CN104194177A - Novel expandable polystyrene (EPS) functional material - Google Patents
Novel expandable polystyrene (EPS) functional material Download PDFInfo
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Abstract
The invention belongs to the technical field of novel materials, particularly a novel expandable polystyrene (EPS) functional material. The preparation method comprises the following steps: modifying polystyrene or styrene copolymer containing styrene monomer and other monomers, wherein the auxiliary materials for modification comprise graphite, halogen flame-retardant synergistic agent antimony trioxide or antimony pentoxide colloid, halogen flame retardant, phosphorus flame retardant, nitrogen or nitrogen-phosphorus flame retardant, compatilizer, heat stabilizer, plasticizer, nucleating agent, smoke suppressor, colorant and the like; and carrying out effective melting and compounding on the materials by an extruder, sufficiently mixing the materials, sending the plastified melt into a melt pump to perform pressure increase and pressure stabilization, sending the melt into a copolymerized to filter out impurities, sending the filtered melt into a conversion valve and a template, sending into a granulating chamber, and granulating the high-molecular polymer mixed with the pentane and auxiliary materials to obtain the graphite flame-retardant-grade EPS. The novel material has passed through B1-grade detection, is a novel energy-saving environment-friendly safe architectural material, and has broad market prospects.
Description
Technical field
The invention belongs to new material technology field, specifically belong to a kind of Expandable Polystyrene (EPS) function novel material.
Background technology
By the modification of p-poly-phenyl ethene, prepare Expandable Polystyrene (EPS) novel material; be specially and pass through melt-blending process; in single screw rod, twin screw extruder, make the shear-mixed such as graphite, carbon black, antimonous oxide, halogen flame, phosphorus flame retardant, nitrogen system or nitrogen-phosphorus flame retardant, softening agent, compatilizer, polyethylene wax; utilize and shear the hot melt polymkeric substance producing and modified materials is evenly mixed; subsequently; by high-pressure pump, quantitatively add appropriate pentane; then granulation in tablets press, obtains Expandable Polystyrene (EPS) function novel material.This material has good flame retardant resistance, high strength, foaming density is low, antistatic, antibacterial and anti-mildew becomes, and as engineering plastics, is widely used in the fields such as heat insulating of high-end construction market.
Expandable Polystyrene (EPS) EPS is widely used in building materials and packaging field, has the functions such as adiabatic heat-insulation, cold insulation, protection against the tide, shockproof, sound insulation.Its synthetic method is generally suspension polymerization process, as patent: CN101092462,102585392A discloses the technique that expandable polystyrene particle adopts suspension method to prepare, this process using calcium phosphate is made suspension agent, sodium sulfonate is as emulsifying agent, water-fast styrene monomer, initiator, fire retardant, retardant synergist, softening agent etc. are separated into drop under suspension stabilizer and high-speed stirring, then generate polymer beads, become solid dispersed phase; Whipping agent is impregnated in solid dispersed phase under certain condition, through operations such as cooling, dehydration, dry, surface treatments, obtains Expandable Polystyrene (EPS), and these EPS can meet heat-insulation and heat-preservation, the purposes such as shockproof.The production method that EPS is manufactured in this suspension polymerization is extensively known, except above-mentioned Chinese patent, also has: US5 for example, 240967, RU2087486C1, DE19548311A1, FR2820427A1 etc.
Seriously deficient in current water resources, environmental issue is subject in the situation of social pay attention to day by day, the need of suspesion process consume great lot of water resources, organic volatile divide be easily diffused in atmosphere, technician that shortcoming that heating suspension system need to consume a large amount of energy requires to be engaged in Expandable Polystyrene (EPS) develops novel process, new technology solves above-mentioned environmental issue and energy problem becomes the task of top priority.
EP0668139A1 provides a kind of production method of expanding styrene polymer granules, and polystyrene melt stream and whipping agent stream are provided in the first static mixer, makes it abundant shear-mixed; Said mixture is further abundant shear-mixed in the second static mixing district; In the 3rd static mixer, this mixture is cooled to pelletizing temperature required, by spinning nozzle quenching extruded polymer silk and be cut into the EPS particulate that whipping agent was uniformly distributed and had same size, shortcoming is the narrow molecular weight distribution of requirement polymkeric substance, and type is single.
