CN104592662A - High-thermal-resistance expandable polystyrene (EPS) composition particles and preparation method thereof - Google Patents
High-thermal-resistance expandable polystyrene (EPS) composition particles and preparation method thereof Download PDFInfo
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Abstract
The invention relates to flame-retardant high-thermal-resistance expandable polystyrene (EPS) composition particles with excellent heat-insulating property and a preparation method of the composition particles. Specifically, the expandable polystyrene composition particles disclosed by the invention contain ingredients, such as polystyrene, hard carbon particles, a physical foamer and an optional flame retardant. The preparation method of the expandable polystyrene composition particles comprises the steps of thoroughly mixing all the ingredients in an extruder or static mixer, then, cooling and granulating. The expandable polystyrene composition particles with high thermal resistance and high flame retardance, disclosed by the invention, are prepared from materials, such as coal- or petroleum-based oxidized asphalt, plant fibers and polymer base material resin, by a simple process.
Description
Technical field
The present invention relates to a kind of fire-retardant expandable polystyrene composition particle (EPS) with excellent thermal insulation performance, and preparation method thereof.
Background technology
Expandable polystyrene particle (EPS) is the granules of polystyrene containing pneumatogen, this polymer beads to expand and after slaking through heating pre-sending out, hot briquetting is required styrofoam in a mold, the expansion ratio of these foams can reach 20 ~ 80 times, has the constructional feature of fine closed pore.
Expandable polystyrene particle (EPS) foams the foam board made owing to having excellent lasting heat insulation property, is thus widely used in field of thermal insulation such as building, freezer, refrigerator cars.Adopt the external wall insulating layer of polystyrol plastic foam plate material, realize building energy conservation, improve the thermal environment quality in hot-summer and cold-winter area residential building, improve efficiency of energy utilization simultaneously.In order to construction and installation safety, the eps foam plate for building flame retardant regulation requirement that also demand fulfillment is relevant.
In order to improve the effect of building energy conservation environmental protection further, reduce building energy consumption, industry member is being developed always has higher thermal resistance and environmental protection flame retardant lagging material with low cost, and new production technique.
Propose at patent documentation 1, carbon black is directly joined in General Purpose Polystyrenre resin (GPPS), then manufacture expandable styrene particle (EPS) by plastic extrusion machinery.But what adopt in this invention is the carbon black of 10 ~ 100nm, from invention actual effect, needs the nano-particle carbon of interpolation 10%, thermal conductivity (improving thermal resistance more than 10%) obviously could be reduced.The addition of the carbon black inorganics of 10% can reduce the elasticity of EPS foam, reduces the mechanical property of foaming plate; Simultaneously in this patent, EPS is in extrusion, and the temperature of forcing machine section only has 95 DEG C, and the temperature of mould only has 65 DEG C, and under this temperature condition, GPPS resin is difficult to processing, and the resin extruded temperature processing of common GPPS is generally 140 ~ 260 DEG C.So the extrusion molding mentioned in this patent produces EPS, be also difficult to extensive continuous and stable production.
Patent documentation 2 proposes, graphite can be dispersed in general purpose polystyrene GPPS resin by forcing machine, so graphite granule is first become the GPPS particulate of graphitiferous by this patent with GPPS extruding pelletization, again by the GPPS particle suspension of above-mentioned graphitiferous in water, the monomer of styrene-based is added and other aromatic hydrocarbons carry out seeding polymerization to prepare polymerisate in water, and infiltrate by adding whipping agent, obtain final EPS particle.Although the method part avoids the problem that graphite cannot evenly effectively disperse, graphite is dispersed in GPPS by processing step extrusion molding, and then aggregates into final EPS with suspension polymerization, and the process costs of two-step approach is very high.
The additive that patent documentation 3 proposes to select to be applicable to reduce thermal conductivity is carbon granule, such as carbon black and graphite.The carbon black of all conventional grades is all suitable, and preferable particle size is the carbon black of 80 ~ 120nm.The consumption of carbon black preferably 2 ~ 10 % by weight.Also propose in this patent to introduce water as whipping agent, graphite is particularly suitable, and preferred median size is 0.5 ~ 200 μm, more preferably 1 ~ 25 μm, particularly 2 ~ 20 μm.But water is as whipping agent, has the residual of moisture in the abscess of goods, the thermal resistance of final foaming product can be reduced, in this patent, do not provide concrete thermal resistance data.
From current industrialization technology present situation, improve thermal resistance and realize basically by interpolation graphite or carbon black pellet.But graphite is a kind of very expensive material, and natural graphite (degree of graphitization is greater than 80%) resource is day by day exhausted, and the manufacturing processed energy consumption of synthetic graphite is high.Natural graphite is by the sedimentogeneous rock being rich in organic matter or carbonaceous, under special geologic condition, through what could be formed in up to ten million year, belong to non-renewable precious resources, natural graphite can deep processing be lithium ion battery negative, widespread use and power truck and consumer electronics power supply, so industry member strengthens all day by day to the demand of natural graphite and consumption, price is more and more expensive.As everyone knows; organism will need the high temperature sintering through 2000 ~ 3000 DEG C to form graphite-phase; namely basic Carbon Materials need more than 2000 ~ 3000 DEG C; and be in the special ultrahigh-temperature stove under protective atmosphere; sintering even a couple of days a few hours; just can obtain the higher synthetic graphite of degree of graphitization (degree of graphitization is greater than 60%), so synthetic graphite production energy consumption and cost are all very high.
