CN102643490B - Polystyrene resin foam board and manufacturing method thereof - Google Patents
Polystyrene resin foam board and manufacturing method thereof Download PDFInfo
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- CN102643490B CN102643490B CN201210149514.4A CN201210149514A CN102643490B CN 102643490 B CN102643490 B CN 102643490B CN 201210149514 A CN201210149514 A CN 201210149514A CN 102643490 B CN102643490 B CN 102643490B
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Abstract
The invention relates to a polystyrene resin foam board which is prepared by the following steps: preparing a compound polystyrene resin as a base, and a bubble nucleating agent, an antioxidant and a flame retardant as auxiliary materials into a polystyrene resin composition; and manufacturing the polystyrene resin foam board in an extrusion foaming device by an extrusion foaming method by using an supercritical CO2 foaming agent. The compound polystyrene resin is compounded from general purpose polystyrene which is obtained by mass polymerization and high-molecular-weight polystyrene in a mass ratio of 90:10-20:80, wherein the weight average molecular weight Mw of the general purpose polystyrene is 1.5-3.5*10<5>, the weight average molecular weight of the high-molecular-weight polystyrene is 4.5-7.5*10<5>, and the molecular weight distribution indexes Mw/Mn of the two polystyrenes are respectively less than or equal to 4. The foaming ratio of the polystyrene resin foam board is greater than 30 times, the open pore content is lower than 20%, the thickness exceeds 15cm, and the sectional area is greater than 1800cm<2>. The polystyrene resin foam board provided by the invention can be directly used in the fields of thermal insulation of building external walls, high-speed train roadbeds, runway roadbeds, airplane hangars, parking apron foundations and the like.
Description
Technical field
The present invention relates to a kind of sheet material, relate in particular to a kind of polystyrene resin foaming plate and manufacture method thereof.
Background technology
So far carry the polystyrol foam material of " white pollution " bad reputation, due in the difficult degradation of the occurring in nature utmost point, so the non-environmental protection material that is considered to pollute.Research shows that polystyrene material is embedded among the soil of North America, does not degrade for 60 years above.Can learn thus, its " white pollution " bad reputation should belong to and come into reality.So any product introduction of polystyrene foam packing is all forbidded strictly in countries in the world, it is domestic.But concept is changed, the defect of utmost point difficult degradation can become its advantage again, if be made into material of construction, perhaps degradation resistant and corrosion resistance nature do not have other plastics to be equal to it.
Very outstanding insulation, the heat-proof quality of polystyrene foam will make it among the cry of whole world energy-saving and environmental protection, low-carbon (LC), in energy-conservation, field of thermal insulation, yields unusually brilliant results.Polystyrene foamed material is very hydrophobic, when the closed pore polystyrene foam of making by extrusion foaming method (being called for short XPS) is used as buoyancy goods, even if stung riddled with gaping woundsly by sharp sword, also subtracts hardly its buoyancy in water.In addition its very excellent compressive property, for the security application field that is very easily subject to the bullet train roadbed of freezing and damage, express highway roadbed, airstrip roadbed, hangar and basis, hardstand in cold district, XPS has ample scope for one's abilities.
External wall of house is incubated and is subject to already noting very widely at World Developed Countries, and XPS is pursued in recent years especially.It is reported that world wide sales in 2011 reaches 50,000,000,000 Renminbi, Er China not yet starts to walk.Today the whole world all pursuing under the situation of energy-saving and environmental protection, low-carbon (LC), China ought to accomplish something.Under the traditional consumption theory of " not asking; only demand cheap ", the inorganic heat insulation material of mineral wool that the external wall of house insulation of China adopts at first and so on, however the original effect of this class lagging material is just very poor, once meet rain humidity, just become afterwards thermally conductive material, result is poorer than not being incubated.Some Enterprises turns to again and adopts the polyurethane foam that is easy to foaming later, but polyurethane foam also exists several deadly defects.Though first polyurethane foam is easy to foaming, whipping agent is mainly to select freonll-11 and react the CO generating with water
2.The former forbids owing to destroying the atmospheric ozone layer Er Bei world, and the latter exists again a large amount of consumption urethane and the waste problem that causes.In fact the heat insulation and preservation effect of expanded plastic is not decided by plastics itself, but depends on foamed gas, is whipping agent yet.What in all whipping agents, heat insulation and preservation effect was best is freonll-11, is secondly CO
2, under it, be followed successively by stable hydrocarbon, ethers, alcohols, the poorest is water.In addition price is high, to produce not environmental protection of the utmost point be also one of disadvantage of polyurethane foam, once but the most fatal problem is polyurethane foam catches fire, can decomposite hypertoxic prussic acid, and this is also the one of the main reasons that Jiangzhou road, Shanghai fire causes casualties.Although also there is the material of many employing polystyrene bead foaming, referred to as EPS, the former packaging field that is mainly used in.Although this material is easy to preparation, because being forms by expanded bead welding, so bead is very easily separated, main is that rainwater and moisture are easy to go deep into material by bead interface, and material heat insulation and preservation effect is destroyed.The mechanical property of material own is also very poor, makes that it can not be incubated at external wall of house, the field such as bullet train roadbed, airstrip roadbed, hangar and basis, hardstand accomplishes something.The closed pore polystyrene foam (XPS) energy-conservation, that the non-extrusion foaming method of heat-insulating construction material is made of visible a new generation has not belonged to.
Since XPS has so development prospect, the colleges and universities, scientific research institutions and the enterprise that are devoted to research and development are also just many.For example BASF Aktiengesellschaft has applied for International PCT patent, and enters China application in 2001.6, and publication number is CN 1143877C.This disclosure of the invention adopt 1-12wt% without the expanded graphite of top coat as whipping agent, 1-12wt% Halogen phosphide, extrusion foaming, obtaining density is 20-200g/l, sectional area is 50cm at least
2polystyrene foam.2011.6 applications, publication number are that the file of CN 102127269A discloses a kind of flame resistant method that is coated in Foam Plastic Surface after will organic fire-retardant fusing.The file that 2011.11 applications, publication number are CN102229271A discloses a kind of method that adopts polypropylene to make the foamed polystyrene sandwich panel of coating layer.2009.9 publication numbers are that the file of CN 101518941A discloses a kind of two steps type extruder system, prepare the production method of insulating pipe.Yet these inventions do not relate to core technology and key that XPS manufactures.
