CN104520364A - A particulate, expandable polymer, a method for the production thereof and applications thereof - Google Patents

A particulate, expandable polymer, a method for the production thereof and applications thereof Download PDF

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Publication number
CN104520364A
CN104520364A CN201380040880.9A CN201380040880A CN104520364A CN 104520364 A CN104520364 A CN 104520364A CN 201380040880 A CN201380040880 A CN 201380040880A CN 104520364 A CN104520364 A CN 104520364A
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polymkeric substance
microgranular
styrene
foamable
carbon
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J·努尔德格拉夫
F·P·A·高路易特曼
M·盖伯瑞德
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Synbra Technology BV
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Synbra Technology BV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/008—Nanoparticles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention relates to a particulate, expandable polymer that can be processed into a foam with a fine cellular structure and a low density and that contains a carbon-based material increasing the thermal insulation value to increase the thermal insulation value thereof. The present invention further relates to a method for producing a particulate, expandable polymer, and to a foam material obtained with it.

Description

Microgranular foamable polymkeric substance, its manufacture method and application thereof
Technical field
The present invention relates to a kind of microgranular foamable polymkeric substance, this microgranular foamable polymkeric substance can be processed to have fine cell structure and low-density flame-retardant foam, and containing being improved the carbon-based material of insulation value to improve its insulation value.The invention still further relates to the microgranular foamable polymkeric substance of a kind of manufacture, and the foam materials obtained by the method.
Background technology
By the known a kind of composition for the production of thermoplastic polymer foam of international application WO2008/119059, comprise: can foamed polymer material, as 1 of unique required whipping agent, 1,2,2-Tetrafluoroethane and nano-graphite, their concentration range respectively between 80% and 99%, between 3.0% and 12%, between 0.05% and 5.0% (described per-cent is based on dry weight).The nano-graphite adopted is regarded as multi-layer nano graphite, and at least one dimension of multi-layer nano graphite has the thickness being less than 100nm, and be preferably comprised in carrier (namely polyethylene methyl acrylate multipolymer).Claim, the interpolation of nano-graphite improves the thermal characteristics of final froth product, mechanical property and flame retardant properties.
International application WO2007058736 relates to a kind of heat-staple brominated copolymer, and described multipolymer (being polymerization in this article) is containing butadiene fraction and vinyl aromatic portion.Add in polystyrene with flame retarding amount by this multipolymer, the mixture finally obtained has the bromine content of weight in the scope of 0.1wt.% ~ 25wt.% based on described mixture.
US2002/0117769 relates to a kind of spumescence cellular polymer particle, can add the additive of such as carbon black, titanium dioxide, aluminium and graphite wherein to reduce thermal conductivity.
US2012/0123007 relates to a kind of styrene polymer composition, and brominated flame retardant has been added into wherein.
By the known a kind of expandable polystyrene (EPS) (EPS) of the European patent EP 1486530 (corresponding to NL1023638) under the name of the applicant, its granules of polystyrene contains the gac as the material improving insulation value.Relevant gac has≤particle diameter of 12 microns.The foam obtained with the material of this raising insulation value meets according to B2 test, namely DIN4102, the fire resistant requirements of part 2.
By the known polystyrene foamed of the WO2010/041936 under the name of the applicant (EPS), wherein, use the gac with specific size distribution as the mode improving insulation value.
By a kind of known method manufacturing the graphite containing EPS of United States Patent (USP) 6130265, styrene-based polymkeric substance, the graphite of the amount of 0.05 ~ 25wt.% is added into wherein.
By the known a kind of particulate state expandable polystyrene (EPS) of United States Patent (USP) 6340713, wherein, the median size that styrene polymer contains 0.05 to 8wt.% is the equally distributed graphite granule of 1 to 50 μm.
A kind ofly the heat insulation method of EPS is improved by international patent application WO00/43442 is also known; wherein; styrene polymer melting mixing with at least one whipping agent and aluminum particulate in an extruder; mainly the form of plate united are extruded for they; the concentration of the aluminum particulate adopted is 6wt.% at the most, and extrudate is cooled and is reduced to particle thereafter.The aluminium of such polymkeric substance at least containing particle form is to improve their heat-proof quality, and aluminum particulate is evenly distributed over and is merged in the material as infrared radiation reflecting.Aluminum particulate has the plate-like shape being of a size of 1 to 15 μm.
