CN1313876A - Expandable thermoplastic polymer particles and method for making same - Google Patents
Expandable thermoplastic polymer particles and method for making same Download PDFInfo
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- CN1313876A CN1313876A CN99809956A CN99809956A CN1313876A CN 1313876 A CN1313876 A CN 1313876A CN 99809956 A CN99809956 A CN 99809956A CN 99809956 A CN99809956 A CN 99809956A CN 1313876 A CN1313876 A CN 1313876A
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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
- C08J9/16—Making expandable particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B2009/125—Micropellets, microgranules, microparticles
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
An improved process for manufacture of expandable polymer particles is provided. The continuous process disclosed produces expandable polymer pellets in a single step while eliminating many of the dangers inherent in processes of prior art employed for the same. The polymers produced herein are of uniform size, and may be molded into various articles of manufacture using existing equipment and techniques known to those skilled in the art.
Description
The application requires non-temporary patent application of July 24 in 09/158189,1998 submitting with the non-temporary patent application of submitting on September 22nd, 1998 of the U.S. 09/122512 of the U.S. and the PCT application PCT/US98/15446 that submitted on July 24th, 1998 as basis for priority, and they all still are in pending trial at present.The whole contents of these patents is incorporated the present invention into as a reference at this.
The present invention relates to a kind of novel method of producing expandable thermoplastic particles.More particularly, but the foamable polymer particle that the present invention relates to advantageously to adopt atomization technique to produce.The mode that the particle of producing like this can adopt those skilled in the art to know foams and melts, and can form various moulded partss by these particles like this.
Background
Prior art provides the method for producing the expandable thermoplastic polymer material that comprises crystallization and amorphous polymer.Produce like this by the expandable thermoplastic material that crystalline polymer is made: will be generally the solid fluoropolymer resin and carry out thermoplastification, the resin of this thermoplastification is mixed a kind of flowable gel of formation with volatile whipping agent under heat and pressure, then this gel is clamp-oned a district with this gel of cooling that expands, formed required solid polymer foam materials product with lower pressure and temperature.1, the 2-dichloro tetrafluoro ethane has been widely used as this whipping agent, because it gives the foamed products body with enough dimensional stabilitys in solidification process.But because stability in use control agent, as be described in those longer chain fatty acid/polyol partial esters of United States Patent (USP) 3644230 and the ester that is specified in the higher fatty acid of United States Patent (USP) 4214054 and 4395510, other whipping agent, as the hydrocarbon that comprises pentane and so on alkane utilization of having succeeded at present, all incorporate the present invention as a reference in this content with above-mentioned patent.Therefore, can use routine techniques to produce various expandable thermoplastic plastics at present, even comprise crystalline polymer.In currently known methods, whipping agent in proportion compounding in the starting polymer resin blend, in gained foaming cellular product, produce required turgidity, usually the product that aging foam densities is reduced to about 9.6 kilograms/meter 3 (about 0.6 pounds/cubic feet) is produced in the highest about 60 times of volumetric expansions.Foamable composite can mix this resin then by with the olefin polymer resin thermoplastification with stability control agent and whipping agent, activate this whipping agent at last and make to expand this mixture.The typical method of producing these materials is summarized in United States Patent (USP) 4694027,4894395,5304580 and 5605937, incorporates its whole contents into the present invention as a reference at this.But it is not best particle that the currently known methods of producing the expandable thermoplastic material obtains performance.For example, expandable polyolefin particles such as polyethylene must expand before with the whipping agent dipping in advance, and it is that those skilled in the art are known that this pre-expansion requires.This essential pre-expansion is equal to corresponding increase and stores the required storage area of final expandable particles.In addition, those skilled in the art know, but the shelf lives of the pre-expanded thermoplastic foam material of being made by common crystalline polymkeric substance is far below ideal value.