Although carbon black low price, but channel process of the prior art, furnace treated black, direct production be all nano level very fine particle, when running into long wavelength's (5 ~ 100 microns) infrared rays in temperature-30 ~ 50 DEG C of blackbody radiations, according to the principle of Rayleigh scattering and Mie scattering, such nano-particle carbon is very weak to the infrared absorption of this kind of longer wavelength, addition to 10% can only be strengthened and just can have obvious absorption, adding of a large amount of inorganic additive, abscess quality after meeting obvious reduction EPS is shaping, there is no elasticity, easy shrinkage cavity distortion.
Patent documentation 1:EP0372343A1
Patent documentation 2:CN101353439A
Patent documentation 3:CN1484666A
Summary of the invention
the problem that invention will solve
Carrying out the present invention to solve the above-mentioned problems in the prior art, the object of the invention is by the most frequently used material and simple technique, produce high thermal resistance, high flame retardant, the mechanical good expandable polystyrene composition particle of abscess.
for the scheme of dealing with problems
According to a specific embodiment of the present invention, a kind of fire-retardant expandable polystyrene composition particle of high thermal resistance is provided, contains in described composition grain:
A) general purpose polystyrene,
B) median size is the hard charcoal particle of 0.5 ~ 100 micron,
C) pneumatogen.
Described composition grain can also comprise one or more following components further:
D) can with other fluoropolymer resins of polystyrene blend,
E) fire retardant,
F) cell modifiers such as nucleator,
G) infrared reflection agent is as hollow glass micropearl and/or drift pearl,
H) antioxidant,
I) photostabilizer,
J) compatilizer.
In the embodiment of the application, by above-mentioned various component, by fully mixing in forcing machine or static mixer, then cooling granulation, can obtain the fire-retardant expandable polystyrene composition particle of high thermal resistance of the present invention.
According to another embodiment of the present invention, the weight-average molar mass of described general purpose polystyrene is 40000 ~ 800000g/mol, is preferably 110000 ~ 450000g/mol.
According to another embodiment of the present invention, the material that described hard charcoal particle is originated by one or more basic charcoals of oil, coal, vegetable fibre, polymeric matrix resins (as epoxy resin, resol, acrylic resin, polyolefin resin etc.) forms at 200 ~ 2000 DEG C of sintering, median size is preferably 0.5 ~ 45 micron, particularly preferably 1 ~ 15 micron; Carbon content higher than 60 quality %, preferably higher than 90 quality %; Addition is 0.1 ~ 15 quality %, is preferably 1.5 ~ 5 quality %.
According to the specific embodiment of the present invention, pneumatogen is C4 ~ C8 volatile alkane or halohydrocarbon or their combination, be preferably the mixture of Skellysolve A, iso-pentane, pentamethylene, normal hexane etc., usage quantity is 3 ~ 15 quality %, be preferably 3 ~ 9 quality %, most preferably be 3 ~ 7 quality %.
In addition, in Expandable Polystyrene (EPS) combination of the present invention, the resins such as polyphenylene oxide, acrylonitrile-butadiene-styrene copolymer, polyethylene, polyester, impact resistant polystyrene (HIPS) can be blended into; The compatilizers such as Methacrylate-butadiene-styrene, styrene-ethylene-butylene-styrene block copolymer, hydrogenated styrene isoprene segmented copolymer, grafted polyethylene or their combination can be added simultaneously.Preferred addition is 2 ~ 35 quality %.The particularly preferably blended temperature tolerance adding polyphenylene oxide raising material, preferably blended water-repellancy and the chemical proofing adding polyethylene raising material.
Again on the one hand, described in Expandable Polystyrene (EPS) combination of the present invention, institute's fire retardant can adopt the fire retardant based on bromine, as hexabromocyclododecane, tetrabromo cyclooctane, ethylene tetrabromide butylcyclohexane, 2,2' bis-(4-allyloxy-3,5-dibromo phenyl) propane or tribromo phenyl allyl ether, brominated styrene-butadiene-styrene block copolymer etc., preferred bio-toxicity is lower, the better brominated styrene-butadiene-styrene block copolymer of thermostability.The addition of bromide fire retardant is 0.1 ~ 5 quality %, is preferably 0.5 ~ 2.5 quality %.Can also select to add the bromine-free flame-retardant agent such as red phosphorus, phosphoric acid ester, magnesium hydroxide, expansible black lead, nitrogen is Phosphorus.Described non-bromine series fire retardant is preferably red phosphorus, magnesium oxide, magnesium hydroxide.The addition of described non-bromine series fire retardant is 0.1 ~ 5 quality %, is preferably 0.5 ~ 2.5 quality %.Above-mentioned fire retardant can be single or combinationally use.