Japan JSP company produces the enterprise the most well-known with manufacturing each type of foam in the world, has made great efforts untiringly since all the year round in the manufacture field of plastic foam material always, can clearly see the pulse of the said firm's technology growth in XPS field.2002.6.18 in China, applied for two parts of patents of invention, application number is respectively 02122879.5 and 02122878.7 simultaneously.In 02122879.5, for replace destroying fluorochlorohydrocarbon or the hydrofluoric ether of the freonll-11 and so on of atmospheric ozone layer, a kind of employing Trimethylmethane and other blowing agent blends are disclosed as whipping agent, to extrude more than thickness reaches 10mm, apparent density is at 25-60kg/m
3scope, the technology of the good foamed polystyrene plates of bubble deformation rate between 0.7-1.2, and be authorized in 2003.1.29.02122878.7 due to quite similar with foregoing, is not authorized.2003.3.17 the patent that application number is 03154516.5 discloses take Trimethylmethane as main (20-70wt%), adds a small amount of fatty alcohol (1-4wt%) and (5-50wt%) CO
2deng the mixed foaming agent forming, and provided 7>=fatty alcohol/CO
2>=0.5 relational expression, prepares the technology of polystyrene foam, and is authorized by extrusion foaming.
By above-mentioned analysis, can be learnt, although using freonll-11, as whipping agent, in heat insulation, insulation, fire-retardant several respects, all have overwhelming superiority, yet it destroys the critical defect of atmospheric ozone layer, be doomed that it must obtain and exits whipping agent ranks completely.Although at present many small molecules aliphatic hydrocarbons that adopt replace freonll-11 example, have avoided destroying the defect of atmospheric ozone layer, but greatly inferior aspect heat insulation, heat insulation effect.What is more important greatly reduces the flame retardant properties of foam materials, has become a new major defect.The most rising visible whipping agent should be exactly CO
2, it not only will obviously be better than small molecules aliphatic hydrocarbon aspect heat insulation, heat insulation effect, the more important thing is CO
2also give the flame retardant properties that foam materials is good.Yet with CO
2as whipping agent, but not simple.At plastic foamed temperature, must make CO
2can be as whipping agent in supercritical state, pressure now must surpass 10-15MPa.So, CO
2explosive power just quite large, the melt strength of resin is required also just very high.In addition, due to CO
2relative weak with the consistency of resin for small molecules aliphatic hydrocarbon, thereby have higher one-tenth nuclearity, the number of abscess is much bigger, is easy to form micropore, but is not easy to form high foamability.Visible employing supercritical CO
2as whipping agent, in technical difficulty, require very high.
Japan JSP company is on the basis of its early-stage Study, and 2005.4.26 has applied for the patent of invention that application number is 200510067745.0.The manufacture method that discloses polystyrene resin foams, depth of foam is at least 10mm, and transverse cutting area is at least 50cm
2, performance density is 20-35kg/m
3.It is characterized in that: carry out extrusion foaming, use the Z-average molecular weight of this polystyrene resin foam by extrusion of gel permeation chromatography and the ratio Mz/Mn of number-average molecular weight 8.0 or more than.The resin compound obtaining for molecular weight distribution different 2 kinds or above polystyrene resin melting mixing.Can see, in order to obtain good foam, Japanese JSP company has noted the melt strength of matrix resin more.In order to realize this goal, 200510067745.0 by by NMPS, (polystyrene resin of general molecular weight, weight-average molecular weight Mw is 1.5 * 10
5-3.0 * 10
5) (polystyrene with super-high molecular weight, Z-average molecular weight Mz is 6.5 * 10 for 100 weight parts and UHPS
5-2.0 * 10
6) the 0.5-40 weight part melting mixing method of making masterbatch realizes.Obviously, the melt strength of NMPS is not enough, adopts part UHPS to carry out reinforcement.From 200510067745.0 and polymer chemistry general knowledge, such UHPS must adopt the method for letex polymerization to manufacture.Thus, a large amount of residual small molecules tensio-active agents not only produce a very large impact for the flame retardant properties of foam materials, and make UHPS and NMPS be difficult to miscible, add the greatest differences existing on both molecular weight, even if adopt melting mixing to make the mode of masterbatch, also difficult that both are well together compatible.To such an extent as to 200510067745.0 also think that the consumption of UHPS is too much, mobility variation during melting mixing, possibly cannot fully carry out coolingly, and gained foam by extrusion may form thick bubble, and this is obviously the bad performance of consistency in fact.Thereby such method is obviously not reach employing supercritical CO
2as whipping agent, prepare that high quality XPS requires.
Summary of the invention
Object of the present invention, exactly in order to address the above problem, provides a kind of employing supercritical CO
2polystyrene resin foaming plate and the manufacture method thereof as whipping agent, manufactured.
In order to achieve the above object, the present invention has adopted following technical scheme: a kind of polystyrene resin foaming plate, take composite polystyrene resin as matrix, and be aided with bubble nucleating agent, oxidation inhibitor and fire retardant and be made into polystyrene resin composite, adopt supercritical CO
2whipping agent, adopts the manufacture of extrusion foaming method to form by extrusion foaming device;
Described polystyrene resin foaming plate has the expansion ratio that is greater than 30 times, and open cell content is lower than 20%, and thickness surpasses 15cm, and sectional area is greater than 1800cm
2;
Described composite polystyrene resin is composite the obtaining of mass ratio by 90: 10～20: 80 by the general purpose polystyrene that adopts the polymerization of mass polymerization mode to obtain and high molecular weight polystyrene, and the weight-average molecular weight Mw of general purpose polystyrene is 1.5 * 10
5-3.5 * 10
5, the weight-average molecular weight Mw of high molecular weight polystyrene is 4.5 * 10
5-7.5 * 10
5, the molecular weight distributing index Mw/Mn of two kinds of polystyrene all≤4.
Described composite polystyrene resin shows obvious tension strain sclerosis behavior under blowing temperature, simultaneously at 1s
-1rate of extension under, the critical fracture value of melt tension strain surpasses 1.5, and tensile stress σ
emeet dln σ with the relation of tensile deformation ξ
e/ d ξ > 0.5.
The consumption of composite polystyrene resin of take is 100 weight parts, and the consumption of bubble nucleating agent is 0.1-25 weight part, and the consumption of oxidation inhibitor is 0.2-1 weight part, and the consumption of fire retardant is 2-30 weight part, supercritical CO
2the consumption of whipping agent is 5-20 weight part.