On the other hand, the foamable composite that comprises amorphous polymer, production as polystyrene material comprises interrupter method commonly used, wherein pass through well-known process, under intense agitation, various raw materials (comprising the aqeous suspension that contains styrene monomer, tensio-active agent, catalyzer and other additive) are handled, obtained the spherical polystyrol pearl of the about 0.3-1.5 millimeter of diameter.Subsequently, flood these pearls with hydrocarbon or other whipping agent (being generally pentane or halohydrocarbon), promptly, about 100 parts of (weight) polymer beads, 100 parts of water and 1 part of concentrated surfactant (or its mixture, as the mixture of aralkyl Aethoxy Sklerol and dodecylbenzene sulfonate) are packed in the autoclave together with about 3-10 part pentane.This mixture was heated to about 170 Fahrenheit degrees 3 hours under pressure, is cooled to room temperature then, obtain the expandable polystyrene (EPS) pearl, with post rinsing, drying and store for future use.In general, in this batch systems, the size of pearl can be controlled by advantageously selecting processing condition (comprising: time, stirring state, temperature, pressure and reactant concn).But the method itself of this production expandable polystyrene (EPS) pearl has several shortcomings, and a shortcoming is, in polymerization and impregnation steps, all needs a large amount of water polystyrene bead that suspends.This is actually dual shortcoming.At first, when dipping finished, if water is discharged in the environment, just forfeiture was for reaching the energy of temperature required input water.Secondly, before discharging, must be used for treating water with surcharge and could satisfy the practiced strict laws and regulations requirement of each government entity.These energy and processing comprehensive cost account for the considerable part of the expandable polystyrene (EPS) cost that must marry again the polystyrene final user.
Another shortcoming is that the agitator tank reactor that suspension reacts therein is subjected to the destruction of multiple factor easily and causes the reactor agitator stop motion, comprising power and equipment failure.These faults may mean catastrophic effect, promptly, the cohesion of monomer droplet may cause forming one, big, reactive raw material block, owing to do not have effective heat removal apparatus in this case, these raw material blocks can carry out uncontrollable, strong exothermic reaction.Except contaminated equipment, this occasion also obviously means safety hazard.
The expandable thermoplastic polymer material comprises the expandable polystyrene (EPS) that comprises volatilizer according to aforementioned preparation, known can the foaming by heating, and its condition makes volatilizer to evaporate and form a large amount of abscesses in the polymer materials body.(United States Patent (USP) 4174427,5000891,5240657,5525637 and 5573790 has all illustrated its production method, incorporates its content into the present invention as a reference at this.If) in the zone of proper mold, heat, but can use described foamed polymer material to produce various goods so, whether exist irrelevant with these materials with pellet or pearl form.The present invention relates to can the foam method of crystallization and amorphous granular (comprising polyolefine and polystyrene bead) of another kind of preparation, avoided and above-mentioned prior art technology and performance-relevant various shortcoming.But the invention still further relates to the foamable polymer particulate method that a kind of production has suitable dimensional homogeneity, can reduce like this or even get rid of the demand of spherule being carried out the multistep size grading.The spherule particle of gained can comprise various additives in the present invention, includes, but is not limited to: fire retardant, nucleator and known polymkeric substance other chemical substance with desired properties of giving.These other chemical substance is well known to those of ordinary skill in the art.
Summary of the present invention
The invention provides and produce expandable thermoplastic spherule particulate continuation method, it is applicable to crystalline polymer such as polyolefine and amorphous polymer such as polystyrene.Under the situation of expandable polyolefin, more gaseous foaming agent when those materials of Sheng Chaning comprise than the production of use prior art method in this way.Under the situation of amorphous polystyrene, this production can be owing to the thermopositive reaction raw material that forms bulk not bring harm, also not can because of execution environment or other statutory standard to handle big water gaging the increase expense.
