CN1077583C - Preparation of expandable styrene polymers containing graphite particles - Google Patents
Preparation of expandable styrene polymers containing graphite particles Download PDFInfo
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- CN1077583C CN1077583C CN97182185A CN97182185A CN1077583C CN 1077583 C CN1077583 C CN 1077583C CN 97182185 A CN97182185 A CN 97182185A CN 97182185 A CN97182185 A CN 97182185A CN 1077583 C CN1077583 C CN 1077583C
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- styrene
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- graphite
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002245 particle Substances 0.000 title claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 35
- 239000010439 graphite Substances 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 3
- 239000004793 Polystyrene Substances 0.000 claims description 22
- 229920002223 polystyrene Polymers 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 17
- 239000011324 bead Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000004794 expanded polystyrene Substances 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920006327 polystyrene foam Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 3
- 235000019801 trisodium phosphate Nutrition 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SHRRVNVEOIKVSG-UHFFFAOYSA-N 1,1,2,2,3,3-hexabromocyclododecane Chemical class BrC1(Br)CCCCCCCCCC(Br)(Br)C1(Br)Br SHRRVNVEOIKVSG-UHFFFAOYSA-N 0.000 description 1
- LLVVSBBXENOOQY-UHFFFAOYSA-N 1,2,3,4,5-pentabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C(Br)=C1Br LLVVSBBXENOOQY-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000002194 Pithecellobium dulce Nutrition 0.000 description 1
- 235000007891 Pithecellobium lobatum Nutrition 0.000 description 1
- 244000134260 Pithecellobium unguis cati Species 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 aromatic series bromine compounds Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical class C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004620 low density foam Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001007 puffing effect Effects 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
In the technology for preparing expandable styrene polymers containing graphite particles, styrene polymerizes in aqueous suspension in the presence of graphite particles.
Description
But the present invention relates to prepare the technology of the granular extruded styrene polymkeric substance of graphitiferous particle.
The polystyrene particle foam is known very early and obtained application in many fields.The preparation of this type of foamy is, will flood the polystyrene particle foaming of whipping agent, then the foam particle that obtains fused together and forms molding.Important use field is heat insulation in construction work.
As heat insulation expanded polystyrene cystose, has the density of about 30g/l usually, because expanded polystyrene foamy thermal conductivity has minimum value near this density.For saving material and space, wish to use cystose to make thermally-insulated body with less dense, particularly＜15g/l.Preparing this foam is not problem technically.But its heat-proof quality of low-density cystose like this is had a greatly reduced quality so that can't satisfy the requirement (DIN 18164, chapter 1) of thermal insulation level 035.
Known foamy thermal conductivity can be reduced by introducing adiabatic material such as carbon black, metal oxide, metal-powder or pigment.
Therefore, EP-A 372 343 has described and has contained 1～25wt% sooty polystyrene foam.Particle size carbon black 10～100nm.Wherein the polystyrene foam of Miao Shuing preferentially utilizes the extrusion molding preparation, and preferably has density 32～40g/l.In addition, also having described the preparation technology who contains the whipping agent granular polystyrene, is that the carbon black enriched material in the polystyrene is sneaked in the melt of polystyrene together with whipping agent, and extrudes and this mixture of granulation.This is a quite complicated technology.
WO94/13721 has described similar foam, wherein diameter＞the 150nm of carbon black particle.
EP-A 620 246 has described the foam moulded thing of a kind of expanded polystyrene, and it contains granular adiabatic material, particularly carbon black and also mentions graphite.The density of molding is lower than 20g/l.Preferably by on the particle surface that is coated in prefoaming polystyrene or the method that is embedded in as yet in the polystyrene particle of not foaming particle is incorporated in the molding., particle is unfavorable for the fusion of pre-expanded beads at the lip-deep this distributed pole the earth of polystyrene bead, and and then cause low-quality foam; In addition, particle may be wiped from the molding surface.Particle under two kinds of situations all can not be uniformly distributed in the inside of polystyrene particle.
An object of the present invention is to provide a kind of simple technology, but the extruded styrene polymkeric substance that contains graphite with preparation, it can be processed into the expanded polystyrene foam, and it has the physicals that low density, low especially thermal conductivity and good processing characteristics are become reconciled.
We have found that, in the presence of graphite, carry out cinnamic suspension polymerization and can realize this purpose.
The invention provides a kind of technology, but the extruded styrene polymkeric substance that contains graphite particle with preparation, it comprises vinylbenzene, optional together with the comonomer that accounts for its weight 20wt%, in the presence of the graphite particle of median size 1-50 μ m, in aqueous suspension, carry out polymerization, and whipping agent can before the polyreaction, among or add afterwards.
