CN104877223A - Composite enhancing high density polyethylene material and preparation method thereof - Google Patents

Composite enhancing high density polyethylene material and preparation method thereof Download PDF

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Publication number
CN104877223A
CN104877223A CN201510319761.8A CN201510319761A CN104877223A CN 104877223 A CN104877223 A CN 104877223A CN 201510319761 A CN201510319761 A CN 201510319761A CN 104877223 A CN104877223 A CN 104877223A
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density polyethylene
parts
sphere
phenolic aldehyde
polyethylene material
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金政
吴迪
赵东宇
赵静
王宝龙
韩金雨
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Heilongjiang University
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Heilongjiang University
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C08L33/20—Homopolymers or copolymers of acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • 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 relates to a composite enhancing high density polyethylene material and a preparation method thereof. The invention aims to solve the problems that the existing high density polyethylene composite material is insufficient in mechanical property and poorer in heat resistance. The composite enhancing high density polyethylene material is prepared by the following ingredients in parts by mass: 70-98 parts of high density polyethylene, 1-10 parts of phenolic aldehyde balls, 1-20 parts of polyacrylonitrile fiber, 0.1-5 parts of coupling reagent and 0.1-2 parts of antioxygen. The method comprises the following steps of (1) weighing; (2) preprocessing the phenolic aldehyde balls; (3) pre-oxidizing the polyacrylonitrile fiber; (4) mixing. The composite enhancing high density polyethylene material prepared by the invention has the excellent performances of wear resistance, fire resistance, electric resistance and the like, has great improvement on mechanical property and heat-resistant quality, and can be applied to the fields of building pipes, electric wires and cables, medical supplies, food processing and the like. The preparation method provided by the invention is simple to operate, low in price and suitable for industrial production.

Description

A kind of composite strengthening high-density polyethylene material and preparation method thereof
Technical field
The present invention relates to a kind of composite strengthening high-density polyethylene material and preparation method thereof.
Background technology
High density polyethylene(HDPE) (HDPE) is one of important five large general-purpose plastics, has that source is wide and abundant, good, the long-term anti-compression property of physical strength, corrosion-resistant, wear resistance good, the processing of long service life, easy-formation, the nontoxic feature such as inexpensive are widely used in the field such as blow-molded article, film and board product, injection-molded item, tubing article, fiber, electric wire.But high density polyethylene(HDPE) also exists some shortcomings, such as ageing resistance is poor, ESCR is poor, intensity and toughness are not enough, limits its application in some aspects.Therefore activeness and quietness modification is carried out to high density polyethylene(HDPE), prepare the high-density polyethylene composite material of high performance, functionalization, just become the focus of academia and business circles research.
High-density polyethylene modified method has a lot, and comparatively conventional is carry out filling enhancing modified to it, filling-modifiedly can be divided into two kinds by filler modified kind, i.e. mineral filler and organic filler.Although add the effect that mineral filler such as calcium carbonate, talcum powder, glass microballon, mica etc. can play the performance such as intensity, rigidity, dimensional stability improving material in high density polyethylene(HDPE), but these mineral filler relative densities are larger, add in polymkeric substance the matrix material relative density making to prepare large, quality product is caused to rise, and consistency is bad between mineral filler and organic polyethylene, need to carry out finishing to inorganic materials, just can better and matrix carry out compound, preparation technology is comparatively complicated, and cost is higher.
Summary of the invention
The present invention is the problem that mechanical property is not enough, thermotolerance is poor that will solve existing high-density polyethylene composite material, and provides a kind of composite strengthening high-density polyethylene material and preparation method thereof.
A kind of composite strengthening high-density polyethylene material is made up of 70 ~ 98 parts of high density polyethylene(HDPE)s, 1 ~ 10 part of phenolic aldehyde sphere, 1 ~ 20 part of polyacrylonitrile fibre, 0.1 ~ 5 part of coupling agent and 0.1 ~ 2 part of oxidation inhibitor by mass fraction; The particle diameter of described phenolic aldehyde sphere is 0.05 μm ~ 5 μm; The length of described polyacrylonitrile fibre is 0.5mm ~ 10mm; Described coupling agent is KH-550 treatment agent.