The inventive method comprises, a kind of molten mixture that comprises thermoplastic polymer and at least a whipping agent is provided, and forms particle by this thermoplastic polymer then.Formed particle is the quenching of Rapid Thermal mechanics immediately, and the whipping agent that is dispersed in the whole polymer melt is in place at the solid substrate internal fixing.In a method, advantageously carry out a kind ofly comprising that technology that the thermoplastics that will have whipping agent atomizes with the nascent particle of degree of depth thermodynamics quenching, can be fixed on whipping agent in the particle matrix like this.Particulate so forms has avoided relevant with polymer crystallization usually foamed gas to repel a difficult problem, because this cooling raio is used the rapider of prior art method.According to the present invention, the quenching of polymkeric substance such as isotactic polyprophlene and polyethylene by adiabatic cooling, this takes place after the atomizing nozzle place forms immediately at particle, and this paper is described this elsewhere.In addition; can use a kind of wherein fluid polymer when appearing at die head with the extrudate form immediately in liquid cooling is bathed the extrusion technique of quenching form particle by thermoplastic polymer; wherein said liquid cooling is bathed and is selected from cold water, liquid nitrogen or liquid helium, and this technology is similar to mode used when producing lead button or jeweller's casting particle.This optimal process but nonessential comprising under the controlled atmosphere of whipping agent carries out under pressure.Under these conditions, can when use be generally the crystalline material, postpone or suppress the crystallization rate of thermoplastics basically, otherwise crystallization is almost in instantaneous generation.Pellet can form by the surperficial cutting action that acts on the extrudate that become by conventional polymer extruder die capitiform, and these pellets fall within the implication of the used word " particle " of this specification sheets and appended claims thereof.Under the situation that is generally the crystalline material, polymkeric substance has limited the ability that gaseous foaming agent is gone out by the particle bulk diffusion basically in the quick cooling under the condition that can suppress or postpone polymer crystallization speed when cooling off.Therefore, whipping agent is tied in the particle.This notion is the common design that the open method of this paper is had.
Being used to form the particulate most preferred method is that the molten mixture that will comprise whipping agent is being enough to be sent to atomizing nozzle under the condition that this molten mixture is atomized, form the drop that comprises this molten mixture like this, then drop is carried out enough time coolings, form the polymer beads that wherein constraint has whipping agent.These particles are collected standby subsequently.This method is applicable to crystallization and amorphous polymer.
In a preferred embodiment, the expandable polystyrene (EPS) spherule can be produced like this: a kind of logistics or reservoir of molten polymer material at first are provided, and it comprises at least a equally distributed whipping agent being enough to guarantee that gas phase can not be present under the temperature and pressure condition in the molten mass.Also being equipped with atomizing nozzle carries out fluid with molten mass and contacts.Stay the melting material of polymer stream or reservoir and transfer to the zone that a pressure is lower than this reservoir or logistics via the hole in the nozzle.The pressure change that is run into, add the effect of the physical configuration and the atomizing gas of upper spray nozzle, cause comprising the molten polymer that wherein is evenly distributed with whipping agent and atomize.Any outer cooling of following atomizing gas expansible Joule/Thompson cooling during atomizing and optionally adopting makes this molten polymer form the spherule that comprises uniform distribution whipping agent wherein.After the collection, these spherules are suitable for adopting the known various technology of those of ordinary skills to be molded as various goods.
Brief description of the drawings
Accompanying drawing is the sectional view that can be used for the atomizing nozzle of production expandable thermoplastic polymer particles of the present invention.
Detailed description of the preferred embodiments
The present invention is a kind of method of being produced expandable thermoplastic particles by the polymer melt that comprises at least a whipping agent.Adopt extrusion technique in conjunction with Cooling Mode, or most preferably adopt a kind of adiabatic cooling or outer refrigerative atomising method of comprising itself, make particle by this melt.The gained particle can be used for the spherule of the moulding technology that those of ordinary skills know after being.Usually, the spherical body particle of polymkeric substance comprises polypropylene, polyethylene or polystyrene.