Not only can by raw material for the manufacture of expandable polystyrene (EPS) (EPS) can also be obtained by suspension polymerization by the known expressing technique of aforementioned international patent application.The EPS particle of such acquisition is used as raw material usually in packaging industry and building.The method of further process comprises pre-foaming, wherein, makes a certain amount of steam by the layer of the EPS particle in expansion vessel, thus makes the whipping agent (normally pentane) comprised in EPS particle evaporate and the foaming of particle is occurred.After preservation (the being also referred to as solidification) period of about 4 ~ 48 hours, the so pre-particle bubbled is introduced in mould, and particle foams further under the effect of steam in a mold.The mould adopted has little opening, and the whipping agent still existed during allowing foaming is overflowed when the shape needed for particle fusion becomes.The size of this shape does not limit in principle, therefore, it is possible to obtain the dividing plate (block) that is used for building trade and the wrapping material for food and non-food industries simultaneously.Aforesaid method is different from the method known to WO2008119059 substantially, and the method relates to the foam bubbled continuously in single step process in continuous extruder.
Fire retardant is often added in the manufacture of foam.This foam materials is further processed into product and the article that fire line or flame retardant resistance must meet the requirement of national competent authorities defined.According to hypothesis, such fire retardant has unacceptable chemical affect to human body and environment.Just because of this, some fire retardant is progressively eliminated.
Summary of the invention
An object of the present invention is to prove a kind of microgranular foamable polymer fine particles, further to after its processing, can obtain having the enough low thermal conductivity of actual needs with the flame retardant resistance foam making it be suitable for the heat-proof quality of expecting.
Another aspect of the present invention is to provide a kind of manufacture can the method for foamable polymer particulate, wherein, styrene polymer can be converted under the existence of one or more annexing ingredients foaming and molded after there is the material of the insulation value of raising.
Another aspect of the present invention is to provide a kind of method manufacturing foamable polymer fine particles, and wherein, use the fire retardant that minimum bio-toxicity is shown, this fire retardant is safe to human and animal and meets security requirement general in building trade.
That mentions above the invention is characterized in, polymer beads contains the carbon of particle diameter <1 μm as the material improving insulation value and the bromination SBS (styrene-butadiene-styrene) contained as fire retardant.
One or more aspect of the present invention meets as the material improving insulation value by using such carbon.Above-mentioned fire retardant can also be regarded as the mode meeting security requirement general in building trade, and also has minimum impact to the mankind and environment.
The preferred value of 0.1 μm is designated as the lower limit of particle diameter.The present invention eliminates especially and uses carbon black as carbon source.
It is desirable for that particle diameter D50 is at most 1 μm especially, more specifically, particle diameter D 50be at most 0.8 μm.
D 90value and D 50value is understood to the 90th percentile and the 50th percentile respectively, lower than D 90value and D 50the particle diameter of value falls into overall 90% and 50% respectively.Easily can infer D10 (size lower than D10 falls into overall 10%), D50 (size lower than D50 falls into overall half) and D90 (size lower than D90 falls into overall 90%) by the integral distribution curve using the Malvern instrument (Malvern Instruments) of product Master particle size analyzer (Mastersizer) and Lazer particle size analyzer (Lazersizer) to obtain, and these three values (D10, D50 and D90) can be used to the size distribution characterizing powder.Particularly, (D90-D10)/D50 ratio (being also referred to as size distribution) provides the good instruction of the distribution of the size comprised in powder.
In other words, the 10th percentile be 10% particle be less than or equal to the particle diameter of this value, therefore, the particle of 90% is greater than described value.
In other words, the 50th percentile be 50% particle be less than or equal to the particle diameter of this value, therefore, the particle of 50% is greater than described value.D50 is preferably at most 1.0 μm, is particularly at most 0.8 μm.
In other words, the 90th percentile be 90% particle be less than or equal to the particle diameter of this value, therefore, the particle of 10% is greater than described value.