But the present invention further provides the extruded styrene polymkeric substance, it contains the equally distributed graphite particle of the median size 1-50 μ m of 0.05～25wt%, and shows as the circular bead of median size 0.2～2mm.
In WO95/10558, recommend to apply the consistency that carbon black can increase carbon black and polystyrene with softening agent.Introduced preparation this type of foamy many methods, be included in the cinnamic polymerization under the existence of pyrolytic carbon black of coating, the interpolation of whipping agent, then cool off final can expanded particle., cinnamic this mass polymerization is 100% owing to not proceeding to transformation efficiency, so that can still contain remaining monomer in the expanded particle.Beat allly be that the suspension polymerization of vinylbenzene in the presence of graphite but can carry out and on the contrary smoothly until fully.
In the present invention, but the extruded styrene polymkeric substance is exactly the styrene polymer that contains whipping agent.
But extruded styrene polymkeric substance of the present invention comprises as polymeric matrix, particularly, styrene homopolymers or contain alkene type unsaturated comonomer, it can reach the styrol copolymer of 20wt%, particularly ring-alkylated styrenes, Vinylstyrene, vinyl cyanide or alpha-methyl styrene based on polymer weight.
In suspension polymerization of the present invention, auxiliary agent such as peroxide initiator, suspension stabilizer, whipping agent, chain-transfer agent, puffing adjuvant, nucleator and softening agent commonly used can add.Especially preferably add fire retardant, preferred amounts is 0.6～6wt%, and the amount of retardant synergist is 0.1～1wt%, and the two is all based on final styrene polymer.Preferred fire retardant is aliphatic, alicyclic and aromatic series bromine compounds such as hexabromocyclododecane, pentabromo-monochloro hexanaphthene and pentabromobenzene allyl ether.Suitable synergistic agent is the labile organic compound of C-C-or O-O-such as bicummyl and dicumyl peroxide.The whipping agent addition is 3～10wt%, the styrene-based polymkeric substance, can be before polyreaction, among or add in the suspension system afterwards.Suitable whipping agent is the aliphatic hydrocarbon that 4～6 carbon atoms are arranged.The inorganic Pichering dispersion agent of suitable employing is such as magnesium pyrophosphate or calcium phosphate, as dispersion stabilizer.
Finding, if what adopt in initial stage of suspension polymerization is vinylbenzene (or mixture of vinylbenzene and other comonomers) solution of polystyrene (or corresponding styrol copolymer), is favourable to the stable of dispersion system.Preferably start from 0.5～30wt% concentration, the particularly styrene solution of 3～20wt% concentration polystyrene.The polystyrene of new system can be dissolved in the monomer and prepare, but suitable preparation is to adopt the excessive or too small particle level part of particle diameter, but screening is come out the bead that can obtain when expanded polystyrene prepares.In fact, these useless excessive or too small its diameters of particle level part are respectively greater than 2.0mm with less than 0.2mm.Also can use the polystyrene of recovery and the polystyrene foam of recovery.Can also be 0.5～70% to transformation efficiency with the pre-polymerization of vinylbenzene body, then this prepolymer and graphite particle are suspended in aqueous phase together and finish polyreaction.
The graphite median size is 1～50 μ m, 2.5～12 μ m particularly, tap density 100～500g/l, specific surface area 5～20m2/g.The synthetic graphite that can select natural graphite for use or grind.
In suspension polymerization of the present invention, the addition of graphite particle is preferably 0.05～25wt%, and 2～8wt% particularly is based on final styrene polymer.They are used with powder or with the form of the particle enriched material in the polystyrene.Feasible substantially is only to add graphite particle in the suspension polymerization process, preferably half stage before the polyreaction round-robin.In the case, it is unnecessary adding polystyrene.Suspension polymerization has formed the subcircular particle of pearl, and median size is 0.2～2mm, and graphite particle is uniform distribution therein.They can apply with the silicate of stearate, glyceryl ester and the superfine grinding of coating agent commonly used such as metal.
But the extruded styrene polymkeric substance that contains graphite particle can be processed into the polystyrene foam that density is 5～35g/l, preferred 8～25g/l, particularly 10～15g/l.
For this reason, can expanded particle pre-frothing.Normally in the pre-frothing device, realize with the steam heating particle.
Then in this way the particle fusion of pre-frothing together with the formation molding.For this reason, the particle transfer with pre-frothing also is to handle in the non-bubble-tight mould and with steam to non-tight.Molding is taken out in the cooling back.
But preparation shows good heat-insulating property from the foam of the present invention's extruded styrene polymkeric substance.Effect is especially obvious under low-density situation.Therefore, but the graphite that adds 2wt% in the extruded styrene polymkeric substance just can make density is that the foamy thermal conductivity of 10g/l drops to from 44mW/m K and is lower than 35mW/mK.