In addition, in Expandable Polystyrene (EPS) combination of the present invention, also can be blended into nucleator and regulate abscess-size, as polyethylene wax, ethylenebis stearylamide, calcium carbonate, calcium stearate, clay, nano imvite, silicon-dioxide, diatomite, citric acid and common flaky inorganic thing talcum powder, mica etc., addition is 0.1 ~ 4 quality %.
According to the embodiment of the present invention, the thermal resistance adding the Expandable Polystyrene (EPS) that can further improve in the present invention of hollow glass micropearl and/or drift pearl, be preferably hollow glass micropearl, addition is 0.1 ~ 10 quality %, preferred addition is 0.1 ~ 5 quality %, is particularly preferably 0.5 ~ 2 quality %.
In Expandable Polystyrene (EPS) combination of the present invention, the aging antioxidant that the factors such as light, heat, oxygen can be suppressed further to cause can also be blended into, as antioxidant B225, and prevent Expandable Polystyrene (EPS) uviolize occur degraded solarization photostabilizer.The invention still further relates to a kind of method manufacturing the fire-retardant expandable polystyrene composition particle of high thermal resistance of the present invention, each component of the fire-retardant expandable polystyrene composition particle of the high thermal resistance of composition is passed through fully to mix in forcing machine or static mixer by described method, then cooling granulation, can obtain the fire-retardant expandable polystyrene composition particle of high thermal resistance of the present invention.
the effect of invention
The fire-retardant expandable polystyrene composition particle of high thermal resistance of the present invention and its manufacture method, overcome the interpolation of a large amount of carbon black, graphite in prior art to the disadvantageous effect of the stability and mechanical property that maintain fretting map sheet material inner cell microtexture.Feedstock treating of the present invention and manufacturing process simply, have saved process costs.Meanwhile, owing to can control patterns such as the particle diameter of carbon raw material, shapes in manufacturing processed, therefore, the problem that in prior art, graphite flake effectively cannot disperse in suspension polymerization is overcome.The present invention, by the most frequently used material and simple technique, obtains the expandable polystyrene composition particle of high thermal resistance, high flame retardant, abscess satisfactory mechanical property.
Embodiment
Expandable polystyrene composition of the present invention, its base resin is general purpose polystyrene GPPS, and its weight-average molar mass Mw is: 40000 ~ 800000g/mol, is preferably 110000 ~ 350000g/mol.
The present invention adopts the material in one or more basic charcoal sources of coal-based or petroleum-based oxidized bitumen with low cost, vegetable fibre, polymeric matrix resins (as epoxy resin, resol, acrylic resin, polyolefin resin etc.), in 500 ~ 1800 DEG C under low temperature, through the sintering of a few hours, remove the volatile material (element such as sulphur, phosphorus and volatile small molecule) being unfavorable for polymer processing, suitable unformed Carbon Materials (hard charcoal particle) can be obtained.This hard charcoal particle sieves through levigate, obtains the particle that diameter is 0.5 ~ 100 micron.The hard charcoal particle of micron level is joined in general purpose polystyrene GPPS, although the order of carbon atom arrangement is also very poor in such charcoal particle, i.e. most of space structure or turbostratic arrangement, be different from three-dimensional space ordered arrangement that is natural or synthetic graphite, but infrared rays can be absorbed well equally.Because charcoal particle diameter is micron level, not only save production process energy consumption, and compare nano level carbon black and have and better absorb ultrared effect.
Prepare in the process of this micron order charcoal particle, the sphericity of particle can be controlled, the hard charcoal particle that sphericity is high, easilier to disperse in general purpose polystyrene GPPS.The charcoal particle of such pattern, to the maintenance of the ultrared absorption of multi-angle and the mechanical property to end article abscess, is all better than the graphite packing of sheet.
As everyone knows, graphite itself is extraordinary heat conductor, the graphite flake thermal conductivity of high graphitization degree is greater than 100W/ (mk), is usually used in adding in plastics the thermal conductivity improving plastics, or directly does the radiator element of slabbing as consumption electronic products such as mobile phones.So in Expandable Polystyrene (EPS) EPS, although add graphite can improve thermal resistance by absorbing infrared rays, the heat-conduction coefficient of the direct contact of EPS can be improved to a certain extent, unfavorable to insulation.The unformed Carbon Materials (hard charcoal particle) that the present invention adopts, degree of graphitization is very low, does not also form fairly regular carbon atom arrangement to provide heat conduction via, and the thermal conductivity of itself is far below graphite.
The infrared absorbing agents that the present invention adds, preferably hard charcoal particle, median size is 0.5 ~ 45 micron, particularly preferably 1 ~ 15 micron; Carbon content higher than 60 quality %, preferably higher than 90 quality %; Addition is 0.1 ~ 15 quality %, is preferably 1.5 ~ 5 quality %.