Be used to form in the preferred method of thermoplastic granulates in the present invention, the polymer melt logistics that will comprise whipping agent is fed in the atomizing nozzle being enough to form fast under the particulate condition, then simultaneously or immediately with its quick cooling.Adopt this method, can form particle by crystalline polymer such as polypropylene and polyethylene and amorphous polymer such as polystyrene.
In according to other method of the present invention; adopt a kind of extrusion technique by mixture forming particle; include, but is not limited to the logistics of molten thermoplastic is imported in a quench bath such as cold water, liquid nitrogen or the liquid helium to be similar to production lead button or jeweller's casting particulate mode; whole quench process preferably comprising under the controlled atmosphere of whipping agent, is carried out under pressure.Preferably, the pressure in the controlled atmosphere is enough to reduce basically whipping agent isolating any tendency from molten mass.May mean that polymkeric substance fades under these condition of fast cooling of bearing 78 degrees centigrade by 250 degrees centigrade in less than 1 second, can postpone or suppress the crystallization rate of thermoplastics basically, this crystallization otherwise can take place when polymkeric substance solidifies, these polymkeric substance be it is generally acknowledged crystallization under normal operation.The pellet of the polymkeric substance that forms by the surperficial cutting action that acts on the extrudate that is formed by polymer-extruded machine die head or tubular piece fall within the implication of the used word " particle " of this specification sheets and appended claims thereof.This granulating process can make water carry out as the heat-eliminating medium that contacts with extrudate, or uses the cooling pool of other fluent material such as liquid nitrogen, liquid helium or mercury metal.Although the inventor is reluctant to be subjected to the limitation of any particular theory, infer that polymkeric substance has limited the ability that gaseous foaming agent is gone out by the particle bulk diffusion basically in the quick cooling under the condition that can suppress or postpone polymer crystallization speed when cooling off.Therefore, whipping agent is bound in the particle, even and also keep after the normal subsequent crystallisation of polymkeric substance carrying the baby in particle.This normal subsequent crystallisation of polymkeric substance takes place owing to polymer temperature increases to envrionment temperature by quench temperature in the particle.
The polymer crystallization degree is measured by its intrinsic performance that is called melting heat usually, and this can carry out conventional determining by testing method ASTM D-3417 or ASTM E-793-85.In general, for thermoplastic polymer, the crystallinity value of surveying of the given sample of commercial grade material is the part of the numerical value of pure isotaxy material.This is the cause owing to many production parameters of the degree of crystallinity total amount of the given material sample of influence, and its net result is that the amount that is present in the crystalline material that is considered to highly crystalline usually in the material only is about 40-60%.Therefore, the melting heat of given sample just occurs in the part of the melting heat in the pure material.Therefore, each sample of polymkeric substance has the fusing calorific value of a feature, and its direct representation is present in the crystallinity value in this sample.In order to make the present invention bring into play its predictive role, new preparation (aging be lower than 1 minute) but the degree of crystallinity of foaming granule material must be lower than fusion and injection or with 90% of polymer crystallization degree before whipping agent mixes.The degree of crystallinity of this reduction is that the molten polymer logistics is instructed quick refrigerative result according to this paper, and its direct representation is to the effective inhibition or the delayed action of polymer crystallization.Certainly, finally storing, especially after the pellet that room temperature storage is made according to the present invention, the degree of crystallinity of this pellet should increase to the normal observed value (after the existence of correction whipping agent) of the polymkeric substance of discussing.But this crystallization not can to the carrying of gaseous foaming agent in polymkeric substance produce with this polymkeric substance fade to when solid-state according to its aptitude identical harmful effect under the complete crystalline situation by molten state, because gaseous foaming agent is strapped in the pellet body effectively.This inference is not suitable for the amorphous polymer that keeps gaseous foaming agent when solidifying.
