CN103937072A - Composite granule colored high-density polyethylene material and preparation method thereof - Google Patents

Composite granule colored high-density polyethylene material and preparation method thereof Download PDF

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Publication number
CN103937072A
CN103937072A CN201410178760.1A CN201410178760A CN103937072A CN 103937072 A CN103937072 A CN 103937072A CN 201410178760 A CN201410178760 A CN 201410178760A CN 103937072 A CN103937072 A CN 103937072A
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density polyethylene
parts
nano
composite particles
polyethylene material
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CN201410178760.1A
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CN103937072B (en
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汪晨
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GUANGDONG WEITIAN ENVIRONMENTAL PROTECTION NEW MATERIAL CO., LTD.
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ZHEJIANG PRIMACY PLASTICS INDUSTRY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Abstract

The invention provides a composite granule colored high-density polyethylene material and a preparation method thereof. The composite granule colored high-density polyethylene material is prepared from the following raw materials in parts by weight: 100-120 parts of high-density polyethylene, 30-50 parts of composite granules, 8-14 parts of ethylene bis-stearamide, 0.5-0.9 part of chlorinated polyethylene and 0.2-0.6 part of antioxidant, wherein the composite granules are prepared from the following ingredients in parts by weight: 10-30 parts of BaCO3 nano-whiskers, 5-10 parts of TiO2 nanoparticles, 2-5 parts of inorganic pigment nanoparticles and 5 parts of binder, and the TiO2 nanoparticles and the inorganic pigment nanoparticles are bonded to the BaCO3 nano-whiskers by use of the binder. According to the composite granule colored high-density polyethylene material and the preparation method thereof, through adding the composite granules to color a high-density polyethylene material, high-density polyethylene which is uniformly colored and has excellent mechanical properties is provided, and meanwhile, the production cost of colored high-density polyethylene is reduced.