Described supercritical CO
2whipping agent is by supercritical CO
2constitute blowing promotor and supercritical CO with blowing promotor
2mass ratio be 0～20: 100～80, blowing promotor is selected from one or several in dme, diethyl ether, methyl ethyl ether, methylvinylether, methyl chloride, monochloroethane, methyl alcohol, ethanol, water, butane, pentane, Trimethylmethane.
Described fire retardant is selected from hexabromocyclododecane, poly-bromstyrol, dibromoneopentyl glycol, tetrabromo-bisphenol, tetrabromophthalate glycol, tetrabromo phenol, poly-pentabromobenzyl acrylate, clorafin, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, hexachloro endoethylene tetrahydrophthalic acid, triallyl phosphate, alkyl allyl group phosphoric acid ester, alkyl phosphate, bromophosphonate, chlorinated phosphate, phosphoric acid is narrowed base urea, polyphosphonitrile, phosphamide, Tripyrophosphoric acid amine, red phosphorus, barium metaborate, zinc borate, melamine phosphate, phosphoguanidine, melamine prepolymer, trimeric cyanamide, melamine cyanurate, tetrazolium class, stannic oxide, aluminium hydroxide, weisspiessglanz, molybdenum oxide, ammonium molybdate, zirconium white, zirconium hydroxide, aluminium hydroxide, magnesium hydroxide, one or several in calcium plumbite.
Described bubble nucleating agent is selected from one or more in talcum powder, kaolin, mica, silicon-dioxide, glass, quartz, calcium carbonate, carbon black, magnesium oxide, zinc oxide, aluminum oxide, titanium oxide, barium sulfate, Attapulgite, polynite, clay, wilkinite, diatomite, and the particle diameter of bubble nucleating agent is 300～5000 orders.
Described oxidation inhibitor is selected from 2,6-di-t-butyl-4-ethylphenol, 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4,6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215, oxidation inhibitor B225, four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, ethylenebis (oxygen ethylidene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic acid] ester, 1,3,5-tri-(3,5-tertiary butyl-4-hydroxy benzyl)-1,3,5 triazine-2,4,6 (1H, 3H, 5H)-triketones, 2,6-di-t-butyl-4-(4,6-bis-(octyl group sulphur)-1,3,5-triazines-2-base is amino) phenol, tricresyl phosphite (2,4 tri-tert phenyl) ester, one or more in 5,7-di-t-butyl-3-(3,4-3,5-dimethylphenyl)-3H benzofuran-2-ones.
The manufacture method of above-mentioned polystyrene resin foaming plate, adopts extrusion foaming method to manufacture by extrusion foaming device; Described extrusion foaming device comprises forcing machine, is equipped with the metered charge mechanism of polystyrene resin composite and the injection metering mechanism of whipping agent on forcing machine, is equipped with and can makes polystyrene resin composite and supercritical CO
2the strong solution of whipping agent fully mixes, cooling static mixer, is equipped with and can makes supercritical CO
2whipping agent and polystyrene resin composite melt be full and uniform to be mixed and the whipping agent that prevents gas backflow hold one's breath system and a foaming mouthful mould; Polystyrene resin composite and supercritical CO
2whipping agent carries out melt blending in melt zone temperature is the forcing machine of 150～230 ℃, obtains the melted blend of homogeneous, and this mixture is that 1～40MPa, temperature are under the condition of 80～180 ℃ at die pressure, keeps 0.01～30kg/h/mm
2the flow of extruding by a foaming mouthful mould, carry out extrusion foaming, obtain polystyrene resin foaming plate.
Described forcing machine is two rank forcing machine of single screw extrusion machine, twin screw extruder or twin screw extruder and single screw extrusion machine series connection, and the length-to-diameter ratio L/D of screw rod is 20～100.
Described foaming mouth mould is flat mouthful of mould of annular die or clothes hanger type runner; when very moment mould is flat mouthful of mould of clothes hanger type runner; outside mouth mould, wide cut of configuration is the planer of 1～6 times of flat mouthful of Mould Breadth degree of clothes hanger type runner, and two surfaces up and down of this planer form by polytetrafluoroethylmaterial material.
Polystyrene resin foaming plate of the present invention, has 30 times of above high foamabilities, and open cell content is lower than 20%, and thickness surpasses 15cm, and cross-sectional area can surmount 1800cm
2.Method of the present invention is with adding the hold one's breath specific forcing machine of system, measuring apparatus, static mixer and foaming mouth mould of whipping agent; under wider processing condition, just can obtain high foamability, abscess evenly, the polystyrene foamed slab of high compressive strength, can directly be used in the fields such as external wall of house insulation, bullet train roadbed, airstrip roadbed, hangar and basis, hardstand.
Accompanying drawing explanation
Fig. 1 is twin screw sealing ring type screw element;
Fig. 2 is the SEM sectional drawing of embodiment 1 foaming plate;
Fig. 3 is the SEM sectional drawing of comparative example 1 foaming plate.
Embodiment
Polystyrene resin foaming plate of the present invention, is to take composite polystyrene resin as matrix, is aided with bubble nucleating agent, oxidation inhibitor and fire retardant and is made into polystyrene resin composite, adopts supercritical CO
2whipping agent, adopts the manufacture of extrusion foaming method to form by extrusion foaming device; This polystyrene resin foaming plate has the expansion ratio that is greater than 30 times, and open cell content is lower than 20%, and thickness surpasses 15cm, and sectional area is greater than 1800cm
2.
This composite polystyrene resin is composite the obtaining of mass ratio by 90: 10～20: 80 by the general purpose polystyrene that adopts the polymerization of mass polymerization mode to obtain and high molecular weight polystyrene, and the weight-average molecular weight Mw of general purpose polystyrene is 1.5 * 10
5-3.5 * 10
5, the weight-average molecular weight Mw of high molecular weight polystyrene is 4.5 * 10
5-7.5 * 10
5, the molecular weight distributing index Mw/Mn of two kinds of polystyrene all≤4.