A kind of preparation method of composite strengthening high-density polyethylene material completes according to the following steps:
One, weigh: take 70 ~ 98 parts of high density polyethylene(HDPE)s, 1 ~ 10 part of phenolic aldehyde sphere, 1 ~ 20 part of polyacrylonitrile fibre, 0.1 ~ 5 part of coupling agent and 0.1 ~ 2 part of oxidation inhibitor by mass fraction; The particle diameter of described phenolic aldehyde sphere is 0.05 μm ~ 5 μm; The length of described polyacrylonitrile fibre is 0.5mm ~ 10mm; Described coupling agent is KH-550 treatment agent;
Two, 1 ~ 10 part of phenolic aldehyde sphere step one taken is placed in three-necked bottle, adds dehydrated alcohol, washs after ultrasonic agitation 1h ~ 4h, is then dry 1h ~ 24h under the condition of 80 DEG C in temperature, obtains pretreated phenolic aldehyde sphere;
Three, it is that the air dry oven of 130 DEG C ~ 180 DEG C carries out preoxidation that 1 ~ 20 part of polyacrylonitrile fibre step one taken is placed in temperature, and time of drying is 1h ~ 5h, obtains the polyacrylonitrile fibre of preoxidation;
Four, 70 ~ 98 parts of high density polyethylene(HDPE)s that step one is taken, 0.1 ~ 5 part of coupling agent that step one takes, 0.1 ~ 2 part of oxidation inhibitor that step one takes, the polyacrylonitrile fibre of the pretreated phenolic aldehyde sphere that step 2 obtains and the preoxidation that step 3 obtains is placed in low speed mixer, be mix under the condition of 10r/min ~ 40r/min at rotating speed, obtain the raw material mixed, the raw material mixed is added in twin screw extruder, by the matrix material extruded through dicing machine pelletizing, then be dry 24h ~ 36h under the condition of 80 DEG C in temperature, phenolic aldehyde sphere/polyacrylonitrile fibre/high-density polyethylene composite material is obtained again by injector is shaping, i.e. composite strengthening high-density polyethylene material, the temperature of described twin screw extruder is set as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, and screw speed is 100r/min ~ 150r/min.
Beneficial effect of the present invention:
1, composite strengthening high-density polyethylene material packing material phenolic aldehyde sphere of the present invention, polyacrylonitrile fibre are organic filler, in mixing process, do not need just can have good consistency with resin matrix through finishing, and matrix material has good mechanical property, Heat stability is good, the advantage such as cheap, practical, can be used as the fields such as building pipe, electric wire, medical devices, food-processing.Preparation method's operating procedure that this invention provides is easy, cheap, has good industrial prospect.
2, the tensile strength of composite strengthening high-density polyethylene material of the present invention can reach 23 ~ 40MPa, and shock strength is 20 ~ 39kJ/m 2, flexural strength is 35 ~ 70MPa, and modulus in flexure is 1300 ~ 2000MPa, and Vicat softening point is 129 DEG C ~ 145 DEG C, and over-all properties is good.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the composite strengthening high-density polyethylene material that embodiment six obtains.
Embodiment
Embodiment one: a kind of composite strengthening high-density polyethylene material of present embodiment is made up of 70 ~ 98 parts of high density polyethylene(HDPE)s, 1 ~ 10 part of phenolic aldehyde sphere, 1 ~ 20 part of polyacrylonitrile fibre, 0.1 ~ 5 part of coupling agent and 0.1 ~ 2 part of oxidation inhibitor by mass fraction; The particle diameter of described phenolic aldehyde sphere is 0.05 μm ~ 5 μm; The length of described polyacrylonitrile fibre is 0.5mm ~ 10mm; Described coupling agent is KH-550 treatment agent.
Oxidation inhibitor described in present embodiment is antioxidant 1010.
Phenolic resin balls in present embodiment has that density is little, good heat resistance, consistency are good and the advantage such as better mechanical property, because it is micro-sphere structure, good fluidity tap density high even air hole distribution, not easily produces stress concentration in the course of processing, and is that point cantact is not easily reunited.Polyacrylonitrile fibre has cheap, light weight, corrosion-resistant, specific tenacity advantages of higher, and be good composite reinforcing material, the two is organic filler, and not needing in mixing process just can have good consistency with resin matrix through finishing.