Description

Painted high-density polyethylene material of composite particles and preparation method thereof
Technical field
The present invention relates to a kind of high-density polyethylene material, relate in particular to painted high-density polyethylene material of a kind of composite particles and preparation method thereof.
Background technology
Use TiCl from nineteen fifty-three Ziegler 4and AlEt 3under low pressure make vinyl polymerization generate HDPE, existing more than 50 year so far, the Development and Production of high density polyethylene(HDPE) constantly obtained innovation, and because of its high comprehensive performance, raw material sources are abundant, and cost is compared with low and continually develop the purposes and the market that make new advances.The HDPE translucent waxy solid that is creamy white is high, the nonpolar thermoplastic resin of a kind of degree of crystallinity, with LDPE, LLDPE comparison, HDPE collateralization degree minimum, molecular energy is closely piled up, density maximum (0.941～0.965gPcm3), and degree of crystallinity is high.HDPE has higher rigidity and toughness, good mechanical property and higher use temperature.With LDPE comparison, there are higher heatproof, oil-proofness, resistance to vapour permeability and environmental stress crack resistance, electrical insulating property and shock resistance and winter hardiness are all fine.HDPE is better than LDPE aspect intensity and stiffness, and Toughness Ratio PVC, LDPE are high.HDPE water-absorbent is atomic little, nontoxic, chemical stability and good, and film is little to the perviousness of water vapor, air.HDPE is the polyolefine kind that world production ability and demand occupy the third-largest class at present, and it is mainly used in film, blowing, tubing etc.
The tinting material using in known high density polyethylene(HDPE) molded-in-color processing mainly contains dry colorant and color concentrate.
Dry colorant is dry powder, and pigment and dispersion agent easily disperse, and brings that workability is poor, problem and problem of environmental pollution in labour hygiene.In addition, it is low that dry colorant depth of shade, disperses badly, in the time manufacturing high density and the high goods of painted precision, is unfavorable.
Color concentrate is current popular macromolecular material special coloring agent.It is made up of pigment or dyestuff, carrier and three kinds of fundamentals of additive, is the pigment of super quantity or dyestuff are attached among resin and the aggregate obtaining equably.The pigment that color concentrate uses, its state can be divided into primary particle, aggregate, coacervate.When pigment is in primary particle state time, its dispersiveness is best, and tinting strength is the strongest, hides performance the best.Primary particle state is the optimum regime of pigment coloring performance.But the pigment of primary particle state, due to intermolecular reactive force, can form the aggregate of the large manyfold of particle diameter, the reactive force between aggregate can form again the coacervate that particle diameter is larger.Pigment in packaging, transport, the process that stores due to extruding, the moisture absorption can form than the granules of pigments of the large manyfold of aggregation size.The secondary shearing of traditional stains masterbatch production technique, due to the technological deficiency of himself, can not fully be reduced into primary particle state by pigment, so the dispersed raising that waits multinomial performance is restricted.And the manufacturing processed of color concentrate is long, step complexity, manufacturing price is very high, generally all will pass through pre-dispersed-mixing-treating processess such as granulation.
In addition be that dry colorant pigment or color concentrate all have adverse influence to the mechanical property of HDPE.The two kinds of tinting materials trend that affects broadly similar on HDPE mechanical property, is all the increase along with adding of colorants, and notched Izod impact strength, tensile strength, elongation, heat-drawn wire are on a declining curve.This is mainly that dry colorant pigment and polyacrylic affinity are poor, and the physical and mechanical properties causing declines; Color concentrate is owing to containing more organic low molecular thing (tinting material, halogen flame, dispersion agent etc.) and mineral compound (Sb in masterbatch 2o 3, ATH etc.), polyolefinic mechanical property is affected.
Summary of the invention
The present invention carries out painted to high-density polyethylene material by interpolation composite particles, the high density polyethylene(HDPE) of a kind of uniform coloring and good mechanical performance is provided, and has also reduced the production cost of painted high density polyethylene(HDPE) simultaneously.
Technical scheme of the present invention is as follows: the painted high-density polyethylene material of a kind of composite particles, and raw materials by weight portion takes:
100～120 parts of high density polyethylene(HDPE)s, 30～50 parts of composite particles, 8～14 parts of ethylene bis stearamides, 0.5～0.9 part of chlorinatedpolyethylene, oxidation inhibitor 0.2-0.6 part.
Described composite particles is by nanometer BaCO 3whisker, nano-TiO 2particle, nano inorganic granules of pigments and binding agent composition, described nano-TiO 2particle, nano inorganic granules of pigments are bonded in nanometer BaCO by binding agent 3on whisker; Wherein, nanometer BaCO 3whisker 10-30 part, nano-TiO 25-10 part, nano inorganic granules of pigments 2-5 part, 5 parts of binding agents.
Binding agent is selected from the soap of aluminium, calcium, lithium, magnesium, titanium, zinc and zirconium, higher than 60 DEG C lower than the temperature of 160 DEG C under softening or partial melting.
Nano inorganic granules of pigments is selected from cadmium red, chrome yellow, red iron oxide, iron oxide yellow, carbon black.
Oxidation inhibitor is selected from the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or their mixture.
A preparation method for the painted high-density polyethylene material of composite particles, described method is carried out according to following step:
1. by binding agent higher than 60 DEG C of softening or partial meltings at lower than the temperature of 160 DEG C with at nanometer BaCO 3whisker surface filming, adds nano-TiO 2particle and nano inorganic granules of pigments, be mixed with rapidly composite particles;
2. high density polyethylene(HDPE), composite particles are measured in accordance with regulations and added high-speed mixer just mixed;
3. ethylene bis stearamide, chlorinatedpolyethylene, oxidation inhibitor are measured in accordance with regulations and added in high-speed mixer, high-speed mixing intensification are heated to 80-110 DEG C, after Hybrid Heating 10-20 minute, are cooled to room temperature;
4. mixture is added in twin screw extruder, extrude, granulation.