Preferably, use the segmented copolymer of polystyrene and brominated polybutadiene can the bromination SBS (styrene-butadiene-styrene) of foamable polymer as particulate state of the present invention.
Based on bromination SBS (styrene-butadiene-styrene), the scope of the weight percent of bromine is preferably between 60wt.% and 70wt.%.Based on bromination SBS (styrene-butadiene-styrene), the preferred scope of 30wt.% ~ 50wt.% is specifically used to cinnamic weight percent.
In special embodiment, the scope of the molecular weight of bromination SBS (styrene-butadiene-styrene) is preferably between 60000 and 150000.
Based on the gross weight of microgranular foamable polymkeric substance, the scope of the amount of bromination SBS (styrene-butadiene-styrene) is preferably between 0.7wt.% and 2.2wt.%.
In special embodiment, the basis of the gross weight of described microgranular foamable polymkeric substance calculates, and the amount of hexabromocyclododecane (HBCD) is less than 1.0wt.%, is particularly less than 0.6wt.%, more especially be less than 0.2wt.%, be preferably less than 0.05wt.%.
By the viewpoint with the consistency of polymkeric substance, required flame retardant properties, bio-toxicity, thermostability and persistence, find that above-mentioned value is advantageous particularly.
The polymkeric substance used in the present invention is selected from the group comprising polystyrene, expanded polypropylene (EPP), the polyethylene foamed (EPE) having abscess, polyphenylene oxide (PPO), poly(propylene oxide) and poly(lactic acid) or their combination.
Poly(lactic acid) (PLA) is the collective noun of the polymkeric substance based on lactic acid monomer, can make poly(lactic acid) according to its composition and from completely amorphous be changing into hemicrystalline or crystallization.Poly(lactic acid) can be made up of such as milk-product, starch, flour and corn.Lactic acid is the monomer of composition poly(lactic acid), and this monomer is with two kinds of steric isomers, and namely Pfansteihl and D-ALPHA-Hydroxypropionic acid occur.Therefore, poly(lactic acid) contains a certain proportion of Pfansteihl monomer and a certain proportion of D-ALPHA-Hydroxypropionic acid monomer.In poly(lactic acid), the ratio of Pfansteihl monomer and D-ALPHA-Hydroxypropionic acid monomer determines its character.Also term " D-value " and " D-content " (per-cent of D-ALPHA-Hydroxypropionic acid monomer) can be used.Current commercially available poly(lactic acid) has the L:D ratio between 100:0 and 75:25; In other words, the D-content between 0 and 25% or between 0 and 0.25.
The example of the further process of PLA particulate is as follows.With such as 6 ~ 8%CO 2after filling, PLA particulate bubbles under the pressure of such as 20 bar.Then, again using PLA as foam, with such as 6%CO 2fill and vapor pressure lower mould between 0.2 bar and 0.5 bar.In the identical mode as above discussed about EPS particulate to obtain the molded parts of this mode.
In extrusion device, use template to manufacture PLA particulate.For this reason, solid PLA to be incorporated in extrusion equipment and to melt.Then, by mould such as so-called underwater pelletizer (underwater granulator), the PLA of fusing is extruded, and via template cutting PLA particle.In online polymerization (in-linepolymerisation) technique, liquid PLA directly can also be provided to extrusion device, so without the need to first melting.Preferred use twin screw extruder is as extrusion device.In extrusion device, mixture and optional one or more chainextenders, nucleator and the lubricant of poly(lactic acid) or poly(lactic acid) and optional one or more other biodegradable polymkeric substance can be processed into particle.This granular poly(lactic acid) is also illustrated in the PCT/NL2008/000109 of the present inventor.
After extruding poly(lactic acid), add whipping agent to obtain foamable PLA (EPLA) by filling PLA particle.The example of spendable whipping agent is CO 2, MTBE, nitrogen, air, (different) pentane, propane, butane etc., or they one combination or multiple combination.First kind of way is, such as, make poly(lactic acid) be configured as particle by extruding, and makes particle become foamable subsequently by filling with whipping agent.Second method is, poly(lactic acid) is mixed with whipping agent, subsequently by such as extruding and making its direct forming be expandable particles.