The method of producing the EPS bead of narrow diameter distribution is disclosed from US5000801, being about to EPS and nucleator mixes, EPS adopts suspension polymerization process to produce, contain whipping agent 5.7-7.5%, nucleator is the mixture of citric acid and soda, and add-on is 0.25-0.4g/kgEPS, EPS bead and nucleator enter in forcing machine and melting after mixing in mixing tank, and wire drawing granulation under certain condition obtains the expanding styrene polymer granules that contains narrow size distribution.The shortcoming of the method is to use molecular weight (MW) to be less than 200000, and the melt index polymkeric substance that is 4.5～5.0, has limited the use of this method.
Summary of the invention
The present invention carries out modification by p-poly-phenyl ethene or containing styrene monomer and other monomer copolymerization styrenics, modification subsidiary material are graphite, halogen is fire retarding synergist antimonous oxide or Diantimony Pentoxide Colloid, halogenated flame retardant, phosphorus flame retardant, nitrogen system or nitrogen-phosphorus flame retardant, softening agent, nucleator, smoke suppressor, tinting material etc., it is mixing that forcing machine carries out efficient melting to material, material mixes fully, melt after plasticizing enters respectively Melt Pump, after Melt Pump supercharging and voltage stabilizing, enter net-changing device impurity screening, melt after filtration enters cross over valve and template enters pelletizing chamber, to being mixed with the high molecular polymer of pentane and auxiliary material, carrying out pelletizing and obtain graphite flame retardant grade EPS.
Expandable Polystyrene (EPS) function novel material, wherein polystyrene functional novel material comprises GPPS (General Purpose Polystyrenre), HIPS (high-impact polystyrene), EPS (regular grade Expandable Polystyrene (EPS), flame retardant grade Expandable Polystyrene (EPS)), SAN (styrene-propene is fine), ABS (acrylonitrile-butadiene-phenylethylene), SMA (vinylbenzene and maleic anhydride copolymers), SMA-ABS (SMA and ABS blend), ASA (propylene is fine-copolymer in cinnamic acrylic ester, vinylformic acid is generally butyl acrylate, there is weathering resistance and thermal ageing resistant performance), MBS (methacrylic ester-butadiene-styrene), MABS (methyl methacrylate-acrylonitrile-butadiene-phenylethylene), PPE (polyphenylene oxide).
Preferably, described graphite addition with respect to polystyrene from 1.5～8% quality, the high purity graphite that preferred mass is 1.5-5%.
Preferably, described graphite is expansible black lead, micro powder graphite or Graphene.
Preferably, the relative polystyrene quality of described carbon black add-on is 0.2～6%; Particle size carbon black is 5nm-40nm.
Preferably, described antimonous oxide, relative polystyrene quality, its add-on is 0.2～3%.
Preferably, described antimonous oxide, relative polystyrene quality, its add-on is 0.2～3%.
Preferably, described halogenated flame retardant, its addition of polystyrene quality is 0.5～7% relatively, described bromide fire retardant is two (allyl group) ether of hexabromocyclododecane, tetrabromo-bisphenol or tetrabromo-bisphenol, organic bromine fire retardant also can comprise brominated Polystyrene, this brominated Polystyrene can be the synthetic brominated flame-retardant polystyrene that is 1.0～2.5% or with phenylstilbene bromide and styrene copolymerized and add polystyrene, three (2,3-dibromopropyl) the isocyanuric acid ester of part brominated flame-retardant.
Preferably, described phosphorus flame retardant, is 5～20% with respect to its add-on of polystyrene quality.
Preferably, described fire retarding synergist is DCP, dicumyl peroxide, and the relative polystyrene quality of its addition is 0.05～3.5%.
Preferably, described softening agent is mineral oil or o-phthalic acid dibutyl ester, with respect to its addition of polystyrene quality, is 0.01～2%.