Whipping agent generally is that the polymer arts those of ordinary skill is known.Whipping agent used herein comprises that the foamable polymer field knows any whipping agent that can be used for this, includes, but is not limited to gas, comprising: hydrocarbon, nitrogen, carbonic acid gas, halohydrocarbon, hydrofluoric ether, chlorocarbon, fluorochlorohydrocarbon.In this article, be suitable for the solid matter of making whipping agent, know compound as similar Cellmic C 121 of emitting gas when standing heat energy with other and also mean the suitable whipping agent that is included in the polymkeric substance melt.But for the present invention, whipping agent preferably includes Skellysolve A, butane or Trimethylmethane.Whipping agent most preferably comprises Skellysolve A.The preferably about 0.5-7.0% weight of the amount of whipping agent in the melt, and if select Skellysolve A as whipping agent, its amount is the 1.0-10% weight of polymkeric substance total amount, most preferably 5.0% weight so.The molten polymer logistics is remained under the temperature and pressure condition that does not have the existence of gaseous state pentane, then whipping agent is evenly distributed in the polymer stream melt.Any various stirring means that can adopt those of ordinary skills to know promote whipping agent homodisperse in melt.
With the reinforced atomizing nozzle on it of the polymer stream that is loaded with whipping agent can be various configurations, as long as polymer stream can fully atomize, can form the particle of the about 0.3-1.5 millimeter of size like this by cooling atomizing polymkeric substance.
According to the present invention, the nozzle of the polymkeric substance melt that most preferably is used to atomize has adopted airflow collision mechanism with atomizing logistics or film on molten polymer logistics or film.This gas-atomizing nozzle is disclosed in United States Patent (USP) 4619845 and 5228620, incorporates its whole contents into the present invention as a reference at this.With reference to the accompanying drawings, but provided the sectional view that can be used for preparing the present invention's foamable polymer particulate atomizing nozzle.In the figure, 75 expression polymer particles granule products.83 expressions are included in the coextensive structure of stretching in the tubular conduit 71, and molten polymer logistics 26 is sent to range of atomization 69 by conduit 71.The 42nd, the structure in the hole that definite atomizing gas and molten polymer logistics are passed through.When this hole is passed through in the molten polymer logistics, utilize the high speed atomizing gas 17 and the interaction of molten polymer logistics to make its atomizing.Under high pressure, atomizing gas 17 is fed in the atomizing nozzle with subsonic, atomizing nozzle acts in the described molten polymer logistics and makes its atomizing then.The part 30 that forms atomizing particle is low pressure (preferred atmosphere pressure) districts.Along with the pressure decline of atomizing gas, atomizing gas and polymer beads carry out adiabatic cooling simultaneously.Because molten polymer logistics 26 comprises whipping agent, this cooling effect of particulate meeting guarantees whipping agent is wrapped in the product particle 75 itself.
Adiabatic cooling or Joule-Thompson cooling are a kind of phenomenons that physical chemistry field those of skill in the art know, its mathematics and actual being described in detail in the book that is entitled as " physical chemistry (PhysicalChemistry) " provide, this book is write by Peter W.Atkins, the 3rd edition, publish by W.H.Freeman and Company, New York, 1985 (ISBN-O-7167-1749-2) incorporate its whole contents into the present invention as a reference at this.
Atomization mechanism is described in detail in the book (J.Szekely that is entitled as " fluid flow phenomena of process of metal working (FluidFlow Phenomena in Metals Processing) ", publish by Academic Press, New York City, New York (1979), after 340 pages) in, its whole contents incorporated into the present invention as a reference at this.Other atomising unit that is applicable to the inventive method can comprise, for example rotation type atomization dish or plate, be with or without mono-material or many materials nozzle of auxiliary power supply (as, mechanical oscillation) and have interior or outer blended mixing nozzle.One piece of article in " the material world (Materials World) " magazine (the 5th volume, 7,1997 year July of № is after 383 pages) proposes and has described to can be used for another kind of nozzle of the present invention, incorporates its whole contents into the present invention as a reference at this.