In high thermal resistance expandable polystyrene composition particle (EPS) of the present invention, glass microballon (solid or hollow) can also be added, fly ash float etc. that thermal power generation produces has obvious reflex action inorganics to infrared rays, improve thermal resistance further.Particularly hollow glass micropearl, not only strong to infrared-reflecting power, and its hollow structure is conducive to reduce further thermal conduction rate, strengthen effect of heat insulation, be preferably 1 ~ 50 micron of hollow glass micropearl, addition is 0.1 ~ 10%, and preferred addition is 0.1 ~ 5%, is particularly preferably 0.5 ~ 2%.Hollow glass micropearl and fly ash float are all the materials being difficult to burn, also helpful to the flame retardant resistance improving foam.
The fire-retardant expandable polystyrene composition particle (EPS) of high thermal resistance of the present invention, also comprises other conventional auxiliary agents as whipping agent, fire retardant, nucleator, acid scavenger, antioxidant, photostabilizer, softening agent, coating agent, other macromolecule resin and compatilizers etc. thereof.
Whipping agent can adopt C4 ~ C8 whipping agent, comprises butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane, pentamethylene and halohydrocarbon etc.Be preferably the mixture of Skellysolve A, iso-pentane, pentamethylene, normal hexane etc., usage quantity is 2 ~ 15%, is preferably 3 ~ 9%, more preferably 3 ~ 7%.
Fire retardant can adopt the fire retardant based on bromine, as hexabromocyclododecane, tetrabromo cyclooctane, ethylene tetrabromide butylcyclohexane, 2,2'-bis-(4-allyloxy-3,5-dibromo phenyl) propane or tribromo phenyl allyl ether etc., preferred bio-toxicity is lower, the better brominated styrene-butadiene-styrene block copolymer of thermostability.In order to reach flame retardant rating B1, the addition of bromide fire retardant is 0.1 ~ 5 quality %, is preferably 0.5 ~ 2.5 quality %.Can also select to add the bromine-free flame-retardant agent such as red phosphorus, phosphoric acid ester, magnesium hydroxide, expansible black lead, nitrogen is Phosphorus.Above-mentioned fire retardant can be single or combinationally use.
The adjustable abscess-size of nucleator, can adopt polyethylene, polyethylene wax, ethylenebis stearylamide, calcium carbonate, calcium stearate, clay, nano imvite, silicon-dioxide, diatomite, citric acid and common flaky inorganic thing as talcum powder, mica, graphite etc.Addition is 0.1 ~ 4 quality %.
Acid scavenger in polymer processing can adopt conventional calcium stearate, Zinic stearas, magnesium hydroxide etc.
In order to improve the various performance such as high temperature resistant, chemical-resistant resistance, rebound resilience, interface weldability, water-repellancy of Expandable Polystyrene (EPS), can in above-mentioned expandable polystyrene resin other fluoropolymer resins blended, as resins such as polyphenylene oxide, acrylonitrile-butadiene-styrene copolymer, polyethylene, polyester, HIPS; The compatilizers such as Methacrylate-butadiene-styrene, styrene-ethylene-butylene-styrene block copolymer, hydrogenated styrene isoprene segmented copolymer, grafted polyethylene can be added simultaneously.Above-mentioned substance content is generally less than 50%, is preferably 2 ~ 35%.Particularly preferably the blended polyphenylene oxide that adds is to improve the temperature tolerance of material, and preferably the blended polyethylene that adds is to improve water-repellancy and the chemical proofing of material.
Above-mentioned all kinds of auxiliary addition agent, together with general purpose polystyrene resin GPPS, directly in forcing machine or static mixer, melting fully mixes, and obtains high thermal resistance and fire-retardant expandable polystyrene composition grain (EPS) by supercharging granulation underwater subsequently.In forcing machine or static mixer, the mixing temperature of each material is 120 ~ 280 DEG C, and be preferably 130 ~ 240 DEG C, the water temperature of granulation is 20 ~ 80 DEG C, is preferably 35 ~ 65 DEG C, and the size control of blank, at 0.4 ~ 2mm, is preferably 0.8 ~ 1.2mm.
Above-mentioned expandable polystyrene composition particle, through water vapour pre-frothing conventional in the industry and compression molding, can obtain density is 10 ~ 100kg/m
3foam article, for the EPS panel density of building heat preservation, generally preferred 10 ~ 40kg/m
3.
In order to prevent pre-frothing stage adhesion caking, being convenient to High temperature release, improving shaping speed, can at the mixture of the silicate of above-mentioned EPS SiC p surface plating stearate, glyceryl ester and superfine grinding, this mixture is commercially available conventional EPS coating agent.