Phenolic aldehyde sphere in present embodiment raw material is on July 19th, 2011 by the applying date, application number: 201110202143.7, denomination of invention: the preparation method of phenolic resin microspheres and utilize its preparation method preparing the phenolic resin microspheres described in method of alkyd resin based carbon ball to obtain.
The tensile strength of the composite strengthening high-density polyethylene material of present embodiment can reach 23 ~ 40MPa, and shock strength is 20 ~ 39kJ/m 2, flexural strength is 35 ~ 70MPa, and modulus in flexure is 1300 ~ 2000MPa, and Vicat softening point is 129 DEG C ~ 145 DEG C, and over-all properties is good.
Embodiment two: present embodiment and embodiment one unlike: composite strengthening high-density polyethylene material is made up of 75 ~ 93 parts of high density polyethylene(HDPE)s, 3 ~ 8 parts of phenolic aldehyde sphere, 4 ~ 17 parts of polyacrylonitrile fibres, 1 ~ 4 part of coupling agent and 0.1 ~ 1 part of oxidation inhibitor by mass fraction.Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: composite strengthening high-density polyethylene material is made up of 80 ~ 88 parts of high density polyethylene(HDPE)s, 4 ~ 7 parts of phenolic aldehyde sphere, 8 ~ 13 parts of polyacrylonitrile fibres, 1 ~ 3 part of coupling agent and 0.3 ~ 1 part of oxidation inhibitor by mass fraction.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: composite strengthening high-density polyethylene material is made up of 82 ~ 86 parts of high density polyethylene(HDPE)s, 5 ~ 7 parts of phenolic aldehyde sphere, 9 ~ 11 parts of polyacrylonitrile fibres, 2 ~ 3 parts of coupling agents and 0.5 ~ 1 part of oxidation inhibitor by mass fraction.Other are identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: composite strengthening high-density polyethylene material is made up of 85 parts of high density polyethylene(HDPE)s, 6 parts of phenolic aldehyde sphere, 9 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of oxidation inhibitor by mass fraction.Other are identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the particle diameter of described phenolic aldehyde sphere is 1 μm.Other are identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the particle diameter of described phenolic aldehyde sphere is 1.5 μm.Other are identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the particle diameter of described phenolic aldehyde sphere is 2 μm.Other are identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the particle diameter of described phenolic aldehyde sphere is 2.5 μm.Other are identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the particle diameter of described phenolic aldehyde sphere is 3 μm.Other are identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten unlike: the particle diameter of described phenolic aldehyde sphere is 3.5 μm.Other are identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: the particle diameter of described phenolic aldehyde sphere is 4 μm.Other are identical with one of embodiment one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two unlike: the length of described polyacrylonitrile fibre is 1mm.Other are identical with one of embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten three unlike: the length of described polyacrylonitrile fibre is 2mm.Other are identical with one of embodiment one to ten three.
Embodiment 15: one of present embodiment and embodiment one to ten four unlike: the length of described polyacrylonitrile fibre is 3mm.Other are identical with one of embodiment one to ten four.
Embodiment 16: one of present embodiment and embodiment one to ten five unlike: the length of described polyacrylonitrile fibre is 6mm.Other are identical with one of embodiment one to ten five.
Embodiment 17: one of present embodiment and embodiment one to ten six unlike: the length of described polyacrylonitrile fibre is 7mm.Other are identical with one of embodiment one to ten six.
Embodiment 18: one of present embodiment and embodiment one to ten seven unlike: the length of described polyacrylonitrile fibre is 9mm.Other are identical with one of embodiment one to ten seven.