The present inventor supposes, carbon atom arrangement can be used especially to become the Graphene of honeycomb flat crystal grid (being considered to the monatomic thick plane layer of the carbon atom that sp2 combines) or expanded graphite, be generally used for improving the material of insulation value than this area to obtain, particularly compared with other carbon source of such as graphite or gac, less certain insulation value.Supplementary experiment shows, and the material being called as " Graphene " here also can be regarded as the expanded graphite of the particle diameter with 0.1 ~ 0.8 μm.In the description, " Graphene " therefore should be understood to the expanded graphite of the particle diameter with 0.1 ~ 0.8 μm.This reduction improving the addition of the material of insulation value has favourable effect to the final color that material script is the EPS of white.The grey a little that above-mentioned additive contributes to the EPS of white originally " is faded ".
Particularly, therefore the present invention focuses in the use of special carbon source (particularly expanded graphite), this a small amount of material can have the effect shown, and surprising result is designed the combination with the specific fire retardant meeting insulation request and flame-retardancy requirements simultaneously by the special geometric owing to expanded graphite.The aforesaid combination of special carbon source and specific fire retardant is considered to essence of the present invention.
Term used herein " expanded graphite " should not obscured with the term " nano-graphite " known by WO2008119059, particularly, as long as consider their size and three-dimensional structure.
In special embodiment, the expanded graphite using length-to-diameter ratio >=10:1, more specifically >=100:1 is desirable especially.Such laminate structure has particularly preferred impact to raising insulation value.
Based on polymkeric substance, the amount of carbon is 1 ~ 15wt.%, and to be preferably based on polymkeric substance be 2 ~ 8wt.% is desirable especially.
Must it is clear that, in some embodiments, one or more other reagent being present in the raising insulation value in microgranular foamable polymkeric substance are in addition desirable especially, and one or more other reagent of this raising insulation value are selected from and comprise graphite, carbon black, aluminium powder, Al (OH) 3, Mg (OH) 2and Al 2o 3, the group of iron, zinc, copper and their alloy.
In the past, use hexabromocyclododecane (HBCD) as fire retardant, to obtain good flame retardant effect.The present invention concentrates on the use of alternative HBCD especially, and this produces the finished product compared favourably with the polymeric articles containing HBCD on particularly in fire protection requirement.Particularly, the object of the invention is to make the amount of HBCD to minimize, more specifically the amount of HBCD is reduced to zero.
If the product obtained must meet strict fire safety demands, based on the amount of polymkeric substance, one or more fire retardants providing the amount between 1.0wt.% and 8wt.% are in addition desirable, these one or more fire retardants are selected from and comprise dicumyl peroxide, brominated polymer compound, particularly polystyrene compounds and 2, in the group of 3-dimethyl-2,3-diphenyl butane.Can also add be selected from comprise polyphosphonate, diphenylphosphine acid esters, dihydroxyphenyl propane-bis-(diphenyl phosphoester) and Resorcinol aromatics polyphosphate compound or their combination the P contained compound of group as auxiliary agent.
By making carbon source stand mechanical shear stress, the expanded graphite that particularly can obtain mentioning in the application by making graphite stand such process.The example of this process is expressing technique, and wherein, graphite stands significant shearing force in an extruder, thus make graphite change into flat carbon plate, particularly expanded graphite.The present inventor supposes that above-mentioned flat carbon plate is responsible for the reflection undertaken by thermal-radiating mirrored effect.This makes adopted carbon have to a certain degree flat size or geometrical shape is desirable with the mirror effect realizing expecting.In some embodiments, carbon source quantitatively can give as masterbatch or directly as powdered material, and this powdered material is pretreated to obtain in claim the particle diameter needed for specifying.
The invention still further relates to a kind of for the manufacture of microgranular foamable polymkeric substance, wherein, as appended dependent claims mentioned, polymkeric substance is fed into forcing machine, and mix with at least one whipping agent, bromination SBS (styrene-butadiene-styrene), carbon source and one or more other auxiliary agents, and be extruded subsequently, cool and be reduced to particle further.