Binding agent is softening or partial melting at the temperature lower than 60 DEG C, will be unfavorable for the raising of high-density polyethylene material thermal stability; At the temperature higher than 160 DEG C, softening or partial melting easily causes the reunion of particle in the time preparing composite particles, is unfavorable for particle being uniformly distributed in high-density polyethylene material.
Composite particles can overcome dry colorant, and depth of shade low, disperses bad defect, and the manufacturing processed that can avoid again using color concentrate to bring is long, step complexity, the defect that manufacturing price is high.
The invention has the beneficial effects as follows:
The high-density polyethylene material that composite particles of the present invention is painted, kept the forming property of high density polyethylene(HDPE) good, surface quality is high, dense structure, intensity are high, erosion resistance high, simultaneously, mineral dye and mineral filler are evenly distributed in high-density polyethylene material with the form of composite particles, ensure that high-density polyethylene material uniform coloring and mechanical property are consistent, reduced the segregation that each component causes due to density difference.Composite particles has improved the consistency between high density polyethylene(HDPE) and mineral dye, mineral filler, and two-phase bonding force is improved, can effectively transmission and distribute stress and strain between two-phase.Nanometer BaCO 3whisker and nano particle compound played enhancing and toughening effect simultaneously.Use the painted high-density polyethylene material of composite particles of the present invention, avoided organic low molecular thing (tinting material, halogen flame, dispersion agent etc.) and mineral compound (Sb 2o 3, ATH etc.) disadvantageous effect brought, not only do not reduce the mechanical property of high-density polyethylene material, make on the contrary its mechanical property be greatly improved.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
100 parts of high density polyethylene(HDPE)s, 30 parts of composite particles, 8 parts of ethylene bis stearamides, 0.5 part of chlorinatedpolyethylene, 0.2 part, oxidation inhibitor.
Described composite particles is by nanometer BaCO 3whisker, nano-TiO 2particle, nano inorganic granules of pigments and binding agent composition, described nano-TiO 2particle, nano inorganic granules of pigments are bonded in nanometer BaCO by binding agent 3on whisker; Wherein, nanometer BaCO 315 parts of whiskers, nano-TiO 25 parts, 5 parts of nano inorganic pigment, 5 parts of binding agents.
Binding agent is fatty acid zinc; Nano inorganic pigment is cadmium yellow; Oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Prepare the painted high-density polyethylene material of composite particles according to following step:
1. by binding agent higher than 60 DEG C of softening or partial meltings at lower than the temperature of 160 DEG C with at nanometer BaCO 3whisker surface filming, adds nano-TiO 2particle and nano inorganic granules of pigments, be mixed with rapidly composite particles;
2. high density polyethylene(HDPE), composite particles are measured in accordance with regulations and added high-speed mixer just mixed;
3. ethylene bis stearamide, chlorinatedpolyethylene, oxidation inhibitor are measured in accordance with regulations and added in high-speed mixer, high-speed mixing intensification are heated to 80-110 DEG C, after Hybrid Heating 10-20 minute, are cooled to room temperature;
4. mixture is added in twin screw extruder, extrude, granulation.
Embodiment 2
120 parts of high density polyethylene(HDPE)s, 50 parts of composite particles, 14 parts of ethylene bis stearamides, 0.9 part of chlorinatedpolyethylene, 0.6 part, oxidation inhibitor.
Described composite particles is by nanometer BaCO 3whisker, nano-TiO 2particle, nano inorganic granules of pigments and binding agent composition, described nano-TiO 2particle, nano inorganic granules of pigments are bonded in nanometer BaCO by binding agent 3on whisker; Wherein, nanometer BaCO 330 parts of whiskers, nano-TiO 210 parts, 5 parts of nano inorganic pigment, 5 parts of binding agents.
Binding agent is fatty acid magnesium; Nano inorganic pigment is cadmium red; Oxidation inhibitor is the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid.
Processing step is with embodiment 1.
Embodiment 3
110 parts of high density polyethylene(HDPE)s, 40 parts of composite particles, 10 parts of ethylene bis stearamides, 0.8 part of chlorinatedpolyethylene, 0.5 part, oxidation inhibitor.
Described composite particles is by nanometer BaCO 3whisker, nano-TiO 2particle, nano inorganic granules of pigments and binding agent composition, described nano-TiO 2particle, nano inorganic granules of pigments are by the binding agent nanometer BaCO that bonds 3on whisker; Wherein, nanometer BaCO 325 parts of whiskers, nano-TiO 26 parts, 4 parts of nano inorganic pigment, 5 parts of binding agents.
Binding agent is fatty acid calcium; Nano inorganic pigment is red iron oxide; Oxidation inhibitor is selected from four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Processing step is with embodiment 1.
Comparative example 1
120 parts of high density polyethylene(HDPE)s, nanometer BaCO 330 parts of whiskers, nano-TiO 210 parts, 5 parts of cadmium reds, 14 parts of ethylene bis stearamides, 0.9 part of chlorinatedpolyethylene, 0.6 part, oxidation inhibitor.
Oxidation inhibitor is the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid.
Prepare modification high-density polyethylene material according to following step:
1. by high density polyethylene(HDPE), nanometer BaCO 3whisker, nano-TiO 2, cadmium red is measured in accordance with regulations and is added high-speed mixer just mixed;
2. ethylene bis stearamide, chlorinatedpolyethylene, oxidation inhibitor are measured in accordance with regulations and added in high-speed mixer, high-speed mixing intensification are heated to 80-110 DEG C, after Hybrid Heating 10-20 minute, are cooled to room temperature;
3. mixture is added in twin screw extruder, extrude, granulation.
Comparative example 2
100 parts of high density polyethylene(HDPE)s, nanometer BaCO 315 parts of whiskers, nano-TiO 25 parts, 5 parts of cadmium yellows, 8 parts of ethylene bis stearamides, 0.5 part of chlorinatedpolyethylene, oxidation inhibitor 0.2-part.
Oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Processing step is with comparative example 1.
Comparative example 3
100 parts of high density polyethylene(HDPE)s, nanometer BaCO 315 parts of whiskers, nano-TiO 25 parts, 5 parts of Masterbatchs, 8 parts of ethylene bis stearamides, 0.5 part of chlorinatedpolyethylene, oxidation inhibitor 0.2-part.
Oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
Above-described embodiment, comparative example the performance test results:
Note: each test event is all carried out (flame retardant resistance is by limiting oxygen index(LOI) testing method) by concerned countries standard
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (4)