Embodiment 19: the preparation method of a kind of composite strengthening high-density polyethylene material of present embodiment completes according to the following steps:
One, weigh: take 70 ~ 98 parts of high density polyethylene(HDPE)s, 1 ~ 10 part of phenolic aldehyde sphere, 1 ~ 20 part of polyacrylonitrile fibre, 0.1 ~ 5 part of coupling agent and 0.1 ~ 2 part of oxidation inhibitor by mass fraction; The particle diameter of described phenolic aldehyde sphere is 0.05 μm ~ 5 μm; The length of described polyacrylonitrile fibre is 0.5mm ~ 10mm; Described coupling agent is KH-550 treatment agent;
Two, 1 ~ 10 part of phenolic aldehyde sphere step one taken is placed in three-necked bottle, adds dehydrated alcohol, washs after ultrasonic agitation 1h ~ 4h, is then dry 1h ~ 24h under the condition of 80 DEG C in temperature, obtains pretreated phenolic aldehyde sphere;
Three, it is that the air dry oven of 130 DEG C ~ 180 DEG C carries out preoxidation that 1 ~ 20 part of polyacrylonitrile fibre step one taken is placed in temperature, and time of drying is 1h ~ 5h, obtains the polyacrylonitrile fibre of preoxidation;
Four, 70 ~ 98 parts of high density polyethylene(HDPE)s that step one is taken, 0.1 ~ 5 part of coupling agent that step one takes, 0.1 ~ 2 part of oxidation inhibitor that step one takes, the polyacrylonitrile fibre of the pretreated phenolic aldehyde sphere that step 2 obtains and the preoxidation that step 3 obtains is placed in low speed mixer, be mix under the condition of 10r/min ~ 40r/min at rotating speed, obtain the raw material mixed, the raw material mixed is added in twin screw extruder, by the matrix material extruded through dicing machine pelletizing, then be dry 24h ~ 36h under the condition of 80 DEG C in temperature, phenolic aldehyde sphere/polyacrylonitrile fibre/high-density polyethylene composite material is obtained again by injector is shaping, i.e. composite strengthening high-density polyethylene material, the temperature of described twin screw extruder is set as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, and screw speed is 100r/min ~ 150r/min.
In present embodiment, oxidation inhibitor described in step one is antioxidant 1010.
The composite strengthening high-density polyethylene material packing material phenolic aldehyde sphere of present embodiment, polyacrylonitrile fibre are organic filler, in mixing process, do not need just can have good consistency with resin matrix through finishing, and matrix material has good mechanical property, Heat stability is good, the advantage such as cheap, practical, can be used as the fields such as building pipe, electric wire, medical devices, food-processing.Preparation method's operating procedure that this invention provides is easy, cheap, has good industrial prospect.
The tensile strength of the composite strengthening high-density polyethylene material of present embodiment can reach 23 ~ 40MPa, and shock strength is 20 ~ 39kJ/m 2, flexural strength is 35 ~ 70MPa, and modulus in flexure is 1300 ~ 2000MPa, and Vicat softening point is 129 DEG C ~ 145 DEG C, and over-all properties is good.
Embodiment 20: present embodiment and embodiment 19 unlike: take 75 ~ 93 parts of high density polyethylene(HDPE)s by mass fraction in step one, 3 ~ 8 parts of phenolic aldehyde sphere, 4 ~ 17 parts of polyacrylonitrile fibres, 1 ~ 4 part of coupling agent and 0.1 ~ 1 part of oxidation inhibitor made.Other are identical with embodiment 19.
Embodiment 21: present embodiment and embodiment 19 or 20 unlike: take 80 ~ 88 parts of high density polyethylene(HDPE)s by mass fraction in step one, 4 ~ 7 parts of phenolic aldehyde sphere, 8 ~ 13 parts of polyacrylonitrile fibres, 1 ~ 3 part of coupling agent and 0.3 ~ 1 part of oxidation inhibitor made.Other are identical with embodiment 19 or 20.
Embodiment 22: one of present embodiment and embodiment ten nine to two 11 unlike: take 82 ~ 86 parts of high density polyethylene(HDPE)s by mass fraction in step one, 5 ~ 7 parts of phenolic aldehyde sphere, 9 ~ 11 parts of polyacrylonitrile fibres, 2 ~ 3 parts of coupling agents and 0.5 ~ 1 part of oxidation inhibitor made.Other are one of ten nine to two ten one identical with embodiment.