Embodiment 1:
By the oxidized bitumen of Coal Chemical Industry or petrochemical complex by product, added after pulverizing in tube furnace, in air atmosphere, be warming up to 250 ~ 350 DEG C, be cured, asphalt powder after solidification is added in charring furnace, in a nitrogen atmosphere, be warming up to 700 ~ 1300 DEG C and carry out charing process, obtain the hard charcoal particle of pitch, hard for this pitch charcoal particle screen selecting is decomposed, select 5 ~ 10 microns of hard charcoal particles as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, the median size that the above-mentioned sintering of 5 quality % obtains about 5 ~ 10 microns of hard charcoal particles of pitch.
At 200 DEG C, mix continuously in forcing machine or static mixer, it is 10 minutes that mixing time controls;
Be cooled to 180 ~ 185 DEG C, extruding pelletization becomes the expandable polystyrene particle containing whipping agent and fire retardant, median size 1.0mm.
After applying commercially available antistatic and anti EPS coating-forming agent, carry out pre-frothing and compression molding with industry universal equipment, the density controlling product sheet material is 18kg/m
3.
Subsequently, flame retardant resistance and the thermal conductivity of sheet material is assessed.
According to GB test flame retardant resistance (GB8624-2006) and thermal conductivity (GB/T 1080.1-2002).Thermal conductivity is less, thermal resistance is better, and effect of heat insulation is better, it has been generally acknowledged that EPS has better effect of heat insulation when being less than 33mW/ (mk), and think that effect of heat insulation is very excellent when EPS is less than 30mW/ (mk), when being greater than 33mW/ (mk), effect of heat insulation is poor.
Should contain the black expandable polystyrene composition grain of the hard charcoal particle of pitch, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 30mW/ (mK).The foaming plate abscess made is evenly fine and closely woven, not only has higher thermal resistance (lower thermal conductivity), equally also demonstrates lower shrinkability and good dimensional stability
Embodiment 2:
As embodiment 1, prepare the hard charcoal particle of pitch, choosing median size is that the particle of 5 ~ 10 microns is as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=180000g/mol), the pentane foaming agent of 5 quality % content, brominated styrene-the butadiene-styrene block copolymer of 2.5 quality % content, the hard charcoal particle of 5 ~ 10 microns of pitches that the above-mentioned sintering of 5 quality % obtains.In an extruder at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandability black polystyrene composition grain that median size is 1.0mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
Should contain the black expandable polystyrene composition grain of the hard charcoal particle of pitch, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 30mW/ (mK).The foaming plate abscess made is evenly fine and closely woven, not only has higher thermal resistance (lower thermal conductivity), equally also demonstrates lower shrinkability and good dimensional stability.
Embodiment 3:
As embodiment 1, the hard charcoal particle of pitch of preparation median size 5 ~ 10 microns.
By general purpose polystyrene GPPS (Mw=280000g/mol), the pentane foaming agent of 6 quality % content, 1.5 the brominated styrene-butadiene-styrene block copolymer of quality % content, the hard charcoal particle of pitch that the above-mentioned sintering of 5 quality % obtains, the hollow glass micropearl of the median size 30 microns of 0.5 quality % content, the polyphenylene oxide (PPO) of 15% mass percentage, the antioxidant B225 (hindered phenol 1010 and phosphorous acid ester 168 mixture) that 0.1 quality % is commercially available.In static mixer at 220 DEG C of temperature, fully mix, be cooled to 180 ~ 215 DEG C, be then a granulated into the black expandable polystyrene composition grain that median size is 1.0mm.
By this expandable polystyrene composition particle, in pre-frothing and the moulding press making sheet of routine, pre-frothing compares traditional E PS with molding temperature, all will slightly do to improve, and the density controlling foaming product is 30kg/m
3, test foaming product flame retardant rating is B1 and thermal conductivity is 29mW/ (mK), and the heat-drawn wire of foam improves 10 DEG C, and temperature resistant grade significantly improves.
Embodiment 4:
As embodiment 1, the hard charcoal particle of pitch of preparation median size 5 ~ 10 microns.
By general purpose polystyrene GPPS (Mw=320000g/mol), the pentane foaming agent of 6 quality % content, 1.5 the brominated styrene-butadiene-styrene block copolymer of quality % content, 0.2 quality % red phosphorus, 0.2 quality % magnesium hydroxide, the hard charcoal particle of micron pitch that the above-mentioned sintering of 4.5 quality % obtains, median size 30 microns of hollow glass micropearls of 1%, 0.5 quality % coal fly ash hollow micro bead (drift pearl).In static mixer at 200 degree of temperature, mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the black expandable polystyrene composition grain that median size is 1.0mm.
By this expandable polystyrene composition particle, in pre-frothing and the moulding press making sheet of routine, the density controlling foaming product is 20kg/m
3, test flame retardant rating is B1 and thermal conductivity is 29mW/ (mK).
Embodiment 5:
As embodiment 1, the hard charcoal particle of pitch of preparation median size 5 ~ 10 microns.