Preferably, described nucleator is polyethylene wax, and its addition of polystyrene quality is 0.02～3% relatively.
Preferably, described whipping agent is not halogen-containing C
nhm compound, n=4～6, comprise butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane and hexane, conventionally use Skellysolve A and iso-pentane, Skellysolve A: iso-pentane=7:3 or 6:4, the quality of relative polystyrene, its add-on is 3.5～10%.
Novel material and novel process that the present invention obtains have the following advantages:
1, overcome the shortcoming that the synthetic Expandable Polystyrene (EPS) of suspension polymerization process need to consume a large amount of water, saved precious water resources;
2, having overcome suspension polymerization process need to be by whole suspension system (process water: vinylbenzene oil system=1.2:1) heating, consumed a large amount of energy, meanwhile, suspension system is cooling also needs to consume a large amount of electric energy, novel process has been saved the energy, has reduced production cost;
3, in novel process production process, without waste water,waste gas and industrial residue etc. three wastes, producing, is environment-friendly production process; Novel material meets ROHS (the The RestrictionofHazardousSubstancesinElectricalEquipment that European Union promulgates simultaneously, Directive2002/95/EC) and WEEE (WasteElectricalandElectronic Equipment, Directive2002/96/EC) instruction;
4, product innovation has the thermal conductivity lower than common Expandable Polystyrene (EPS), after testing, product innovation thermal conductivity is 0.031w/m.k, and the thermal conductivity of common Expandable Polystyrene (EPS) is 0.041w/m.k, thermal conductivity reduces by 32.25%, and heat-proof quality significantly improves;
5, owing to thering is better heat-proof quality, requiring under the condition of same heat-insulating property, the usage quantity of polymer materials can save 30～50%;
6, novel material goods have good antistatic property, anti-microbial property;
7, novel material reaches the detection of GB8624B1 (B-S2, d0, t2) level by the performance of burning, is the new building material of energy-saving and environmental protection, safety, has wide market outlook.
Accompanying drawing explanation
Fig. 1 is Expandable Polystyrene (EPS) function novel material production equipment special a;
Fig. 2 is Expandable Polystyrene (EPS) function novel material production equipment special b;
Fig. 3 is Expandable Polystyrene (EPS) function novel material production equipment special c.
Embodiment
For making technical scheme of the present invention and feature clearer, below in conjunction with embodiment, the present invention is described in further detail.At this, following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment mono-:
As shown in Figure 1; Expandable Polystyrene (EPS) function novel material production equipment special, comprising: forcing machine (single screw extrusion machine or twin screw extruder), weightless title, liquid infusion pump, Melt Pump, net-changing device, cross over valve, tablets press, drying machine, wrapping machine.
Technological process explanation:
1. utilize twin screw extruder or single screw extrusion machine that main raw material (polystyrene and other resins thereof, Expandable Polystyrene (EPS)) is carried out to melting;
2. other auxiliary materials (fire retardant, graphite etc.) are added from main spout or with the form of side feeding;
3. liquid material (pentane, butane) is injected in forcing machine with the form of volume pump; As adopt Expandable Polystyrene (EPS) whipping agent volume pump can close to enter liquid material or enter less liquid material;
4. principal goods material dynamically mixes in forcing machine with auxiliary material;
5. mass transport is to Melt Pump, and what Melt Pump was uniform and stable is fed forward;
6. net-changing device falls the contaminant filter of mixed melt;
7. material samples by cross over valve again, sampling observation;
8. normal mass transport is carried out granulation to tablets press;
9. the microparticle of making is transported to centrifugal drier by recirculated water, is dried;
10. finished product is transported to next workshop section's processing;
Embodiment bis-:
As shown in Figure 2; Expandable Polystyrene (EPS) function novel material production equipment special, comprising: forcing machine (single screw extrusion machine or twin screw extruder), weightless title, liquid infusion pump, Melt Pump, net-changing device, cross over valve, tablets press, drying machine, wrapping machine.
