl benzyl) tricarbimide, and molecular formula is: C
48H
69N
3O
6, structural formula is:
Described auxiliary antioxidant is the two stearyl alcohol esters of thio-2 acid, and molecular formula is: C
42H
82O
4S, structural formula is:
Described processing aid is that the part by weight of Zinic stearas and calcium stearate is 1:0.95～1:1.05 in Zinic stearas and calcium stearate hybrid process auxiliary agent and the described processing aid;
Described metallic ion passivation agent is polyhydroxy-alcohol metalloid ion passivator; Described polyhydroxy-alcohol metalloid ion passivator is polyoxyethylene glycol and/or glycerol;
Described white dyes is two (the 5-tertiary butyl-2-benzoxazolyl) thiophene of 2,5-.
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| CN103310908B (en) * | 2013-03-18 | 2016-12-07 | 滁州品创生物科技有限公司 | A kind of manufacture method of carbon fiber composite material cable wire |
| CN107434920A (en) * | 2016-05-26 | 2017-12-05 | 上海羽迪新材料科技有限公司 | A kind of preparation method of high whiteness sheet material master batch |
| CN109575394A (en) * | 2017-09-28 | 2019-04-05 | 中国石化扬子石油化工有限公司 | A kind of tubing polyethylene composition and preparation method thereof that yellow colour index improves |
| CN108794862A (en) * | 2018-07-06 | 2018-11-13 | 湖北工程学院 | A kind of superhigh intensity high-density polyethylene composite material and preparation method thereof |
| CN109401044A (en) * | 2018-12-17 | 2019-03-01 | 上海至正道化高分子材料股份有限公司 | A kind of low-smoke halogen-free polyolefin cable material and preparation method thereof |
| CN111286109A (en) * | 2020-04-17 | 2020-06-16 | 上海赛科石油化工有限责任公司 | Preparation method of anti-yellowing high-density polyethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1113489A (en) * | 1994-05-05 | 1995-12-20 | 通用电气公司 | Benzoxazolyl optical brightners in and for thermoplastic compositions |
| CN101143945A (en) * | 2007-09-04 | 2008-03-19 | 上海新上化高分子材料有限公司 | Color weatherable silane crosslinked polyethylene plastic and application thereof |
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|---|---|---|---|---|
| CN1113489A (en) * | 1994-05-05 | 1995-12-20 | 通用电气公司 | Benzoxazolyl optical brightners in and for thermoplastic compositions |
| CN101143945A (en) * | 2007-09-04 | 2008-03-19 | 上海新上化高分子材料有限公司 | Color weatherable silane crosslinked polyethylene plastic and application thereof |
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Inventor after: Xie Guozhang Inventor after: Qiu Hanliang Inventor after: Feng Youyue Inventor after: Sun Xiaotong Inventor after: Ye Jun Inventor after: Huang Chen Inventor after: Wang Tao Inventor after: Qian Xiaomin Inventor after: Li Shiming Inventor after: Mao Zhengang Inventor before: Xie Guozhang Inventor before: Feng Youyue Inventor before: Sun Xiaotong Inventor before: Ye Jun Inventor before: Huang Chen Inventor before: Wang Tao Inventor before: Qian Xiaomin Inventor before: Li Shiming Inventor before: Mao Zhengang |
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