By general purpose polystyrene GPPS (Mw=280000g/mol), the iso-pentane whipping agent of 6 quality % content, brominated styrene-the butadiene-styrene block copolymer of 2 quality % content, 0.3 quality % red phosphorus, 1 quality % magnesium hydroxide, the hard charcoal particle of micron pitch that the above-mentioned sintering of 5 quality % obtains, 0.5 quality % talcum powder, the polyethylene of 5 quality %, 2 quality % styrene-ethylene-butylene-styrene block copolymers are as compatilizer.In an extruder at 160 DEG C of temperature, mix, be cooled to 180 ~ 205 DEG C and be then a granulated into the black expandable polystyrene composition grain that median size is 1.0mm.
By this black expandable polystyrene composition, in pre-frothing and the moulding press making sheet of routine, the density controlling foaming product is 25kg/m
3, test flame retardant rating is B1 and thermal conductivity is 30mW/ (mK), and the cohesiveness in foaming product between each expanded beads is better than common white expandable polystyrene particle, and the water-repellancy of foaming product improves; Simultaneously high resistance to chemicals medicine polyethylene component add the chemical proofing also improving foam itself.In acetone soln, the present embodiment is blended poly expandability EPS, and swelling speed is considerably slower than common expandability EPS.
Embodiment 6:
By the resol be cross-linked; carbonize in advance between 400 ~ 600 DEG C under protection of inert gas; pulverize afterwards, then obtain hard carbon particle about 1000 ~ 1500 DEG C thermo-crackings, finishing screen selects the hard charcoal particle of median size about 5 microns as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, 8 quality % are by the hard charcoal particle of median size about 5 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandable polystyrene particle that median size is 1.2mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The grey black expandable polystyrene composition particle of this hard charcoal particle, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 28mW/ (mK).The foaming plate abscess made is evenly fine and closely woven, and not only have higher thermal resistance (lower thermal conductivity), but also demonstrate lower shrinkability and better dimensional stability, a rear performance is very important for the manufacture of large-scale moulded piece.
Embodiment 7
Crosslinked epoxy resin is carbonized in advance at rare gas element, at 400 ~ 600 DEG C, pulverize afterwards, then obtain hard carbon particle about 1000 ~ 1600 DEG C thermo-crackings, finishing screen selects the hard charcoal particle of median size about 5 ~ 10 microns as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, the hard charcoal particle of 4.5 quality % median sizes about 5 ~ 10 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandable polystyrene particle that median size is 1.2mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The grey black expandable polystyrene composition particle of this hard charcoal particle, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 32mW/ (mK).Particle profile rule, the foaming plate abscess made is evenly fine and closely woven, and dimensional stability is better.
Embodiment 8
By rice husk (major ingredient of rice husk is the compound of Mierocrystalline cellulose, xylogen, silicon) in protective atmosphere; in programme controlled process furnace; carbonize at the temperature of 500 ~ 1200 DEG C, the rice husk after carbonization obtains rice husk hard carbon material through washing further, drying, pulverizing, screening.Choosing median size is that the hard carbon particle of 5 ~ 10 microns is as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=180000g/mol), the pentane foaming agent of 5 quality % content, brominated styrene-the butadiene-styrene block copolymer of 2.5 quality % content, the hard charcoal particle of 5 ~ 10 microns of pitches that the above-mentioned sintering of 6% mass content obtains.In an extruder, at the temperature of 200 DEG C, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandability black polystyrene composition grain that median size is 1.0mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The black expandable polystyrene composition grain of hard charcoal particle should be contained, after foaming, the flame retardant rating of goods is B1, thermal conductivity is 30mW/ (mK), the foaming plate abscess made is evenly fine and closely woven, not only there is higher thermal resistance (lower thermal conductivity), equally also demonstrate lower shrinkability and good dimensional stability.
Comparative example 1:
Prepare expandable polystyrene composition particle in accordance with the following steps:
Material prepares: general purpose polystyrene GPPS (Mw=220000g/mol), pentane foaming agent mass percentage 6%, fire retardant hexabromocyclododecane mass percentage 1.5%.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
Test result, this white expandable polystyrene foam board, fire-retardantly reaches B1 grade, thermal conductivity 39mW/ (mk).
Comparative example 2
Add in tube furnace after the oxidized bitumen of Coal Chemical Industry or petrochemical complex by product is pulverized, in air atmosphere, be warming up to 250 ~ 350 DEG C, be cured.Subsequently, the asphalt powder after solidification is added in charring furnace, in a nitrogen atmosphere, be warming up to 700 ~ 1300 DEG C and carry out charing process, obtain the hard charcoal particle of pitch.By hard for this pitch charcoal particle screen selecting processing, filter out the hard charcoal particle of median size about 0.1 micron as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, 4.5 quality % are by the hard charcoal particle of median size about 0.1 micron.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandable polystyrene particle that median size is 1.2mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The grey black expandable polystyrene composition particle of this hard charcoal particle, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 36mW/ (mK).The foaming plate abscess made is evenly fine and closely woven, has certain thermal resistance, also has certain shrinkability and dimensional stability.