First, polystyrene as matrix resin must be to adopt mass polymerization mode to obtain, because adopt the method for letex polymerization or the method for suspension polymerization all can residual a large amount of micromolecular tensio-active agents, suspension agent or emulsifying agent, result not only produces a very large impact for the flame retardant properties of final foam materials, and it is mutually miscible that polystyrene resin molecule is difficult to, can not get uniform body material, also just can not obtain the foam materials that foam performance is good.On the other hand, as adopted solution polymerization process, although can obtain well behaved body material, but because solvent must reclaim, purify, result has not only improved raw materials cost greatly, and expends a large amount of energy more and easily produce environmental pollution, so can not apply equally.So the polystyrene resin as body material must adopt mass polymerization mode to obtain.Weight-average molecular weight Mw is 1.5 * 10
5-3.5 * 10
5general purpose polystyrene resin can adopt free radical body Continuous Heat polymerization process to obtain, price is also more cheap, is suitable for industrialization.But its melt strength is not enough, cannot be applicable to adopt supercritical CO
2system as whipping agent.If improve polymerizable molecular amount to preassigned, this polymerization system does not almost have possibility.Therefore, Mw is 4.5 * 10
5-7.5 * 10
5high molecular weight polystyrene resin, must adopt negatively charged ion mass polymerization polymerization process to obtain, for example adopt the technology of patent publication No. CN101717555A, obtain line style or star-like high molecular weight polystyrene resin.The massfraction ratio of two components is 90: 10～20: 80, and the massfraction of general purpose polystyrene resin is higher, and manufacturing cost is just lower, but because melt strength is also lower, is more unfavorable for sending the foam materials of stablizing high-quality.On the contrary, the massfraction of high molecular weight polystyrene resin is higher, and manufacturing cost is just higher, but because melt strength is also higher, more easily sends the foam materials of stablizing high-quality.
How to control to the most appropriate ratio? the described composite resin of polystyrene must show obvious tension strain sclerosis behavior under blowing temperature in the method for the invention, simultaneously at 1s
-1rate of extension under, the critical fracture value of melt tension strain surpasses 1.5, and tensile stress (σ
e) meet dln σ with the relation of tensile deformation (ξ)
e/ d ξ > 0.5.This is to be controlled at the minimum add-on of high molecular weight polystyrene resin, is also under least cost condition, guarantees to obtain the criterion of high-quality foam material.The foaming process of polystyrene is the three-dimensional expansion process of numerous abscess, in this process, melt will be subject to stretching action fast, therefore, the essential condition of preparing high magnification polystyrene foamed is that foam melt in the process expanding can not break, once in expansion process melt break too early will cause foam produce holes or and hole, expansion ratio is reduced, and this just requires polystyrene melt not only will bear certain drawing force effect, but also will have larger deformability.Therefore,, when the draft flowing deformation behavior of test polystyrene melt, rate of extension is more than or equal to 1s
-1time the melt rheological property that shows more close to the expansion behavior of melt in actual foaming process, this foaming for polystyrene more has actual directive significance.
Polystyrene resin composite in the present invention is when carrying out draft flowing deformation test, and under blowing temperature, rate of extension is more than or equal to 1s
-1time the critical fracture value of melt tension strain must be greater than 1.5, be preferably greater than 3.If the critical fracture value of melt tension strain is less than 1.5, while foaming, the wall of abscess easily breaks, can not get the foaming plate of desirable foam structure, and the critical fracture value of melt tension strain is larger, when foaming, steep wall and just be more not easy to break, more easily obtain the extrusion foaming sheet material that rate of closed hole is high.
In the present invention, used the supercritical CO of 5%～20% mass fraction
2whipping agent (take composite polystyrene resin as 100%), wherein comprises ethers, alcohols and saturated hydrocarbons blowing promotor, blowing promotor and the supercritical CO of specified quantitative
2mass ratio be 0～20: 100～80, specific blowing promotor is selected from: one or several in dme, diethyl ether, methyl ethyl ether, methylvinylether, methyl chloride, monochloroethane, methyl alcohol, ethanol, water, butane, pentane, Trimethylmethane.As mentioned above, the most rising whipping agent should be exactly CO
2, not only aspect heat insulation, heat insulation effect, to obviously be better than small molecules aliphatic hydrocarbon, more not mediocrely said ethers and alcohols, the more important thing is CO
2also give the flame retardant properties that foam materials is good.Yet with CO
2as whipping agent, at plastic foamed temperature, must allow CO
2in supercritical state, can use as whipping agent, pressure now must surpass 10-15MPa.So, CO
2explosive power just quite large, the melt strength of resin is required just very high.In addition, due to CO
2relative weak with the consistency of resin for small molecules aliphatic hydrocarbon, thereby have higher one-tenth nuclearity, the number of abscess is much bigger, is easy to form micropore, but does not allow to obtain into high foamability, therefore needs certain blowing promotor to play regulatory role.But the addition of blowing promotor can not be excessive, otherwise not only aspect heat insulation, heat insulation effect, greatly decline, and large havoc the flame retardant properties of foam materials.
In polystyrene resin composite in the present invention, the fire retardant that contains 2%～30% mass fraction (the pure composite polystyrene resin of take is 100%), all fire retardants are to be all selected from the kind that meets international environmental protection standard, as hexabromocyclododecane, poly-bromstyrol, dibromoneopentyl glycol, tetrabromo-bisphenol, tetrabromophthalate glycol, tetrabromo phenol, the bromide fire retardant of poly-pentabromobenzyl acrylate etc., clorafin, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, the chlorine-based flame retardant of hexachloro endoethylene tetrahydrophthalic acid etc., triallyl phosphate, alkyl allyl group phosphoric acid ester, the phosphoric acid ester of alkyl phosphate etc., bromophosphonate, the Firemaster 836 of chlorinated phosphate etc., phosphoric acid is narrowed base urea, polyphosphonitrile, phosphamide, Tripyrophosphoric acid amine, the phosphorus system resistance fire retardant of red phosphorus etc., barium metaborate, the boron compound of the borate metal salt of zinc borate etc. etc., melamine phosphate, phosphoguanidine, melamine prepolymer, trimeric cyanamide, the ammonia flame retardant of melamine cyanurate etc., in addition, tetrazolium class, stannic oxide, aluminium hydroxide, weisspiessglanz, molybdenum oxide, ammonium molybdate, zirconium white, zirconium hydroxide, aluminium hydroxide, magnesium hydroxide, the fire retardant of calcium plumbite etc.
In polystyrene resin composite in the present invention, the bubble nucleating agent that contains 0.1%～25% mass fraction (the pure composite polystyrene resin of take is 100%), is selected from one or more in talcum powder, kaolin, mica, silicon-dioxide, glass, quartz, calcium carbonate, carbon black, magnesium oxide, zinc oxide, aluminum oxide, titanium oxide, barium sulfate, Attapulgite, polynite, clay, wilkinite, diatomite.Preferably use silicon-dioxide, kaolin, polynite, clay, talcum powder, calcium carbonate, further preferably use polynite, talcum powder, calcium carbonate, more preferably talcum powder or polynite.The preferable amount of bubble nucleating agent is 0.2～10% mass parts, most preferably is 0.5～2% mass parts.Bubble nucleating agent add the effect that can play heterogeneous nucleation, the cell density of foaming plate is significantly increased, if but consumption surpasses 25% mass fraction, have the risk that reduces foaming plate mechanical property and worsen polystyrene resins composition draft flowing deformation behavior and even foam performance.