Embodiment 23: one of present embodiment and embodiment ten nine to two 12 unlike: take 85 parts of high density polyethylene(HDPE)s by mass fraction in step one, 6 parts of phenolic aldehyde sphere, 9 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of oxidation inhibitor made.Other are one of ten nine to two ten two identical with embodiment.
Embodiment 24: one of present embodiment and embodiment ten nine to two 13 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 1 μm.Other are one of ten nine to two ten three identical with embodiment.
Embodiment 25: one of present embodiment and embodiment ten nine to two 14 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 1.5 μm.Other are one of ten nine to two ten four identical with embodiment.
Embodiment 26: one of present embodiment and embodiment ten nine to two 15 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 2 μm.Other are one of ten nine to two ten five identical with embodiment.
Embodiment 27: one of present embodiment and embodiment ten nine to two 16 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 2.5 μm.Other are one of ten nine to two ten six identical with embodiment.
Embodiment 28: one of present embodiment and embodiment ten nine to two 17 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 3 μm.Other are one of ten nine to two ten seven identical with embodiment.
Embodiment 29: one of present embodiment and embodiment ten nine to two 18 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 3.5 μm.Other are one of ten nine to two ten eight identical with embodiment.
Embodiment 30: one of present embodiment and embodiment ten nine to two 19 unlike: the particle diameter of phenolic aldehyde sphere described in step one is 4 μm.Other are one of ten nine to two ten nine identical with embodiment.
Embodiment 31: one of present embodiment and embodiment ten nine to three ten unlike: the length of polyacrylonitrile fibre described in step one is 1mm.Other are identical with one of embodiment ten nine to three ten.
Embodiment 32: one of present embodiment and embodiment ten nine to three 11 unlike: the length of polyacrylonitrile fibre described in step one is 2mm.Other are one of ten nine to three ten one identical with embodiment.
Embodiment 33: one of present embodiment and embodiment ten nine to three 12 unlike: the length of polyacrylonitrile fibre described in step one is 3mm.Other are one of ten nine to three ten two identical with embodiment.
Embodiment 34: one of present embodiment and embodiment ten nine to three 13 unlike: the length of polyacrylonitrile fibre described in step one is 6mm.Other are one of ten nine to three ten three identical with embodiment.
Embodiment 35: one of present embodiment and embodiment ten nine to three 14 unlike: the length of polyacrylonitrile fibre described in step one is 7mm.Other are one of one to three ten four identical with embodiment.
Embodiment 36: one of present embodiment and embodiment ten nine to three 15 unlike: the length of polyacrylonitrile fibre described in step one is 9mm.Other are one of ten nine to three ten five identical with embodiment.
Embodiment 37: it is that the air dry oven of 140 DEG C ~ 170 DEG C carries out preoxidation that one of present embodiment and embodiment ten nine to three 16 are placed in temperature unlike: 1 ~ 20 part of polyacrylonitrile fibre step one taken in step 3.Other are one of ten nine to three ten six identical with embodiment.
Embodiment 38: it is that the air dry oven of 150 DEG C ~ 160 DEG C carries out preoxidation that one of present embodiment and embodiment ten nine to three 17 are placed in temperature unlike: 1 ~ 20 part of polyacrylonitrile fibre step one taken in step 3.Other are one of ten nine to three ten seven identical with embodiment.
Embodiment 39: one of present embodiment and embodiment ten nine to three 18 unlike: in step 3, time of drying is 2h ~ 3h.Other are one of ten nine to three ten eight identical with embodiment.
Embodiment 40: one of present embodiment and embodiment ten nine to three 19 unlike: the temperature of injector described in step 4 is 180 DEG C ~ 200 DEG C, and injection pressure is 75 ~ 90MPa.Other are one of ten nine to three ten nine identical with embodiment.
Embodiment 41: one of present embodiment and embodiment ten nine to four ten unlike: the temperature of injector described in step 4 is 200 DEG C, and injection pressure is 80MPa.Screw speed described in step 4 is 120r/min ~ 130r/min.Other are identical with one of embodiment ten nine to four ten.
Embodiment 42: one of present embodiment and embodiment ten nine to four 11 unlike: screw speed described in step 4 is 110r/min ~ 130r/min.Other are one of ten nine to four ten one identical with embodiment.