Technological process explanation:
1. utilize twin screw extruder that main raw material (polystyrene and other resins thereof, Expandable Polystyrene (EPS)) is carried out to melting;
2. other auxiliary materials (fire retardant, graphite etc.) are added from main spout or with the form of side feeding;
3. melt being injected to single screw mixer carries out effectively mixing again;
4. liquid material (pentane, butane) is injected in single screw extrusion machine with the form of volume pump; As adopt Expandable Polystyrene (EPS) whipping agent volume pump can close to enter liquid material or enter less liquid material;
5. principal goods material dynamically mixes in forcing machine with auxiliary material;
6. mass transport is to Melt Pump, and what Melt Pump was uniform and stable is fed forward;
7. net-changing device falls the contaminant filter of mixed melt;
8. material samples by cross over valve again, sampling observation;
9. normal mass transport is carried out granulation to tablets press;
10. the microparticle of making is transported to centrifugal drier by recirculated water, is dried;
11. finished products are transported to next workshop section and process.
Embodiment tri-:
As shown in Figure 3; Expandable Polystyrene (EPS) function novel material production equipment special, comprising: forcing machine (single screw extrusion machine or twin screw extruder), weightless title, liquid infusion pump, Melt Pump, net-changing device, cross over valve, tablets press, drying machine, wrapping machine, mixed heat exchanger.
Technological process explanation:
1. utilize twin screw extruder or single screw extrusion machine that main raw material (polystyrene and other resins thereof) is carried out to melting;
2. other auxiliary materials (fire retardant, graphite etc.) are added from main spout or with the form of side feeding;
3. mixed heat exchanger control effectively to melt temperature and material is had to mixing effect;
4. Auxiliary Liquid Material can inject or inject from mixed heat exchanger from forcing machine, and liquid material (pentane, butane) injects with the form of volume pump; As adopt Expandable Polystyrene (EPS) whipping agent volume pump can close to enter liquid material or enter less liquid material;
5. principal goods material and auxiliary material carry out static mixing at forcing machine and mixed heat exchanger thereof;
6. mass transport is to Melt Pump, and what Melt Pump was uniform and stable is fed forward;
7. net-changing device falls the contaminant filter of mixed melt;
8. material samples by cross over valve again, sampling observation;
9. normal mass transport is carried out granulation to tablets press;
10. the microparticle of making is transported to centrifugal drier by recirculated water, is dried;
11. finished products are transported to next workshop section and process.
The present invention is a kind of polymkeric substance polymer novel material, the specifically production of Expandable Polystyrene (EPS) (EPS) function novel material, common EPS is because containing whipping agent pentane, when in continuous or intermittent type pre-foaming machine, temperature is 90～105 ℃, can foam by one or many, expand into the uniform bead of abscess, the density of bubble grain is from 5～40KG/m
3, the field such as widespread use insulation, cold insulation, heat insulation, damping, is mainly inside and outside wall thermal insulation, freezer cold insulation; Electrical equipment, ceramic package; Fishing case, fruit case, vegetables box are fresh-keeping; The damping of artwork or other fragile articles, is particularly used in engineering aspect at present, as evaporative pattern, the buffer layer of high motorway, the damping antiseepage of divert water from the south to the north project etc. of vehicle mould casting.
As the best lagging material of cost performance, the most important character of Expandable Polystyrene (EPS) is thermal conductivity.Participating in heat conducting type has: the thermal convection that in the thermal conduction in polystyrene, the thermal conduction that is filled with gas, photothermal transfer and airtight particle, convection flow produces.In particle, the effect in whole heat is transmitted of the thermal conductivity of air is maximum, along with the increase thermal conductivity of the density of expanded particle reduces,
The present invention carries out modification by p-poly-phenyl ethene or containing styrene monomer and other monomer copolymerization styrenics, modification subsidiary material are graphite, halogen is fire retarding synergist antimonous oxide or Diantimony Pentoxide Colloid, halogenated flame retardant, phosphorus flame retardant, nitrogen system or nitrogen-phosphorus flame retardant, softening agent, nucleator, smoke suppressor, tinting material etc., it is mixing that forcing machine carries out efficient melting to material, material mixes fully, melt after plasticizing enters respectively Melt Pump, after Melt Pump supercharging and voltage stabilizing, enter net-changing device impurity screening, melt after filtration enters cross over valve and template enters pelletizing chamber, to being mixed with the high molecular polymer of pentane and auxiliary material, carrying out pelletizing and obtain Expandable Polystyrene (EPS) function novel material.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give all embodiments exhaustive.Every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention extends out or change that belong to.