Gravel size decision 300～5000 orders of above-mentioned bubble nucleating agent, most preferably 600-1500 order.If the size of bubble nucleating agent is less than 300 orders; larger inorganic filler particle can worsen the mechanical property of polystyrene resins matrix or make the abscess of foaming plate produce more holes; on the contrary; if the size of bubble nucleating agent surpasses 5000 orders; inorganic nanoparticles may be reunited; can not be dispersed in resin matrix, have the danger reducing with resin matrix consistency.
In polystyrene resin composite in the present invention, the oxidation inhibitor that contains 0.2%～1% mass parts (preferably 0.4%～0.8% mass parts) (the pure composite polystyrene resin of take is 100%), is selected from 2,6-di-t-butyl-4-ethylphenol, 2,6 di tert butyl 4 methyl phenol, 2,6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2,4,6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, oxidation inhibitor B215 and oxidation inhibitor B225, four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, ethylenebis (oxygen ethylidene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic acid] ester, 1,3,5-tri-(3,5-tertiary butyl-4-hydroxy benzyl)-1,3,5 triazine-2,4,6 (1H, 3H, 5H)-triketones, 2,6-di-t-butyl-4-(4,6-bis-(octyl group sulphur)-1,3,5-triazines-2-base is amino) phenol, tricresyl phosphite (2,4 tri-tert phenyl) ester, 5,7-di-t-butyl-3-(3,4-3,5-dimethylphenyl)-3H benzofuran-2-ones, can be used wherein one or more to combine use.Oxidation inhibitor add the fluidity of molten that can regulate polystyrene resins, prevent from producing in its course of processing too much degraded, if but add-on is greater than 1%, may worsen mechanical property and the foam performance of resin matrix.
The manufacture method of polystyrene resin foaming plate of the present invention is to adopt extrusion foaming method to manufacture by extrusion foaming device; Described extrusion foaming device comprises forcing machine, is equipped with the metered charge mechanism of polystyrene resin composite and the injection metering mechanism of whipping agent on forcing machine, is equipped with and can makes polystyrene resin composite and supercritical CO
2the strong solution of whipping agent fully mixes, cooling static mixer, is equipped with and can makes supercritical CO
2whipping agent and polystyrene resin composite melt be full and uniform to be mixed and the whipping agent that prevents gas backflow hold one's breath system and a foaming mouthful mould; Polystyrene resin composite and supercritical CO
2whipping agent carries out melt blending in melt zone temperature is the forcing machine of 150～230 ℃, obtains the melted blend of homogeneous, and this mixture is that 1～40MPa, temperature are under the condition of 80～180 ℃ at die pressure, keeps 0.01～30kg/h/mm
2the flow of extruding by a foaming mouthful mould, carry out extrusion foaming, obtain polystyrene resin foaming plate.
The throughput of the forcing machine in the present invention is 1～3000kg/h.The diameter of screw rod (Φ D) can be determined according to the height of the size of output and moment of torsion.But the length-to-diameter ratio of screw rod (L/D) is better 20～100, preferably 40～60.The length-to-diameter ratio of screw rod is too little not only can make the residence time of material too short, and molten state is not good, but also can cause polystyrene resins composition inhomogeneous with mixing of whipping agent.On the other hand, if the length-to-diameter ratio of screw rod is too large, can make the residence time of material oversize, can there is the danger of degraded in polystyrene resins component.Guaranteeing that material has under the condition of the suitable residence time, forcing machine type used can be common single screw extrusion machine, twin screw extruder or two rank type forcing machine of connecting with single screw rod for twin screw, preferred twin screw extruder wherein, two rank forcing machine of tandem type preferably, so just can make foaming composition evenly mix better with whipping agent, and there have grace time to maintain foaming system to be stable.
Forcing machine in the present invention need to be equipped the whipping agent that can the prevent gas backflow system of holding one's breath.Its effect is that the high-pressure foam agent that prevents from being injected in forcing machine is flowed before and after screw rod, has hindered whipping agent and has fully mixed with polystyrene resins composition.Conventionally the system of holding one's breath comprises 3 major portions: the left-hand thread district that (1) consists of left-hand thread piece; (2) the kneading district being formed by kneading block; (3) by the mixing zone that there is intense mixing threaded block and form.Special occasions need to be used the special use system of holding one's breath, as shown in Figure 1.Polystyrene resin composite and whipping agent carry out melt blending in melt zone temperature is the forcing machine of 150～230 ℃, obtain the melted blend of homogeneous.More preferably 170～200 ℃ of melt zone Temperature Settings, if temperature is lower than 150 ℃, polystyrene resins is difficult to melting, can strengthen moment of torsion and the pressure of forcing machine, and the more important thing is that whipping agent is difficult to be dissolved in polystyrene resin matrix, and if temperature surpasses 230 ℃, polystyrene resins component has the danger that degraded occurs.By this mixture, at die pressure, be 1～40MPa, temperature is under the condition of 80～180 ℃, keeps 0.01～30kg/h/mm
2the flow of extruding discharge into the atmosphere, carry out extrusion foaming, can manufacture expansion ratio is 1～60 times, corresponding density is 15kg/m
3～900kg/m
3polystyrene resin foaming plate.
Forcing machine in the present invention need to be equipped the device of accurate measurement, comprises injection measuring apparatus and the accurate measurement charging device of each component of polystyrene resin composite of whipping agent.Each Measuring Precision must be quality control precision but not volume metering precision, and trueness error scope is within 0.1%～1.5%, and preferably, within 0.5%～1%, more high technology is more stable for tolerance range undoubtedly, but equipment cost is also higher, preferably considers.
Forcing machine in the present invention need to be equipped with and can make that polystyrene resins composition fully mixes with the strong solution of whipping agent, cooling static mixer.Its kind can be according to determined forcing machine type and fixed all kinds of standard static mixing tanks.