Embodiment 43: one of present embodiment and embodiment ten nine to four 12 unlike: screw speed described in step 4 is 120r/min ~ 130r/min.Other are one of ten nine to four ten two identical with embodiment.
Embodiment 44: one of present embodiment and embodiment ten nine to four 13 unlike: screw speed described in step 4 is 125r/min.Other are one of ten nine to four ten three identical with embodiment.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: a kind of preparation method of composite strengthening high-density polyethylene material completes according to the following steps:
One, weigh: take 98 parts of high density polyethylene(HDPE)s, 1 part of phenolic aldehyde sphere, 1 part of polyacrylonitrile fibre, 2 parts of coupling agents and 1 part of antioxidant 1010 by mass fraction; The particle diameter of described phenolic aldehyde sphere is 1 μm; The length of described polyacrylonitrile fibre is 3mm; Described coupling agent is KH-550 treatment agent;
Two, 1 ~ 10 part of phenolic aldehyde sphere step one taken is placed in three-necked bottle, adds dehydrated alcohol, washs after ultrasonic agitation 2h, is then dry 12h under the condition of 80 DEG C in temperature, obtains pretreated phenolic aldehyde sphere;
Three, it is that the air dry oven of 130 DEG C ~ 180 DEG C carries out preoxidation that 1 part of polyacrylonitrile fibre step one taken is placed in temperature, and time of drying is 1h ~ 5h, obtains the polyacrylonitrile fibre of preoxidation;
Four, 98 parts of high density polyethylene(HDPE)s that step one is taken, 2 parts of coupling agents that step one takes, 1 part of antioxidant 1010 that step one takes, the polyacrylonitrile fibre of the pretreated phenolic aldehyde sphere that step 2 obtains and the preoxidation that step 3 obtains is placed in low speed mixer, be mix under the condition of 10r/min ~ 40r/min at rotating speed, obtain the raw material mixed, the raw material mixed is added in twin screw extruder, by the matrix material extruded through dicing machine pelletizing, then be dry 24h under the condition of 80 DEG C in temperature, phenolic aldehyde sphere/polyacrylonitrile fibre/high-density polyethylene composite material is obtained again by injector is shaping, i.e. composite strengthening high-density polyethylene material, the temperature of described injector is 200 DEG C, and injection pressure is 80MPa, the temperature of described twin screw extruder is set as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, and screw speed is 125r/min.
Embodiment two: the present embodiment and embodiment one difference are: take 90 parts of high density polyethylene(HDPE)s, 4 parts of phenolic aldehyde sphere, 6 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of antioxidant 1010 by mass fraction in step one.Other are identical with embodiment one.
Embodiment three: the present embodiment and embodiment one or two difference are: take 80 parts of high density polyethylene(HDPE)s, 7 parts of phenolic aldehyde sphere, 13 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of antioxidant 1010 by mass fraction in step one.Other are identical with embodiment one or two.
Embodiment four: one of the present embodiment and embodiment one to three difference is: take 75 parts of high density polyethylene(HDPE)s, 8 parts of phenolic aldehyde sphere, 17 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of antioxidant 1010 by mass fraction in step one.Other are identical with one of embodiment one to three.
Embodiment five: one of the present embodiment and embodiment one to four difference is: take 85 parts of high density polyethylene(HDPE)s, 6 parts of phenolic aldehyde sphere, 9 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of antioxidant 1010 by mass fraction in step one.Other are identical with one of embodiment one to four.
Embodiment six: the present embodiment and embodiment five difference are: the particle diameter of phenolic aldehyde sphere described in step one is 1.5 μm; The length of described polyacrylonitrile fibre is 6mm.Other are identical with embodiment five.
Embodiment seven: the present embodiment and embodiment five difference are: the particle diameter of phenolic aldehyde sphere described in step one is 2 μm; The length of described polyacrylonitrile fibre is 7mm.Other are identical with embodiment five.
Embodiment eight: the present embodiment and embodiment five difference are: the particle diameter of phenolic aldehyde sphere described in step one is 3 μm; The length of described polyacrylonitrile fibre is 9mm.Other are identical with embodiment five.