In special embodiment, the invention further relates to a kind of method manufacturing microgranular foamable polymkeric substance, wherein, as appended dependent claims mentioned, make the reagent of monomer, bromination SBS (styrene-butadiene-styrene), whipping agent, raising insulation value and one or more other auxiliary agents stand polyreaction in the reactor.Particularly, as the density of the EPS of preferred polymkeric substance at 850kg/m 3and 1050kg/m 3between scope in be desirable.Preferred whipping agent is (different) pentane.Getting rid of fluorine-containing hydrocarbon compound is desirable as whipping agent.Therefore, preferably, microgranular foamable polymkeric substance is manufactured, wherein, based on above-mentioned particulate can the amount of foamable polymer, the amount of hydrochlorofluorocar,ons compound is minimized, preferably be less than 2.0wt.%, be particularly less than 1.0wt.%, be more specifically less than 0.5wt.%.Owing to minimizing the cause of the above-mentioned hydrochlorofluorocar,ons compound in microgranular foamable polymkeric substance, the final frothed product obtained there is no fluorine-containing hydrocarbon compound.
The invention further relates to based on microgranular as above can the polymer foams of foamable polymer, this polymer foams is preferably used to such as heat insulation in building trade object, is also used as the wrapping material in food and non-food industries.
Accompanying drawing explanation
Set forth the present invention referring now to some embodiments, must supplement, the present invention is defined as these embodiments never in any form.
Fig. 1 shows the measuring result of various carbon source.
Fig. 2 is the diagram of the various density of EPS material and the relation of λ value.
Embodiment
Mensuration as shown in the table, the size distribution of various product.
Product, the type of carbon D10 D50 D90
Commercially available EPS molding part, graphite 2 4 12
By the EPS molding part of the commercially available introducing of applicant, gac 2 5 31
The present invention, the micronized graphite of Graphene 0.4 0.8 1
D50 value is 1 μm at the most, more specifically at the most 0.8 μm be desirable especially.
To the multiple mechanical property of multiple commercially available products measures, and carry out flammability test.Can infer clearly from measuring result, the thermal conductivity of interpolation to the moulding part of the final foaming based on EPS of graphite or expanded graphite has favorable influence.
Numeral in table below has following implication:
1=HBCD is as fire retardant
2=is without fire retardant
3=Resorcinol is as fire retardant
4=emerald shiner 3000 (Emerald 3000) (by Chemtura (Chemtura) commercially available introducing) is as fire retardant
5=FR122P (by ICI commercially available introducing) is as fire retardant
6=XP-7720FR122P (by refined treasured (Albemarle) commercially available introducing) is as fire retardant.
This table sequentially show: the row of the row of the row of the type of parent material, the row of wt.% fire retardant, wt.% dicumyl peroxide, the row of density (g/l), lambda (W/mK's), the row of density (g/l), the row of compressive strength (kPa), the row of density (g/l), the row of fracture tensile strength (kPa), and the row of last flammability test DIN 4102-1B2, wherein, the unmeasured and pass=of nt=passes through.
This material EPS 710F 0.7 ~ 1.0mm particle diameter Synbra science and technology (Synbra Technology) is melted in twin screw extruder with 5.5% pentane with 125kg/h, along with interpolation P1000 polyethylene (BakerHuigjes) 0.1% and Graphene masterbatch and Graphene concentration, 4% Graphene is effectively introduced in polystyrene.The temperature of forcing machine is preferably between 150 DEG C and 230 DEG C; In the present embodiment, the pentane that also interpolation 0.8% is extra is as whipping agent.Mixture is fed in the cooling extruded machine of temperature between 60 DEG C and 150 DEG C, manufactures the XPS plate of grey with it.
The foam obtained has 35kg/m 3density.Having found the insulation value of foam: when masterbatch, is 31.1mW/mK; Further, when enriched material, be 30.9mw/mK.Further, two kinds of products all have passed flammability test DIN4102B2.