Foaming mould in the present invention can be annular die, also can be flat mouthful of mould of clothes hanger type runner, when very moment mould is flat mouthful of mould of clothes hanger type runner, needing wide cut of the outer configuration of mouthful mould is the planer of 1～6 times of flat mouthful of Mould Breadth degree of clothes hanger type runner, and upper and lower two surfaces of this planer consist of polytetrafluoroethylmaterial material.During extrusion foaming, the pressure of die head remains 1～40 MPa, most preferably is 6～20MPa.If the pressure at extruder die head place is lower than 1 MPa, the whipping agent being dissolved in polystyrene resins composition is easy to just produce gasification in forcing machine or before the outlet of mouth mould, generate precocious complex, this type of complex is not further growth again of abscess after discharging into the atmosphere, thereby can make expansion ratio decline.In addition, the too low abscess of pressure also can produce merging, and cell diameter is increased, and causes the inhomogeneous of foam structure.And if the pressure of mouthful mould surpasses 40MPa, can make whipping agent surpass in polystyrene resins composition substrate saturated, these whipping agents not only can not be participated in the nucleation process of complex, and can in the process of foaming, destroy bubble wall, make to steep wall and break, thus the elastic recovery of deterioration foaming plate, when used as insulation or cushioning material, such holes structure can be in heat insulation, insulation, and mechanical property aspect is all very poor.
The extruding dies using in the present invention can be the flat mouthful mould of clothes hanger type runner, can be also circular ring type mouth mould, specifically uses which kind of mouthful mould not do special restriction, is that the thickness by the foaming plate of manufacturing decides.When the foaming plate thickness of manufacturing is greater than 5mm, preferably use flat mouthful of mould of the clothes hanger type runner that is equipped with planer; When the sheet metal thickness of manufacturing is less than or equal to the foaming plate of 5mm, preferably use circular ring type mouth mould.
While using flat mouthful of mould of clothes hanger type runner, will be used in conjunction with the planer that upper and lower surface is polytetrafluoroethylmaterial material, the wide cut of planer mouth mould is 1～6 times of flat mouthful of Mould Breadth degree of clothes hanger type runner.Using the reason of planer is when polystyrene extrusion foaming, three dimensional growth due to bubble, the longitudinally not restriction of foaming plate, abscess can free expansion, and laterally between abscess, can mutually produce extruding, thereby make the surface of foamed polystyrene board material occur fold, can not obtain the foaming plate of surface smoothing.And free expansion that can limited thickness direction by planer.Therefore,, by using planer can effectively eliminate fold, also can make the surface of foaming plate more level and smooth.
In the present invention, Kou Mo unit's port area discharge-amount is 0.01～30kg/h/mm
2, accurate calculation can be calculated by through type (1):
The total feeding capacity of discharge-amount=forcing machine (kg/h)/mould openings area (mm of unit port area
2).(1)
Can, by regulating the methods such as screw speed, feeding capacity and mould openings area of forcing machine, the discharge-amount of the unit port area of mould be adjusted to above-mentioned scope.
The open cell content of polystyrene resin foaming plate of the present invention, lower than 20%, is more preferably lower than 15%, preferably can be lower than 10%.Open cell content is higher than in 20% situation, and the elastic recovery of foaming plate and thermal and insulating performance do not reach specific requirement.
The mean cell diameter of polystyrene resins foaming plate of the present invention is better 50～500 μ m, 50～100 μ m preferably, and thermal conductivity is better 20～34mw/mK, preferably 20～25mw/mK.
Below by several embodiment and comparative example, the invention will be further described.
The measurement and calculation method of the various physicalies in embodiment and comparative example is as follows:
Mean cell diameter: first by brittle failure after cooled with liquid nitrogen for foaming plate, then use scanning electron microscope (SEM) to observe the section of foaming plate, utilize given scale to calculate respectively the diameter of 10 abscesses, then ask its mean value.
The rate of closed hole of abscess: the standard according to ASTM-D2856 is measured.
Foaming plate density: the sample that foaming plate is cut into high each 2cm left and right of length and width, weigh up its weight, then with superfine wire, sample is sunk to and be equipped with in the graduated cylinder of known water amount, according to the actual volume of the change detection sample of water level, through type (2) calculates its density.
Foaming plate density=sample quality/sample volume (2)
Expansion ratio: expansion ratio=1.05/ foaming plate density.
Light weight: evaluate with zero (good), △ (qualified), * (defective) 3 grades.
Flame retardant resistance: evaluate with zero (good), △ (qualified), * (defective) 3 grades.
Thermal insulation: evaluate with zero (good), △ (qualified), * (defective) 3 grades.
Sheet material outward appearance (surface smoothness): evaluate with zero (good), △ (qualified), * (defective) 3 grades.
Sheet material outward appearance (having non-wrinkled): evaluate with zero (good), △ (qualified), * (defective) 3 grades.
Embodiment 1
Use twin-screw extrusion foam device as described below: the screw diameter of forcing machine (D) is Φ 35mm, length-to-diameter ratio (L/D) is 48, be equipped with whipping agent hold one's breath system, melt metering pump and SK type static mixer, it is 100mm that front end is equipped with A/F, flat mouthful of mould of the clothes hanger type runner that open height is 1mm.After mould, be furnished with the planer that upper and lower surface is polytetrafluoroethylene film, the wide cut of planer mouth mould is 500mm.
In polystyrene resin composite, by Mw, be 2.0 * 10
5, Mw/Mn is 3.3 general purpose polystyrene is 60 mass parts, Mw is 7.0 * 10
5, Mw/Mn high molecular weight polystyrene 40 mass parts that are 2.3, form matrix resin.This polystyrene resin composite is 1s in rate of extension
-1time, the critical fracture value of melt tension strain is 3.5, tensile stress (σ
e) with tensile deformation (ξ) be related to dln σ
e/ d ξ > 1, melt flow rate (MFR) is 2.5g/10min.The composite polystyrene resin matrix of 100 mass parts of take is benchmark, is added with 0.5 mass parts oxidation inhibitor B215,1 mass parts as 1000 order talcum powder of bubble nucleating agent and 2 mass parts hexabromocyclododecanes and the poly-bromstyrol of 4 mass parts as fire retardant.Said components is carried out in high mixer fully mix and form polystyrene resin composite, stand-by.