Embodiment nine: the present embodiment and embodiment five difference are: the particle diameter of phenolic aldehyde sphere described in step one is 5 μm; The length of described polyacrylonitrile fibre is 10mm.Other are identical with embodiment five.
Fig. 1 is the SEM figure of the composite strengthening high-density polyethylene material that embodiment six obtains; From then on figure can find out that phenolic aldehyde sphere, polyacrylonitrile fibre are uniformly dispersed between high density polyethylene(HDPE) matrix, and interfacial bonding property is good.
Composite strengthening high-density polyethylene material embodiment one to nine obtained carries out mechanical property and thermal property test, sample testing tensile strength, shock strength, flexural strength and shore hardness are undertaken by GB/T 1040.1-06, ASTM D256-10, GB/T 9341-08, GB/T 2411-08 standard respectively, and test result is in table 1.
The mechanical property of the composite strengthening high-density polyethylene material that table 1 embodiment one to nine obtains and thermal property
Project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9
Tensile strength MPa 23.1 25.7 29.5 35.8 38.3 40.1 36.5 37.2 38.5
Elongation at break % 400 325 278 256 200 175 247 236 268
Shock strength kJ/m 2 25.0 32.3 28.7 24.2 35.3 38.9 35.6 33.2 36.1
Flexural strength MPa 35.1 39.5 48.4 57.5 64.4 69.8 62.5 63.8 53.1
Modulus in flexure MPa 1305 1452 1546 1724 1835 1976 1867 1745 1654
Shore hardness D 68 70 73 75 73 72 73 73 72
Vicat softening point DEG C 129 134 140 145 137 140 137 139 138
Excellent mechanical property and thermal property is embodied by upper table known composite strengthening high density polyethylene(HDPE).

Claims (10)

1. a composite strengthening high-density polyethylene material, is characterized in that composite strengthening high-density polyethylene material is made up of 70 ~ 98 parts of high density polyethylene(HDPE)s, 1 ~ 10 part of phenolic aldehyde sphere, 1 ~ 20 part of polyacrylonitrile fibre, 0.1 ~ 5 part of coupling agent and 0.1 ~ 2 part of oxidation inhibitor by mass fraction; The particle diameter of described phenolic aldehyde sphere is 0.05 μm ~ 5 μm; The length of described polyacrylonitrile fibre is 0.5mm ~ 10mm; Described coupling agent is KH-550 treatment agent.
2. a kind of composite strengthening high-density polyethylene material according to claim 1, is characterized in that composite strengthening high-density polyethylene material is made up of 82 ~ 86 parts of high density polyethylene(HDPE)s, 5 ~ 7 parts of phenolic aldehyde sphere, 9 ~ 11 parts of polyacrylonitrile fibres, 2 ~ 3 parts of coupling agents and 0.5 ~ 1 part of oxidation inhibitor by mass fraction.
3. a kind of composite strengthening high-density polyethylene material according to claim 1, is characterized in that the particle diameter of described phenolic aldehyde sphere is 2 μm.
4. a kind of composite strengthening high-density polyethylene material according to claim 1, is characterized in that the length of described polyacrylonitrile fibre is 2mm.