1. the painted high-density polyethylene material of composite particles, raw materials by weight portion takes: 100～120 parts of high density polyethylene(HDPE)s, 30～50 parts of composite particles, 8～14 parts of ethylene bis stearamides, 0.5～0.9 part of chlorinatedpolyethylene, oxidation inhibitor 0.2-0.6 part; Described composite particles is by nanometer BaCO 3whisker, nano-TiO 2particle, nano inorganic granules of pigments and binding agent composition, described nano-TiO 2particle, nano inorganic granules of pigments are bonded in nanometer BaCO by binding agent 3on whisker; Wherein, nanometer BaCO 3whisker 10-30 part, nano-TiO 25-10 part, nano inorganic granules of pigments 2-5 part, 5 parts of binding agents; Binding agent is selected from the soap of aluminium, calcium, lithium, magnesium, titanium, zinc and zirconium, higher than 60 DEG C lower than the temperature of 160 DEG C under softening or partial melting.
Oxidation inhibitor is selected from the positive octadecanol ester of β-(4-hydroxy phenyl-3,5-di-t-butyl) propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or their mixture.
2. the painted high-density polyethylene material of composite particles as claimed in claim 1, is characterized in that: nano inorganic granules of pigments is selected from cadmium red, chrome yellow, red iron oxide, iron oxide yellow, carbon black.
3. the painted high-density polyethylene material of composite particles as claimed in claim 1, it is characterized in that: oxidation inhibitor is selected from β-(4-hydroxy phenyl-3,5-di-t-butyl) the positive octadecanol ester of propionic acid, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester or their mixture.
4. the preparation method of the painted high-density polyethylene material of composite particles as described in claim 1-3, carries out according to following step:
1. by binding agent higher than 60 DEG C of softening or partial meltings at lower than the temperature of 160 DEG C with at nanometer BaCO 3whisker surface filming, adds nano-TiO 2particle and nano inorganic granules of pigments, be mixed with rapidly composite particles;
2. high density polyethylene(HDPE), composite particles are measured in accordance with regulations and added high-speed mixer just mixed;
3. ethylene bis stearamide, chlorinatedpolyethylene, oxidation inhibitor are measured in accordance with regulations and added in high-speed mixer, high-speed mixing intensification are heated to 80-110 DEG C, after Hybrid Heating 10-20 minute, are cooled to room temperature;
4. mixture is added in twin screw extruder, extrude, granulation.
CN201410178760.1A 2014-04-29 2014-04-29 Composite granule colored high-density polyethylene material and preparation method thereof Active CN103937072B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN107829117A (en) * 2017-10-24 2018-03-23 成都新柯力化工科技有限公司 A kind of method that no Screw Extrusion prepares plastic color master material
CN108690343A (en) * 2017-04-11 2018-10-23 合肥杰事杰新材料股份有限公司 A kind of polyphenyl ether material and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN108690343A (en) * 2017-04-11 2018-10-23 合肥杰事杰新材料股份有限公司 A kind of polyphenyl ether material and preparation method thereof
CN107829117A (en) * 2017-10-24 2018-03-23 成都新柯力化工科技有限公司 A kind of method that no Screw Extrusion prepares plastic color master material
CN107829117B (en) * 2017-10-24 2019-05-07 汕头市雷氏塑化科技有限公司 A method of no Screw Extrusion prepares plastic color master material

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