Appended Fig. 2 is the diagram of multiple measurement, and wherein, transverse axis represents density, and vertical axes represents λ (W/mK).Can infer clearly from this diagram, under the density identical with the EPS adding expanded graphite (particle diameter between 0.1 and 0.8 μm) with certainweight per-cent, the commercially available Neopor containing 4wt.% graphite (being mainly particle diameter >1 μm, particularly 1 ~ 50 μm) obtains higher λ value.
the mensuration of the particle diameter of expanded graphite
The EPS of the foaming of the grey of the amount of 10g is dissolved in the toluene of 28ml.This slurry is made to stand to analyze.Make resistates carry out ultrasonic disperse under the interpolation of more toluene, and use ALV instrument to analyze.Particle diameter is measured with Malvern laser particle analyzer (Malvern Zetasizer).If desired, dilute further with toluene.Laser particle analyzer GMA is so-called dynamic light scattering, there is following specification: the outside protractor correlator of correlator ALV5000/60X0: ALV-125 detector: ALV/SO SIPD single-photon detector, there is Static and dynamic intensifier booster ALV laser fiber: Cobolt Samba 300DPSS laser apparatus, wavelength: 532nm, 300mW power temperature controls: static heating bath: Haake F8-C35.Do not use special standard; The pedesis of this apparatus measures particle, and, under solvent is water and particle is roughly spherical hypothesis, via einstein-Stokes equations, observed value is changed into particle diameter.Pair radius is measured.
It is apparent that graphite reference material has larger particle diameter and aggregate, this is also visually observable.The expanded graphite comprised in EPS shows more tiny particle, and the particle diameter of average specific graphite is little 3 to 5 times.Although there are some gatherings of little particle, when graphite, aggregate is not occupied an leading position.Its result is illustrated in appended Fig. 1.

Claims (24)

1. a microgranular foamable polymkeric substance, described microgranular foamable polymkeric substance can be processed to have fine cell structure and low-density flame-retardant foam, and described microgranular foamable polymkeric substance is containing being improved the carbon-based material of insulation value to improve the insulation value of described microgranular foamable polymkeric substance, it is characterized in that, polymer beads contains the carbon of particle diameter <1 μm as the material improving insulation value, and comprises the bromination SBS (styrene-butadiene-styrene) as fire retardant.
2. microgranular foamable polymkeric substance according to claim 1, is characterized in that, D50 particle diameter is 1 μm at the most.
3. according to the microgranular foamable polymkeric substance in aforementioned claim described in or two, it is characterized in that, D50 particle diameter is 0.8 μm at the most.
4. according to described microgranular foamable polymkeric substance one or more in aforementioned claim, it is characterized in that, described polymkeric substance is selected from the group comprising polystyrene, expanded polypropylene (EPP), the polyethylene foamed (EPE) having abscess, polyphenylene oxide (PPO), poly(propylene oxide) and poly(lactic acid) or their combination.
5. according to described microgranular foamable polymkeric substance one or more in aforementioned claim, it is characterized in that, expanded graphite, expanded graphite particularly in the scope of particle diameter between 0.1 μm and 0.8 μm is used as carbon, length-to-diameter ratio >=the 10:1 of described expanded graphite, wherein, described expanded graphite has the structure of flat carbon plate especially.
6. microgranular foamable polymkeric substance according to claim 5, is characterized in that, the length-to-diameter ratio >=100:1 of described expanded graphite.
7., according to described microgranular foamable polymkeric substance one or more in aforementioned claim, it is characterized in that, based on the amount of described microgranular foamable polymkeric substance, the amount of described carbon is 1wt.% ~ 15wt.%.
8. microgranular foamable polymkeric substance according to claim 7, is characterized in that, the amount of described carbon is 2wt.% ~ 8wt.%.
9. according to described microgranular foamable polymkeric substance one or more in claim 5 ~ 8, it is characterized in that, expanded graphite in described expanded graphite, the particularly particle diameter scope between 0.1 μm and 0.8 μm is by carbon source, particularly graphite mechanical shearing and obtain.
10. according to the microgranular foamable polymkeric substance in aforementioned claim described in or two, it is characterized in that, the lower limit >0.1 μm of the particle diameter of described carbon.