5. the preparation method of a kind of composite strengthening high-density polyethylene material as claimed in claim 1, is characterized in that the preparation method of composite strengthening high-density polyethylene material completes according to the following steps:
One, weigh: take 70 ~ 98 parts of high density polyethylene(HDPE)s, 1 ~ 10 part of phenolic aldehyde sphere, 1 ~ 20 part of polyacrylonitrile fibre, 0.1 ~ 5 part of coupling agent and 0.1 ~ 2 part of oxidation inhibitor by mass fraction; The particle diameter of described phenolic aldehyde sphere is 0.05 μm ~ 5 μm; The length of described polyacrylonitrile fibre is 0.5mm ~ 10mm; Described coupling agent is KH-550 treatment agent;
Two, 1 ~ 10 part of phenolic aldehyde sphere step one taken is placed in three-necked bottle, adds dehydrated alcohol, washs after ultrasonic agitation 1h ~ 4h, is then dry 1h ~ 24h under the condition of 80 DEG C in temperature, obtains pretreated phenolic aldehyde sphere;
Three, it is that the air dry oven of 130 DEG C ~ 180 DEG C carries out preoxidation that 1 ~ 20 part of polyacrylonitrile fibre step one taken is placed in temperature, and time of drying is 1h ~ 5h, obtains the polyacrylonitrile fibre of preoxidation;
Four, 70 ~ 98 parts of high density polyethylene(HDPE)s that step one is taken, 0.1 ~ 5 part of coupling agent that step one takes, 0.1 ~ 2 part of oxidation inhibitor that step one takes, the polyacrylonitrile fibre of the pretreated phenolic aldehyde sphere that step 2 obtains and the preoxidation that step 3 obtains is placed in low speed mixer, be mix under the condition of 10r/min ~ 40r/min at rotating speed, obtain the raw material mixed, the raw material mixed is added in twin screw extruder, by the matrix material extruded through dicing machine pelletizing, then be dry 24h ~ 36h under the condition of 80 DEG C in temperature, phenolic aldehyde sphere/polyacrylonitrile fibre/high-density polyethylene composite material is obtained again by injector is shaping, i.e. composite strengthening high-density polyethylene material, the temperature of described twin screw extruder is set as 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, and screw speed is 100r/min ~ 150r/min.
6. the preparation method of a kind of composite strengthening high-density polyethylene material according to claim 5, is characterized in that taking 85 parts of high density polyethylene(HDPE)s by mass fraction in step one, 6 parts of phenolic aldehyde sphere, 9 parts of polyacrylonitrile fibres, 2 parts of coupling agents and 1 part of oxidation inhibitor is made.
7. the preparation method of a kind of composite strengthening high-density polyethylene material according to claim 5, is characterized in that the particle diameter of phenolic aldehyde sphere described in step one is 2 μm.
8. the preparation method of a kind of composite strengthening high-density polyethylene material according to claim 5, is characterized in that the length of polyacrylonitrile fibre described in step one is 6mm.
9. the preparation method of a kind of composite strengthening high-density polyethylene material according to claim 5, it is characterized in that the temperature of injector described in step 4 is 200 DEG C, injection pressure is 80MPa.
10. the preparation method of a kind of composite strengthening high-density polyethylene material according to claim 5, is characterized in that screw speed described in step 4 is 125r/min.
CN201510319761.8A 2015-06-11 2015-06-11 Composite enhancing high density polyethylene material and preparation method thereof Pending CN104877223A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601849A (en) * 2016-01-27 2016-05-25 安徽猎塔电缆集团有限公司 Insectbite-proof environment-friendly cold-resistant cable formula
CN106633292A (en) * 2016-11-30 2017-05-10 芜湖立创包装有限公司 Anti-corrosion plastic material composition, anti-corrosion plastic bottle and preparation method of anti-corrosion plastic bottle

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352003A (en) * 2011-07-19 2012-02-15 黑龙江大学 Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method
CN103694558A (en) * 2013-12-06 2014-04-02 黑龙江大学 Phenolic aldehyde sphere/polypropylene composite material and preparation method thereof
CN104194123A (en) * 2014-09-10 2014-12-10 黑龙江大学 Polyacrylonitrile fiber/high-density polyethylene composite material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352003A (en) * 2011-07-19 2012-02-15 黑龙江大学 Preparation method of phenolic resin microballoons and method for preparing phenolic resin-based carbon spheres by use of preparation method
CN103694558A (en) * 2013-12-06 2014-04-02 黑龙江大学 Phenolic aldehyde sphere/polypropylene composite material and preparation method thereof
CN104194123A (en) * 2014-09-10 2014-12-10 黑龙江大学 Polyacrylonitrile fiber/high-density polyethylene composite material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105601849A (en) * 2016-01-27 2016-05-25 安徽猎塔电缆集团有限公司 Insectbite-proof environment-friendly cold-resistant cable formula
CN106633292A (en) * 2016-11-30 2017-05-10 芜湖立创包装有限公司 Anti-corrosion plastic material composition, anti-corrosion plastic bottle and preparation method of anti-corrosion plastic bottle

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Application publication date: 20150902