Comparative example 3
Added in tube furnace after the oxidized bitumen of Coal Chemical Industry or petrochemical complex by product is pulverized, in air atmosphere, be warming up to 250 ~ 350 DEG C, be cured.Subsequently, the asphalt powder after solidification is added in charring furnace, in a nitrogen atmosphere, be warming up to 700 ~ 1300 DEG C and carry out charing process, obtain the hard charcoal particle of pitch.By hard for this pitch charcoal particle screen selecting processing, finishing screen selects the hard charcoal particle of median size about 10 microns as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, 0.08 quality % content is by the hard charcoal particle of median size about 10 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandable polystyrene particle that median size is 1.2mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The grey black expandable polystyrene composition particle of this hard charcoal particle, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 39mW/ (mK), and thermal conductivity is ordinary white Expandable Polystyrene (EPS) closely.
Comparative example 4
By the oxidized bitumen of Coal Chemical Industry or petrochemical complex by product, added after pulverizing in tube furnace, in air atmosphere, be warming up to 250 ~ 350 DEG C, be cured, asphalt powder after solidification is added in charring furnace, in a nitrogen atmosphere, be warming up to 700 ~ 1300 DEG C and carry out charing process, obtain the hard charcoal particle of pitch, decomposed by hard for this pitch charcoal particle screen selecting, finishing screen selects the hard charcoal particle of median size about 50 microns as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6% mass content, the hexabromocyclododecane of 1.5 quality % content, 16 quality % content are by the hard charcoal particle of median size about 50 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, but because inorganic powder grains addition is too much in granulation process, very easily cause the blocking of granulating equipment, pelletizing becomes Regularia spherical continuously diameter cannot be about the single-size of 1.2mm, in a small amount of product collected, the profile also irregular of particle.Cannot pre-frothing and moulded board be carried out, and then fire-retardant and thermal conductivity cannot be tested.
Comparative example 5
By the coke of the very low cost that coal chemical industry is produced, ball mill pulverizing, the coke granule of screening median size about 5 ~ 100 microns, 1500 DEG C of vacuum pyrolysiss sinter to main body and have carbonized, and form unformed charcoal particle, fixed carbon content is higher than 90 quality %.Sulfur in coke, fugitive constituent and moisture etc. all directly eliminate, and no longer affect the processing of downstream polymerisation thing, finally filter out the particle of median size about 10 microns again as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, 0.1 quality % content is by the particle of median size about 10 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandable polystyrene particle that median size is 1.2mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The grey black expandable polystyrene composition particle of this particle, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 39mW/ (mK), and thermal conductivity is ordinary white Expandable Polystyrene (EPS) closely.
Comparative example 6
By the coke of the very low cost that coal chemical industry is produced, ball mill pulverizing, the coke granule of screening median size about 5 ~ 100 microns, 1500 DEG C of vacuum pyrolysiss sinter to main body and have carbonized, and form unformed charcoal particle, fixed carbon content is higher than 90 quality %.Sulfur in coke, fugitive constituent and moisture etc. all directly eliminate, and no longer affect the processing of downstream polymerisation thing, finally filter out the particle of median size about 50 microns again as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6 quality % content, the hexabromocyclododecane of 1.5 quality % content, 4.5 quality % are by the particle of median size about 50 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, be then a granulated into the expandable polystyrene particle that median size is 1.2mm.Carry out pre-frothing and moulded board as in Example 1, test fire-retardant and thermal conductivity.
The grey black expandable polystyrene composition particle of this particle, after foaming, the flame retardant rating of goods is B1, and thermal conductivity is 33mW/ (mK).But particle profile irregularity, the foaming plate abscess made is fine and closely woven uneven, affects the cohesiveness stability at shaping dimensional stability and interface.
Comparative example 7
By the coke of the very low cost that coal chemical industry is produced, ball mill pulverizing, the coke granule of screening median size about 5 ~ 100 microns, 1500 DEG C of vacuum pyrolysiss sinter to main body and have carbonized, and fixed carbon content is higher than 90 quality %.Sulfur in coke, fugitive constituent and moisture etc. all directly eliminate, and no longer affect the processing of downstream polymerisation thing, finally filter out the unformed charcoal particle of median size about 50 microns again as infrared absorbing agents.
By general purpose polystyrene GPPS (Mw=220000g/mol), the pentane foaming agent of 6% mass content, the hexabromocyclododecane of 1.5 quality % content, 16 quality % content are by the hard charcoal particle of median size about 50 microns.In static mixer at 200 DEG C of temperature, fully mix, be cooled to 180 ~ 205 DEG C, but because inorganic powder grains addition is too much in granulation process, very easily cause the blocking of granulating equipment, pelletizing becomes Regularia spherical continuously diameter cannot be about the single-size of 1.2mm, in a small amount of product collected, the profile also irregular of particle.Cannot pre-frothing and moulded board be carried out, and then fire-retardant and thermal conductivity cannot be tested.