11., according to the microgranular foamable polymkeric substance in aforementioned claim described in or two, is characterized in that, described bromination SBS (styrene-butadiene-styrene) is the segmented copolymer of polystyrene and brominated polybutadiene.
12. microgranular foamable polymkeric substance according to claim 11, it is characterized in that, based on described bromination SBS (styrene-butadiene-styrene), the scope of the weight percent of bromine is between 60wt.% and 70wt.%.
13. according to the microgranular foamable polymkeric substance in claim 11 ~ 12 described in or two, it is characterized in that, based on described bromination SBS (styrene-butadiene-styrene), the scope of cinnamic weight percent is between 30wt.% and 50wt.%.
14. according to described microgranular foamable polymkeric substance one or more in claim 11 ~ 13, and it is characterized in that, the scope of the molecular weight of described bromination SBS (styrene-butadiene-styrene) is between 60000 and 150000.
15. according to described microgranular foamable polymkeric substance one or more in aforementioned claim, it is characterized in that, based on the gross weight of described microgranular foamable polymkeric substance, the scope of the amount of described bromination SBS (styrene-butadiene-styrene) is between 0.7wt.% and 2.2wt.%.
16. according to described microgranular foamable polymkeric substance one or more in aforementioned claim, it is characterized in that, based on the gross weight of described microgranular foamable polymkeric substance, the amount of hexabromocyclododecane (HBCD) is less than 1.0wt.%, particularly be less than 0.6wt.%, more especially be less than 0.2wt.%, be preferably less than 0.05wt.%.
17. 1 kinds of methods manufactured according to described microgranular foamable polymkeric substance one or more in aforementioned claim 1 ~ 16, it is characterized in that, described polymkeric substance is fed into forcing machine, and with the carbon of at least one whipping agent, bromination SBS (styrene-butadiene-styrene), particle diameter <1 μm and one or more other needed for auxiliary agent mix, and be extruded subsequently, cool and be reduced to particle further.
18. 1 kinds of methods manufactured according to described microgranular foamable polymkeric substance one or more in aforementioned claim 1 ~ 16, it is characterized in that, the carbon of monomer, whipping agent, bromination SBS (styrene-butadiene-styrene) and particle diameter <1 μm and one or more other needed for auxiliary agent be polymerized in the reactor, and optionally cooling be reduced to particle further in subsequent step.
19., according to the method in claim 17 ~ 18 described in or two, is characterized in that, are selected from and comprise graphite, carbon black, aluminium powder, Al (OH) 3, Mg (OH) 2, Al 2o 3, one or more reagent improving insulation value in the group of iron, zinc, copper and their alloy are added to auxiliary agent.
20. according to the method described in claim 17 ~ 19, it is characterized in that, be selected from comprise polyphosphonate, diphenylphosphine acid esters, dihydroxyphenyl propane-bis-(diphenyl phosphoester) and Resorcinol aromatics polyphosphate compound or their combination P contained compound be added to auxiliary agent.
21. 1 kinds of polymer foams, based on according to described microgranular foamable polymkeric substance one or more in claim 1 ~ 16.
The carbon of 22. particle diameter <1 μm in fire retardant foam for improving the application of the insulation value of described fire retardant foam, described fire retardant foam comprises the bromination SBS (styrene-butadiene-styrene) as fire retardant, and based on microgranular foamable polymkeric substance.
23. application according to claim 22, are used in building trade.
24. application according to claim 22, are used in packaging industry.
CN201380040880.9A 2012-08-14 2013-08-14 A particulate, expandable polymer, a method for the production thereof and applications thereof Pending CN104520364A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106609008A (en) * 2015-10-22 2017-05-03 贵州五洲新材料科技有限公司 Synthetic method for carbon nanotube/carbon black compound modified styrene resin

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6405781B2 (en) * 2014-08-08 2018-10-17 株式会社ジェイエスピー Expandable styrene resin particles and method for producing the same
NL2014258B1 (en) 2015-02-06 2016-10-13 Synbra Tech B V A process for producing foam mouldings.