According to the present invention, another requirement of making polymer beads is that the molten polymer logistics is fed in the above-mentioned atomisation unit.This can realize by flowed freely into or utilized suitable pump, forcing machine or other melt transfer equipment known in the art by pressurizing vessel.Required temperature and pressure integrated condition is calculated by the temperature-viscosity dependency data of used polymkeric substance or polymeric blends easily when under required flow rate the polymkeric substance melt being sent to atomizing nozzle.Preferably, the pressure in the conduit is greater than normal atmosphere and 200psig most preferably from about.The temperature of polymkeric substance melt is preferably than at least 10 degrees centigrade of the fusing point of polymkeric substance or second-order transition temperature height.If used polymkeric substance is a polystyrene, the preferred temperature of this melt when using 5.0% pentane (in melt) is 180 degrees centigrade so.
Be fed to atomizing nozzle in case will comprise the liquid stream of polymkeric substance melt, can utilize the interaction of atomizing gas and polymkeric substance melt and produced simultaneously pressure change to atomize.Preferably, the outer pressure of nozzle is normal atmosphere, but can adopt the pressure except that normal atmosphere, as long as differ 5psig at least between pressure that the polymkeric substance melt is stood and the external pressure.The preferably about 0.3-1.5 millimeter of gained particulate diameter.Particulate preferred size basis wherein needs uses its final occasion to change, and general diameter is 1.0 millimeters.
In addition, produce gas in order to suppress whipping agent in the stage that forms the spherical body of polymkeric substance, significantly clean the expansion can not appear in particle like this, and in order to promote whipping agent to keep in cured granulate itself, the nascent polymer particle of discharging from atomizing nozzle fully cooled off.
Embodiment 1
Be assembled in 8000 kilograms of/hour continuous batches of producing down molten polystyrenes and aggregate into complete equipment, the molten polymer logistics can use toothed gear pump to obtain from the output stream of this equipment with 50 kilograms/hour speed like this.Toothed gear pump is sent to polymkeric substance in the static mixer of being furnished with injection device, volatile matter, can enter molten polymer and is dissolved in wherein by this injection device as 5.0% pentane (the weight meter is based on polymer weight).By round-robin heat-transfer oil in the chuck around the static mixer, the polymkeric substance that leaves static mixer is remained on 210 degrees centigrade.Polymkeric substance is entered the opening for feed of cooling extruded machine by static mixer, and described forcing machine is with melted polymer cools to 170 degree centigrade.The polymkeric substance that leaves forcing machine is by an atomizing die head, and this die head comprises the vertical stuffing pipe of heating of 10 millimeters of internal diameters.Molten polymer forms the free setting bundle by the lower end of stuffing pipe, collides then on nitrogen gas stream and by its atomizing.The pressure of atomizing nitrogen gas stream with 17 crust is transmitted by being arranged in a plurality of holes in the annular array (center of stuffing pipe is the center of this annular array).Nitrogen gas stream from each hole is collided on polymkeric substance with the angle of 15 degree (axis of polymer stream relatively).A resonator is all arranged in each nitrogen transmitting catheter, and it can produce 50 kilo hertzs pressure and rate oscillation in nitrogen gas stream.Nitrogen flow rate is set in 5 cubic metres/hour (calculating) under standard temperature and pressure (STP).The polymkeric substance of carrying pentane atomizes by collision gas and forms the spherule particle form of 1 millimeter of mean diameter.These particulate samples of heating in boiling water, the inflatable so low-density foamed granules of polystyrene that obtains having unicellular structure, this shows that the pentane of significant quantity keeps in the nascent polymer particle that atomizing obtains so that grain expansion.Produce in the sort of pre-frothing machine of expandable polystyrene (EPS) on the gas impregnated polymer pearl that is usually used in by suspension polymerization, about double centner a large amount of particles in batches are exposed to carry out pre-frothing in the steam.With expanded beads slaking 5 hours, be molded as the thermal baffle of 0.03 watt/meter ℃ of density 40 kilograms per cubic meter and thermal conductivity then.