The ability that significantly reduces styrene polymer density under the condition of identical thermal conductivity makes the saving of material become possibility.Because, but, can be issued to the thermal insulation of ad eundem, but when having adopted the expanded polystyrene particle for preparing according to the present invention in quite low tap density compared with traditional extruded styrene polymkeric substance, just can use thinner cystose, realize the spatial saving.
Beat allly be, but extruded styrene polymkeric substance of the present invention successfully processing and preparing become low-density foam.The not only loss of reactive blowing agent but also do not have into the destruction of bubble meta structure may have to admit that graphite can play the effect of nucleator and generate undesirable junior unit foam though be familiar with the people in this field.In addition, by adding, just can prepare and to pass through B2 combustion test, in most cases even the self-extinguishing foam of B1 with fire retardant.
The present invention describes with regard to following embodiment.Umber that provides and percentage ratio are by weight.
Embodiment 1
2.55kg polystyrene (BASF system PS 158K) is dissolved in the 17.03kg vinylbenzene, Graphite Powder 99 (Graphitwerk Kropfm ü hle with 196g, UF2 96/97), i.e. 1% graphite, the total amount of styrene-based and polystyrene, evenly be suspended in this solution, and add 59.6g dicumyl peroxide and 20.4g dibenzoyl peroxide.This organic phase is transferred in the container of the 501 band stirrings that are added with 19.51 deionized waters.Water contains 69.8g trisodium phosphate and 129.5g sal epsom.Take by weighing the 195.8g pentane and join in the suspensoid, be heated 80 ℃ then.After 140 minutes, add 3.51g emulsifying agent K30/40 (BayerAG).After 30 minutes, be weighed into the 1175.1g pentane again, polyreaction is 134 ℃ of end.Separate water, obtain the even black bead of median size 0.82mm.Bead can utilize the steam foaming, and the tap density after 3 minutes is 11.8g/l.Thermal conductivity is measured at 10 ℃ according to DIN 52612, observed value 35mW/mK.
Embodiment 2
Repeat embodiment 1, graphite consumption 2%.The thermal conductivity of expanded bead when tap density is 10g/l is 34mW/mK.
Embodiment 3
Repeat embodiment 1, graphite consumption 4%.The thermal conductivity of expanded bead when tap density is 12g/l is 34mW/mK.
Embodiment 4 (comparative example)
Repeat embodiment 1, do not add graphite.The thermal conductivity of expanded bead when tap density is 10g/l is 44mW/mK.
Embodiment 5
Repeat embodiment 2, the bicummyl that has added the hexabromocyclododecane of 127g and 85g is as flame retardant system.Polyreaction is carried out under 125 ℃.Thermal conductivity is 34mW/mK and the requirement of having satisfied fire-protection rating B2.
Embodiment 6
In the pressurized vessel of a stirring, the mixture of 150 parts of deionized waters, 0.1 part of trisodium phosphate, 100 parts of vinylbenzene, 0.45 part of benzoyl peroxide, 0.15 part of peroxybenzoic acid tertbutyl ester and 5 parts of Kropfm ü hle Graphite Powder 99 99.5,2 parts of hexabromocyclododecanes of UFT (HBCD) and 0.4 part of dicumyl peroxide under agitation is heated to 90 ℃.
90 ℃ after following 2 hours, add the polyvinylpyrrolidone aqueous solution of 4 part of 10% concentration.
Continue restir 2 hours down at 90 ℃, add the mixture of 7 part of 80% Skellysolve A and 20% iso-pentane.Mixture then stirred 2 hours down at 110 ℃, and is following 2 hours at 140 ℃ at last.
Final expandable polystyrene beads grain is sized to 0.7～1.0mm with washed with de-ionized water, and dry in warm air subsequently.
Bead pre-frothing under the mobile vapor action was stored after 1 day, further handled and fused into one through steam in the mould of sealing, obtained the foam material body of density 15g/l.
Thermal conductivity is measured at 10 ℃ according to DIN 52612, observed value 34mW/mK.
Embodiment 7
0.498kg the excessive or too small EPS of particle diameter be dissolved in the vinylbenzene of 16.6kg, Graphite Powder 99 (Graphitwerk Kropfm ü hle KG with 16.6g, UF2 96/97), i.e. 0.1% graphite, the total amount of styrene-based and EPS, evenly be suspended in this solution, and add 83.0g dicumyl peroxide and 4.15g dibenzoyl peroxide and 112.033g hexabromocyclododecane (HBCD).This organic phase is transferred in the container of the 501 band stirrings that are added with 19.31 deionized waters.Water contains 46.127g trisodium phosphate and 86.348g sal epsom (Epsom salt).Suspensoid was warming up to 80 ℃ through 40 minutes.Add 2.32g emulsifying agent K30/40 (Bayer AG) then.After 40 minutes, be metered into the 1330g pentane, and finish polyreaction at 126 ℃.