The screw speed and the feeding rotating speed that regulate above-mentioned twin-screw extrusion foam device, make the output of forcing machine reach 10kg/h.It is in the forcing machine of 170 ℃～185 ℃ that the above-mentioned polystyrene resin composite mixing is added to melt zone temperature, after preliminary melting, with volume pump, with the flow of 1kg/h, injects supercritical CO
2whipping agent (wherein containing Trimethylmethane 10%, dme 5%), makes it fully mix with polystyrene resin composite, forms the melt of homogeneous.Then, in the static mixer of melted blend on being assemblied in forcing machine, carry out abundant combination cooling, make its temperature-stable before entering foaming mouthful mould at 80 ℃～100 ℃, finally under die temperature is the condition of 80 ℃～100 ℃, be expressed into fast in air, carry out foam shaping by extrusion.By the pressure before foaming mouthful mould, be 12MPa.The foaming plate of manufacturing carries out with SEM, observing after brittle failure the foam structure of section with liquid nitrogen, as shown in Figure 2.The various characteristics of extrusion foaming sheet material is as shown in table 1, and the extrusion foaming sheet material of manufacturing is that abscess is even, diameter is less than 100 μ m, surface smoothing, does not have crisp good light-weight foam sheet material.
Embodiment 2
The flow of 1kg/h of usining injects Trimethylmethane as whipping agent in forcing machine, and other is all identical with embodiment 1.Now the tensimeter at mouthful mould place shows that force value is 1.6MPa.The various characteristics of gained foaming plate is as shown in table 1, and goods are a kind of surface smoothings, do not have crisp good light extruded foaming plate.
Embodiment 3
On the basis of embodiment 1, adjust the temperature that static mixer is set, make its temperature-stable before entering into mouthful mould at 90 ℃, under being also the condition of 90 ℃, die temperature is expressed in air, carry out foam shaping by extrusion.Now the pressure before mouthful mould is 16MPa.The various characteristics of gained foaming plate is as shown in table 1, and goods are a kind of surface smoothings, do not have crisp good light extruded foaming plate.
Embodiment 4
Flow with 0.7kg/h injects supercritical CO in forcing machine
2whipping agent (wherein containing normal butane 10%, ethanol 5%), does not add fire retardant, in addition all identical with embodiment 1.Now the pressure before mouthful mould is 8MPa.The various characteristics of gained foaming plate is as shown in table 1, and goods are a kind of surface smoothings, do not have crisp good light extruded foaming plate.
Embodiment 5
Changing the planer of the flat mouth mould of the clothes hanger type runner of forcing machine front end in embodiment 1 and outfit into interior ring diameter is 20mm, the circular ring type mouth mould that A/F is 1mm.
All identical with embodiment 1 in addition.Now the pressure before mouthful mould is 10MPa.The various characteristics of gained foaming plate is as shown in table 1, and goods are a kind of surface smoothings, do not have crisp good light extruded foaming plate.
Comparative example 1
In the polystyrene resin composite using, Mw is 1.5 * 10
5, the general purpose polystyrene that Mw/Mn is 3.0 is 100 mass parts, in rate of extension, is 1s-
1time, the critical fracture value of melt tension strain is 1.5, tensile stress (σ
e) meet dln σ with the relation of tensile deformation (ξ)
e/ d ξ ≈ 0, melt flow rate (MFR) is 3g/10min.In addition all identical with embodiment 1.
Now the pressure before mouthful mould is 11MPa.The foaming plate of manufacturing carries out with SEM, observing after brittle failure the foam structure of section with liquid nitrogen, as shown in Figure 3.The various characteristics of extrusion foaming sheet material is as shown in table 1, although the extrusion foaming sheet material outward appearance of manufacture is good, foam expansion is very low, holes serious and lack light weight.
Comparative example 2
In polystyrene resin composite, Mw is 2.5 * 10
5, the general purpose polystyrene that Mw/Mn is 3.0 is 90 mass parts, Mw is 6.5 * 10
5, high molecular weight polystyrene 10 mass parts that Mw/Mn is 2.0, do not add bubble nucleating agent talcum powder and crystallization promoter p t butylbenzoic acid aluminium simultaneously, and other is identical with embodiment 1.Now the tensimeter at mouthful mould place shows that force value is 12MPa.The various characteristics of extrusion foaming sheet material is as shown in table 1, although the extrusion foaming sheet material appearance of manufacture is good, cell diameter is larger, and foam expansion is lower, lacks light weight and thermal insulation.
Comparative example 3
The temperature of adjusting forcing machine static mixer, makes its temperature-stable before entering into mouthful mould at 120 ℃, under die temperature is also the condition of 120 ℃, is expressed in air, carries out foam shaping by extrusion.Now the tensimeter at mouthful mould place shows that force value is 20MPa, and other are with comparative example 2.The various characteristics of extrusion foaming sheet material is as shown in table 1, and the extrusion foaming sheet material of manufacture is that a kind of holes is serious, and rate of closed hole is low, and surface lacks smoothness, and the poor goods of heat insulation property.
Comparative example 4
Flow with 0.05kg/h injects supercritical CO in forcing machine
2whipping agent is in addition identical with embodiment 1.Now the tensimeter at mouthful mould place shows that force value is 0.9MPa.The various characteristics of extrusion foaming sheet material is as shown in table 1, and the extrusion foaming sheet material of manufacture is a kind of surface smoothing, but expansion ratio is low, and lacks the goods of light weight and thermal insulation.
Comparative example 5
The extrusion capacity of adjusting forcing machine is 1kg/h, flow injection ring pentane foaming agent in forcing machine with 0.05kg/h, adjust the temperature of forcing machine static mixer, make its temperature-stable before entering into mouthful mould at 80 ℃～100 ℃, under die temperature is also the condition of 80 ℃～100 ℃, be expressed in air, carry out foam shaping by extrusion.In addition identical with comparative example 2.
Now the tensimeter at mouthful mould place shows that force value is 0.3MPa.The various characteristics of extrusion foaming sheet material is as shown in table 1, and the extrusion foaming sheet material of manufacture is that a kind of appearance is poor, and expansion ratio is low, lacks the foaming product of light weight and thermal insulation.