Although provide and described the present invention with regard to some preferred embodiment, those skilled in the art obviously can carry out equivalence and replace and improve after reading and understanding this specification sheets and claims thereof.Therefore the present invention includes all these improvement and replacement, only limit by the scope of following claim.
Claims (28)
1. method of producing expandable thermoplastic particles comprises:
A) provide a kind of molten mixture that comprises thermoplastic polymer and whipping agent;
B) form particle by this thermoplastic polymer;
C) described particle is cooled under its fusing point; And
D) collect described particle.
2. according to the process of claim 1 wherein that described cooling carries out being enough to described whipping agent is included under the described intragranular speed.
3. according to the method for claim 2, the amount that wherein is included in described intragranular described whipping agent can make described particle be expanded to about 2 times of its green diameter effectively when standing to be higher than 95 degrees centigrade temperature.
4. according to the method for claim 2, wherein form the described step of particle and refrigerative and all in less than 1 second, carry out.
5. according to the method for claim 2, the described cooling of wherein said particulate proceeds to effective low temperature to suppress the crystallization of described polymkeric substance basically with effective speed, obtains 90% the material that a kind of degree of crystallinity is lower than the normal observation value of described polymer crystallization degree.
6. according to the process of claim 1 wherein that described particle is the spherule that is of a size of about 0.3-1.5 millimeter.
7. method of producing expandable thermoplastic particles comprises:
A) provide a kind of molten mixture that comprises thermoplastic polymer and whipping agent;
B) provide a kind of atomizing gas;
C) described molten mixture and described atomizing gas are being enough to atomize described molten mixture and form under the condition of the drop that comprises described molten mixture and be sent to atomizing nozzle;
D) described drop cooling is formed solid polymer particle; And
E) collect described particle.
8. according to the method for claim 7, wherein atomizing gas is fed to described atomizing nozzle.
9. method according to Claim 8, wherein said atomizing gas is selected from rare gas, nitrogen, oxygen, air and carbonic acid gas.
10. method according to Claim 8 wherein uses whipping agent as atomizing gas.
11. method according to Claim 8, wherein said whipping agent is selected from: hydrocarbon, chlorocarbon, fluorochlorohydrocarbon, carbonic acid gas, nitrogen and air.
12. method according to Claim 8, wherein said whipping agent is a Cellmic C 121.
13. method according to Claim 8, wherein said whipping agent is selected from pentane and Trimethylmethane.
14. method according to Claim 8, wherein said thermoplastic polymer comprises the polymkeric substance that is selected from polystyrene, polyethylene and polypropylene or its mixture.
15. method according to Claim 8, wherein said thermoplastic polymer comprises the C of ethene, propylene and vinylbenzene or its mixture
2-C
4Multipolymer.
16. method according to Claim 8, wherein said thermoplastic polymer comprise a kind of polymer materials of crystalline generally.
17. method according to Claim 8, wherein said thermoplastic polymer comprise unbodied basically polymer materials.
18. method according to Claim 8, wherein said cooling are to utilize the expansion of atomizing gas to carry out.
19. according to the method for claim 18, wherein said molten thermoplastic particle is lower than 25 degrees centigrade temperature being enough to the degree of crystallinity of crystalline polymer material suppressed be cooled to 90% speed of the normal observation degree of crystallinity that is lower than described polymkeric substance.
20. according to the method for claim 19, wherein said thermoplasticity integument is cooled to and is lower than 25 degrees centigrade, slowly returns to 25 degrees centigrade then.
21. according to the method for claim 18, wherein said expansion is an adiabatic basically.
22. method according to Claim 8, the temperature of wherein said molten mixture is about 40-300 degree centigrade.
23. method according to Claim 8, the pressure that wherein said molten mixture stood is greater than normal atmosphere.