Claims (11)
1. Expandable Polystyrene (EPS) function novel material, it is characterized in that, described polystyrene functional novel material comprises GPPS (General Purpose Polystyrenre), HIPS (high-impact polystyrene), EPS (regular grade Expandable Polystyrene (EPS), flame retardant grade Expandable Polystyrene (EPS)), SAN (styrene-propene is fine), ABS (acrylonitrile-butadiene-phenylethylene), SMA (vinylbenzene and maleic anhydride copolymers), SMA-ABS (SMA and ABS blend), ASA (propylene is fine-copolymer in cinnamic acrylic ester, propylene is generally butyl acrylate, there is weathering resistance and thermal ageing resistant performance), MBS (methacrylic ester-butadiene-styrene), MABS (methyl methacrylate-acrylonitrile-butadiene-phenylethylene), PPE (polyphenylene oxide).
2. Expandable Polystyrene (EPS) function novel material according to claim 1, it is characterized in that described graphite addition with respect to polystyrene from 1.5～8% quality, the high purity micropowder graphite that preferred mass is 1.5-5%.
3. Expandable Polystyrene (EPS) function novel material according to claim 2, is characterized in that described graphite is expansible black lead, micro powder graphite or Graphene.
4. according to the Expandable Polystyrene (EPS) function novel material described in claim 2 or 3, it is characterized in that the described relative polystyrene quality of carbon black add-on is 0.2～6%; Preferably carbon black is graphitized carbon black, and particle diameter is 5nm-40nm.
5. Expandable Polystyrene (EPS) function novel material according to claim 1, is characterized in that described antimonous oxide, relative polystyrene quality, and its add-on is 0.2～3%.
6. Expandable Polystyrene (EPS) function novel material according to claim 1, it is characterized in that described halogenated flame retardant, its addition of polystyrene quality is 0.5～7% relatively, described bromide fire retardant is hexabromocyclododecane, tetrabromo-bisphenol, or two (allyl group) ether of tetrabromo-bisphenol, organic bromine fire retardant also can comprise brominated Polystyrene, this brominated Polystyrene can be the synthetic brominated flame-retardant polystyrene that is 1.0～2.5% or with phenylstilbene bromide and styrene copolymerized and add the polystyrene of part brominated flame-retardant, three (2, 3-dibromopropyl) isocyanuric acid ester.
7. Expandable Polystyrene (EPS) function novel material according to claim 1, is characterized in that described phosphorus flame retardant, with respect to its add-on of polystyrene quality, is 5～20%.
8. Expandable Polystyrene (EPS) function novel material according to claim 1, is characterized in that described fire retarding synergist is DCP, dicumyl peroxide, and the relative polystyrene quality of its addition is 0.05～3.5%.
9. Expandable Polystyrene (EPS) function novel material according to claim 1, is characterized in that described softening agent is mineral oil or o-phthalic acid dibutyl ester, with respect to its addition of polystyrene quality, is 0.01～2%.
10. Expandable Polystyrene (EPS) function novel material according to claim 1, is characterized in that described nucleator is polyethylene wax, and its addition of polystyrene quality is 0.02～3% relatively.
11. Expandable Polystyrene (EPS) function novel materials according to claim 1, is characterized in that described whipping agent is not halogen-containing C
nhm compound, n=4～6, comprise butane, Trimethylmethane, Skellysolve A, iso-pentane, neopentane and hexane, conventionally use Skellysolve A and iso-pentane, Skellysolve A: iso-pentane=7:3 or 6:4, the quality of relative polystyrene, its add-on is 3.5～10%.
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