Separate water, provide the even grey bead of median size 1.18mm.Through twice steam pre-frothing, the tap density of bead is 10.0g/l.Internal water content＜1.5%, residual styrene content＜1000ppm.Thermal conductivity during tap density 10g/l is 2mW/mK, and is lower than the situation of not adding graphite.The comparative example 8
Surface-coated is with graphite
The EPS bead of pre-frothing and 2.0% graphite mix in mixing tank.Apply also not exclusively, graphite is at the surface of beads skewness.In further treating processes, a large amount of graphite are wiped from surface of beads.Use binding agent (stearin, white oil) and also can't improve the coating effect.The fusion situation of molding is undesirable.
Claims (9)
1. but technology for preparing the extruded styrene polymkeric substance that contains graphite particle, it comprises vinylbenzene, optional together with the comonomer that accounts for its weight 20wt%, in the presence of the graphite particle of median size 1-50 μ m in aqueous suspension and add under the situation of peroxide initiator and carry out polymerization, whipping agent before the polyreaction, among or add afterwards.
2. the technology of claim 1, wherein polyreaction is carried out in the presence of styrene-based polymkeric substance meter 0.05～25wt% graphite.
3. the technology of claim 1, wherein suspension polymerization carries out in the presence of a kind of organbromine compound fire retardant.
4. the technology of claim 1, wherein suspension polymerization has adopted the styrene solution of polystyrene.
5. the technology of claim 4, what wherein adopt is the styrene solution of the polystyrene of concentration 0.5～30wt%.
6. the technology of claim 4, but the polystyrene that wherein adopts is the excessive and/or too small particle fraction of expanded polystyrene.
7. the technology of claim 1, wherein to be incorporated into transformation efficiency be 0.5～70% in the vinylbenzene pre-polymerization, and prepolymer is transferred to aqueous phase together with graphite particle.
8. but press the granular extruded styrene polymkeric substance of the prepared of claim 1, contain 0.05～25wt% graphite particle, wherein graphite particle is evenly distributed in the styrene polymer, and the form of styrene polymer is the circular bead of median size 0.2～2mm.
9. but the purposes of the granular extruded styrene polymkeric substance of claim 8 is in order to the foam of preparation density 5～35g/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97182185A CN1077583C (en) | 1997-05-14 | 1997-05-14 | Preparation of expandable styrene polymers containing graphite particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97182185A CN1077583C (en) | 1997-05-14 | 1997-05-14 | Preparation of expandable styrene polymers containing graphite particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1254356A CN1254356A (en) | 2000-05-24 |
| CN1077583C true CN1077583C (en) | 2002-01-09 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97182185A Expired - Lifetime CN1077583C (en) | 1997-05-14 | 1997-05-14 | Preparation of expandable styrene polymers containing graphite particles |
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| Country | Link |
|---|---|
| CN (1) | CN1077583C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675763B (en) * | 2011-03-17 | 2013-12-25 | 上海容志材料科技有限公司 | Additive composite used for preparing expandable polystyrene, and preparation method and application thereof |
| CN104292680B (en) * | 2014-09-15 | 2017-02-15 | 刘崴崴 | Polystyrene foam insulating material and preparation method thereof |
| CN106117398A (en) * | 2016-01-14 | 2016-11-16 | 新疆蓝山屯河新材料有限公司 | A kind of high fire-retardance low conductive graphite expandable polystyrene product and the production method of this product |
| CN105949360A (en) * | 2016-05-30 | 2016-09-21 | 日照新三明化工有限公司 | Flame-retardant expandable polystyrene containing flake graphite and body polymerization preparation method thereof |
| CN112079610B (en) * | 2019-06-14 | 2022-09-09 | 上海圣奎塑业有限公司 | Manufacturing process of foaming insulation board |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117943A (en) * | 1957-12-05 | 1964-01-14 | Crylor | Pigmented vinyl polymers prepared by adsorbing vinyl monomer on carbon black and then polymerizing said monomer |
| GB1588314A (en) * | 1978-03-20 | 1981-04-23 | Secr Defence | Processes for producing material by bonding expanded plastics granules |
-
1997
- 1997-05-14 CN CN97182185A patent/CN1077583C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117943A (en) * | 1957-12-05 | 1964-01-14 | Crylor | Pigmented vinyl polymers prepared by adsorbing vinyl monomer on carbon black and then polymerizing said monomer |
| GB1588314A (en) * | 1978-03-20 | 1981-04-23 | Secr Defence | Processes for producing material by bonding expanded plastics granules |
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| Publication number | Publication date |
|---|---|
| CN1254356A (en) | 2000-05-24 |
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