24. method according to Claim 8, the concentration of wherein said whipping agent in described polymkeric substance melt are about 0.5-7.0% weight of polymkeric substance melt gross weight.
25. method according to Claim 8, wherein said atomizing gas comprise a kind of can be with the reactive materials of described functionalization of polymers.
26. according to the method for claim 25, wherein said reactive materials is selected from halogen, hydrogen halide, interhalogen compound, nitrogen oxide, ozone, maleic anhydride, amine, oxygen, sulphur trioxide and air.
27. method according to Claim 8, the difference of the pressure outside pressure that wherein said polymer melt stood and the described atomizing nozzle is greater than 5psig.
28. 1-27 and the polymeric articles produced by any method.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12251298A | 1998-07-24 | 1998-07-24 | |
| PCT/US1998/015446 WO1999006477A1 (en) | 1997-08-01 | 1998-07-24 | Expandable thermoplastic particles and atomization method for making same |
| USPCT/US98/15446 | 1998-07-24 | ||
| US09/122,512 | 1998-07-24 | ||
| US09/158,189 US5977195A (en) | 1997-08-01 | 1998-09-22 | Expandable thermoplastic polymer particles and method for making same |
| US09/158,189 | 1998-09-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1313876A true CN1313876A (en) | 2001-09-19 |
Family
ID=27378517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99809956A Pending CN1313876A (en) | 1998-07-24 | 1999-01-21 | Expandable thermoplastic polymer particles and method for making same |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1102808A1 (en) |
| JP (1) | JP2003524667A (en) |
| CN (1) | CN1313876A (en) |
| AU (1) | AU2239999A (en) |
| CA (1) | CA2338464A1 (en) |
| NO (1) | NO20010367L (en) |
| WO (1) | WO2000005296A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10358800A1 (en) * | 2003-12-12 | 2005-07-14 | Basf Ag | Expandable styrene polymer granules |
| JP5386163B2 (en) * | 2008-12-18 | 2014-01-15 | 日機装株式会社 | Polymer bead manufacturing apparatus and polymer bead manufacturing method |
| KR102615889B1 (en) * | 2019-09-11 | 2023-12-20 | (주)엘엑스하우시스 | Thermoplasticity polymer particles and method for preparing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4211972A1 (en) * | 1992-04-09 | 1993-10-14 | Huels Chemische Werke Ag | Process for the production of foam beads |
| IT1255364B (en) * | 1992-09-15 | 1995-10-31 | Himont Inc | PROCESS FOR THE PREPARATION OF EXPANDED POLYPROPYLENE MANUFACTURES THROUGH PRODUCTION OF PRE-EXPANDED GRANULES AND THERMOFORMING FOR SINTERING THEMSELVES |
| DE4319990A1 (en) * | 1993-06-17 | 1994-12-22 | Messer Griesheim Gmbh | Process for producing particles from plastics |
-
1999
- 1999-01-21 AU AU22399/99A patent/AU2239999A/en not_active Abandoned
- 1999-01-21 EP EP99902414A patent/EP1102808A1/en not_active Withdrawn
- 1999-01-21 WO PCT/US1999/001256 patent/WO2000005296A1/en not_active Application Discontinuation
- 1999-01-21 JP JP2000561250A patent/JP2003524667A/en active Pending
- 1999-01-21 CA CA002338464A patent/CA2338464A1/en not_active Abandoned
- 1999-01-21 CN CN99809956A patent/CN1313876A/en active Pending
-
2001
- 2001-01-22 NO NO20010367A patent/NO20010367L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003524667A (en) | 2003-08-19 |
| NO20010367D0 (en) | 2001-01-22 |
| WO2000005296A1 (en) | 2000-02-03 |
| AU2239999A (en) | 2000-02-14 |
| NO20010367L (en) | 2001-03-23 |
| CA2338464A1 (en) | 2000-02-03 |
| EP1102808A1 (en) | 2001-05-30 |
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