The result of above-mentioned comparative example and embodiment is listed in table 1 respectively:
utilizability in industry
By the result of table 1, the effect of heat insulation demonstrating the foamed polystyrene board adding hard charcoal particle is obviously better than the foamed polystyrene board adding agraphitic carbon particle (coke is that raw material is formed), and the abscess adding the described polyethylene foam plate of hard charcoal particle is fine and closely woven evenly, shrinkability, excellent size stability.In addition, see embodiment 3 ~ 5, by the selection of suitable auxiliary agent, swelling rate can be reduced, the characteristic that the thermomechanical stability be improved, temperature resistant grade, water-repellancy, chemical proofing etc. are excellent.
In addition, based on table 1 demonstrate the addition of hard charcoal particle too high when (comparative example 4) final foamed board the profile irregular of particle, cannot pre-frothing and moulded board be carried out.And content too low when (comparative example 3), its thermal conductivity may be caused close to ordinary polystyrene foamed board.
The raw material sources that the application prepares hard charcoal particle are extensive, and it is with low cost, and relative working method is simple, its hard charcoal particle obtained obtains effect of heat insulation more excellent compared with infrared absorbent conventional with graphite, coke etc. as infrared absorbing agents, industry has applicability widely.
Claims (13)
1. an expandable polystyrene composition particle, is characterized in that containing:
A) polystyrene,
B) median size is the hard charcoal particle of 0.5 ~ 100 micron,
C) pneumatogen.
2. polyphenylacetylene combination particle according to claim 1, is characterized in that described hard charcoal particle is sintered at the temperature of 200 ~ 2000 DEG C by the material in one or more the basic charcoals sources be selected from coal-based or petroleum-based oxidized bitumen, vegetable fibre, polymeric matrix resins to be formed.
3. polyphenylacetylene combination particle according to claim 1, it is characterized in that the median size of described hard charcoal particle is 0.5 ~ 45 micron, carbon content is higher than 60 quality %.
4. polyphenylacetylene combination particle according to claim 1, is characterized in that described pneumatogen is C4 ~ C8 volatile alkane or C4 ~ C8 halohydrocarbon or their combination.
5. the polyphenylacetylene combination particle according to any one of Claims 1 to 4, it is characterized in that expandable polystyrene composition particle comprise further fire retardant, infrared reflection agent, compatilizer, cell modifiers, antioxidant and photostabilizer one or more.
6. the polyphenylacetylene combination particle according to any one of Claims 1 to 4, it is characterized in that expandable polystyrene composition particle comprise further can with other fluoropolymer resins of polystyrene blend.
7. polyphenylacetylene combination particle according to claim 5, it is characterized in that described fire retardant is bromine system and/or non-bromine series fire retardant, described bromide fire retardant is selected from hexabromocyclododecane, tetrabromo cyclooctane, ethylene tetrabromide butylcyclohexane, 2,2 '-two (4-allyloxy-3,5-dibromo phenyl) propane, tribromo phenyl allyl ether, brominated styrene-butadiene-styrene block copolymer, described non-bromine series fire retardant is selected from phosphoric acid ester, magnesium hydroxide, expansible black lead, nitrogen phosphorus type flame retardant.
8. polyphenylacetylene combination particle according to claim 5, is characterized in that described infrared reflection agent is hollow glass micropearl and/or drift pearl.
9. polyphenylacetylene combination particle according to claim 5, is characterized in that described compatilizer is selected from Methacrylate-butadiene-styrene, styrene-ethylene-butylene-styrene block copolymer, hydrogenated styrene isoprene segmented copolymer or grafted polyethylene.
10. polyphenylacetylene combination particle according to claim 5, is characterized in that described cell modifiers is selected from following nucleator: polyethylene wax, ethylenebis stearylamide, calcium carbonate, calcium stearate, clay, nano imvite, silicon-dioxide, diatomite, citric acid, talcum powder, mica.
11. polyphenylacetylene combination particles according to claim 6, is characterized in that other fluoropolymer resins described are selected from polyphenylene oxide, acrylonitrile-butadiene-styrene copolymer, polyethylene, polyester, impact resistant polystyrene.
The manufacture method of the polyphenylacetylene combination particle described in 12. any one of claim 1 ~ 11, is characterized in that described method comprises by each component by fully mixing in forcing machine or static mixer, the then step of cooling granulation.
13. manufacture method according to claim 12, it is characterized in that before described mixing step, the material in one or more the basic charcoal sources be selected from coal-based or petroleum-based oxidized bitumen, vegetable fibre, polymeric matrix resins is sintered the step forming hard charcoal particle at the temperature of 200 ~ 2000 DEG C.
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| CN105131617A (en) * | 2015-08-14 | 2015-12-09 | 山西省交通科学研究院 | Polystyrene hybrid material modified asphalt and preparation method thereof |
| CN105384877A (en) * | 2015-12-03 | 2016-03-09 | 绍兴文理学院元培学院 | Black expandable polystyrene resin synthesized by adopting seeding polymerization and preparation method thereof |
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