Table 1
Claims (8)
1. a polystyrene resin foaming plate, is characterized in that: take composite polystyrene resin as matrix, be aided with bubble nucleating agent, oxidation inhibitor and fire retardant and be made into polystyrene resin composite, adopt supercritical CO
2whipping agent, adopts the manufacture of extrusion foaming method to form by extrusion foaming device;
The consumption of composite polystyrene resin of take is 100 weight parts, and the consumption of bubble nucleating agent is 0.1-25 weight part, and the consumption of oxidation inhibitor is 0.2-1 weight part, and the consumption of fire retardant is 2-30 weight part, supercritical CO
2the consumption of whipping agent is 5-20 weight part;
Described polystyrene resin foaming plate has the expansion ratio that is greater than 30 times, expansion ratio=1.05/ foaming plate density, and open cell content is lower than 20%, and thickness surpasses 15cm, and sectional area is greater than 1800cm
2;
Described composite polystyrene resin is composite the obtaining of mass ratio by 90: 10～20: 80 by the general purpose polystyrene that adopts the polymerization of mass polymerization mode to obtain and high molecular weight polystyrene, and the weight-average molecular weight Mw of general purpose polystyrene is 1.5 * 10
5-3.5 * 10
5, the weight-average molecular weight Mw of high molecular weight polystyrene is 4.5 * 10
5-7.5 * 10
5, the molecular weight distributing index Mw/Mn of two kinds of polystyrene all≤4;
Described composite polystyrene resin shows obvious tension strain sclerosis behavior under blowing temperature, simultaneously at 1s
-1rate of extension under, the critical fracture value of melt tension strain surpasses 1.5, and tensile stress σ
emeet dl n σ with the relation of tensile deformation ξ
e/ d ξ > 0.5.
2. according to the polystyrene resin foaming plate described in claims 1, it is characterized in that: described supercritical CO
2whipping agent is by supercritical CO
2constitute blowing promotor and supercritical CO with blowing promotor
2mass ratio be 0～20: 100～80, blowing promotor is selected from one or several in dme, diethyl ether, methyl ethyl ether, methylvinylether, methyl chloride, monochloroethane, methyl alcohol, ethanol, water, butane, pentane, Trimethylmethane.
3. according to the polystyrene resin foaming plate described in claims 1, it is characterized in that: described fire retardant is selected from hexabromocyclododecane, poly-bromstyrol, dibromoneopentyl glycol, tetrabromo-bisphenol, tetrabromo phenol, poly-pentabromobenzyl acrylate, clorafin, hexachloro endoethylene tetrahydrophthalic acid acid anhydride, hexachloro endoethylene tetrahydrophthalic acid, triallyl phosphate, alkyl allyl group phosphoric acid ester, alkyl phosphate, bromophosphonate, chlorinated phosphate, phosphoric acid is narrowed base urea, polyphosphonitrile, ammonium phosphate, ammonium polyphosphate, red phosphorus, barium metaborate, zinc borate, melamine phosphate, phosphoguanidine, melamine prepolymer, trimeric cyanamide, melamine cyanurate, tetrazolium class, stannic oxide, aluminium hydroxide, weisspiessglanz, molybdenum oxide, ammonium molybdate, zirconium white, zirconium hydroxide, magnesium hydroxide, one or several in calcium plumbite.
4. according to the polystyrene resin foaming plate described in claims 1, it is characterized in that: described bubble nucleating agent is selected from one or more in talcum powder, kaolin, mica, silicon-dioxide, glass, quartz, calcium carbonate, carbon black, magnesium oxide, zinc oxide, aluminum oxide, titanium oxide, barium sulfate, Attapulgite, polynite, clay, wilkinite, diatomite, the particle diameter of bubble nucleating agent is 300～5000 orders.
5. according to the polystyrene resin foaming plate described in claims 1, it is characterized in that: described oxidation inhibitor is selected from 2, 6-di-t-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-methy phenol, 2, 6-di-t-butyl-alpha, alpha-dimethyl amino-p-cresol, 2, 4, 6-tri-butyl-phenol, Tyox B, thio-2 acid two (octadecyl ester), thio-2 acid two (14 ester), antioxidant CA, oxidation inhibitor B215, oxidation inhibitor B225, four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, ethylenebis (oxygen ethylidene) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic acid] ester, 1, 3, 5-tri-(3, 5-tertiary butyl-4-hydroxy benzyl)-1, 3, 5 triazine-2, 4, 6 (1H, 3H, 5H)-triketone, tricresyl phosphite (2, 4-di-tert-butyl-phenyl) ester, 5, 7-di-t-butyl-3-(3, 4-3,5-dimethylphenyl) one or more in-3H-benzofuran-2-ones.
6. a manufacture method for the polystyrene resin foaming plate described in claims 1, is characterized in that: by extrusion foaming device, adopt extrusion foaming method to manufacture; Described extrusion foaming device comprises forcing machine, is equipped with the metered charge mechanism of polystyrene resin composite and the injection metering mechanism of whipping agent on forcing machine, is equipped with and can makes polystyrene resin composite and supercritical CO
2the strong solution of whipping agent fully mixes, cooling static mixer, is equipped with and can makes supercritical CO
2whipping agent and polystyrene resin composite melt be full and uniform to be mixed and the whipping agent that prevents gas backflow hold one's breath system and a foaming mouthful mould; Polystyrene resin composite and supercritical CO
2whipping agent carries out melt blending in melt zone temperature is the forcing machine of 150～230 ℃, obtains the melted blend of homogeneous, and this mixture is that 1～40MPa, temperature are under the condition of 80～180 ℃ at die pressure, keeps 0.01～30kg/h/mm
2the flow of extruding by a foaming mouthful mould, carry out extrusion foaming, obtain polystyrene resin foaming plate.
7. according to the manufacture method of the polystyrene resin foaming plate described in claims 6, it is characterized in that: described forcing machine is two rank forcing machine of single screw extrusion machine, twin screw extruder or twin screw extruder and single screw extrusion machine series connection, and the length-to-diameter ratio L/D of screw rod is 20～100.
8. according to the manufacture method of the polystyrene resin foaming plate described in claims 6; it is characterized in that: described foaming mouth mould is flat mouthful of mould of annular die or clothes hanger type runner; when very moment mould is flat mouthful of mould of clothes hanger type runner; outside mouth mould, wide cut of configuration is the planer of 1～6 times of flat mouthful of Mould Breadth degree of clothes hanger type runner, and two surfaces up and down of this planer form by polytetrafluoroethylmaterial material.
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| CN115109298B (en) * | 2022-08-09 | 2023-08-01 | 泗阳蓝天新材料科技股份有限公司 | Flame-retardant polystyrene composite material and preparation method thereof |
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| CN101619139A (en) * | 2009-08-05 | 2010-01-06 | 新疆西龙土工新材料股份有限公司 | Method for producing extrusion molding polystyrene polyfoam for heat insulation by supercritical carbon dioxide foaming |
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| CN101619139A (en) * | 2009-08-05 | 2010-01-06 | 新疆西龙土工新材料股份有限公司 | Method for producing extrusion molding polystyrene polyfoam for heat insulation by supercritical carbon dioxide foaming |
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