AU2017264495A1 (en) 2016-05-11 2018-11-29 Owens Corning Intellectual Capital, Llc Polymeric foam comprising low levels of brominated flame retardant and method of making same
WO2018069186A1 (en) 2016-10-10 2018-04-19 Total Research & Technology Feluy Improved expandable vinyl aromatic polymers
CN107337863A (en) * 2017-05-17 2017-11-10 无锡兴达泡塑新材料股份有限公司 A kind of static conductive polystyrol foam material of graphene-containing and preparation method thereof
JP7239277B2 (en) * 2017-06-13 2023-03-14 株式会社イノアック技術研究所 conductive foam
US11459452B2 (en) * 2017-08-10 2022-10-04 Dow Global Technologies Llc Compositions comprising brominated polymeric flame retardant
CN114341256A (en) 2019-09-04 2022-04-12 道达尔能源一技术比利时公司 Expandable vinyl aromatic polymers with improved flame retardancy
CN113462094B (en) * 2021-07-07 2023-06-23 江苏筑立建筑科技有限公司 Flame-retardant graphene extrusion molding foaming plate and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1486530A1 (en) * 2003-06-11 2004-12-15 Synbra Technology B.V. Activated carbon-containing particulate, expandable polystyrene
CN101305022A (en) * 2005-11-12 2008-11-12 陶氏环球技术公司 Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends
WO2011133034A1 (en) * 2010-04-21 2011-10-27 Synbra Technology B.V. Particulate, expandable polymer, a method for preparing the same as well as the use thereof

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT406477B (en) 1999-01-25 2000-05-25 Sunpor Kunststoff Gmbh PARTICULATE, EXPANDABLE STYRENE POLYMERISATES AND METHOD FOR THE PRODUCTION THEREOF
MXPA03004908A (en) * 2000-12-04 2004-05-24 Nova Chem Inc Foamed cellular particles of an expandable polymer composition.
US20080242752A1 (en) * 2007-03-28 2008-10-02 Yadollah Delaviz Polystyrene foams incorporating nanographite and HFC-134
NL1036039C (en) 2008-10-09 2010-04-12 Synbra Tech Bv PARTICULATE, EXPANDABLE POLYMER, METHOD FOR MANUFACTURING PARTICULAR EXPANDABLE POLYMER, AND A SPECIAL USE OF THE OBTAINED FOAM MATERIAL.
EP2406307B1 (en) * 2009-02-26 2012-12-12 ICL-IP America Inc. Styrenic polymer composition
JP5436024B2 (en) * 2009-04-27 2014-03-05 ダウ化工株式会社 Styrenic resin foam
IT1396918B1 (en) * 2009-11-03 2012-12-20 Polimeri Europa Spa PROCEDURE FOR THE PREPARATION OF GRAPHENIC NANOPIASTRINES WITH HIGH LEVELABILITY IN LOW POLARITY POLYMER MATRICES AND THEIR POLYMERIC COMPOSITIONS
DE102009059781A1 (en) * 2009-12-18 2011-06-22 Basf Se, 67063 Flame retardant polymer foams
NL2004587C2 (en) * 2010-04-21 2011-10-24 Synbra Tech Bv INSULATING FOAMED FORM.
ES2703732T3 (en) * 2010-12-17 2019-03-12 Dow Global Technologies Llc Extrusion process of polystyrene in the molten state

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1486530A1 (en) * 2003-06-11 2004-12-15 Synbra Technology B.V. Activated carbon-containing particulate, expandable polystyrene
CN101305022A (en) * 2005-11-12 2008-11-12 陶氏环球技术公司 Brominated butadiene/vinyl aromatic copolymers, blends of such copolymers with a vinyl aromatic polymer, and polymeric foams formed from such blends
WO2011133034A1 (en) * 2010-04-21 2011-10-27 Synbra Technology B.V. Particulate, expandable polymer, a method for preparing the same as well as the use thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106609008A (en) * 2015-10-22 2017-05-03 贵州五洲新材料科技有限公司 Synthetic method for carbon nanotube/carbon black compound modified styrene resin
CN106609008B (en) * 2015-10-22 2019-04-05 河北五洲开元环保新材料有限公司 The synthetic method of the composite modified polystyrene resin of carbon nanotube/carbon black

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