CN103890066A - Compostable or biobased foams, method of manufacture and use - Google Patents

Compostable or biobased foams, method of manufacture and use Download PDF

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Publication number
CN103890066A
CN103890066A CN201280043807.2A CN201280043807A CN103890066A CN 103890066 A CN103890066 A CN 103890066A CN 201280043807 A CN201280043807 A CN 201280043807A CN 103890066 A CN103890066 A CN 103890066A
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China
Prior art keywords
pore forming
forming material
bead
compost
composition
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Pending
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CN201280043807.2A
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Chinese (zh)
Inventor
阿达姆·帕夫洛斯基
杰弗里·切尔诺豪斯
肯特·卡斯克
加勒特·范·戈登
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Lifoam Industries LLC
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Lifoam Industries LLC
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Priority claimed from US13/178,293 external-priority patent/US20120009420A1/en
Priority claimed from US13/178,272 external-priority patent/US20120010307A1/en
Priority claimed from US13/230,158 external-priority patent/US8962706B2/en
Application filed by Lifoam Industries LLC filed Critical Lifoam Industries LLC
Publication of CN103890066A publication Critical patent/CN103890066A/en
Pending legal-status Critical Current

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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
    • 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
    • B29C44/3469—Cell or pore nucleation
    • B29C44/348—Cell or pore nucleation by regulating the temperature and/or the pressure, e.g. suppression of foaming until the pressure is rapidly decreased
    • 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
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • 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
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/16—Biodegradable polymers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The present invention describes compostable or biobased foamed beads produced by cutting the foamed strand at the face of the extrusion die and the foamed bead or strand is subsequently cooled. The foamed beads are useful for fabricating foamed articles. The foamed beads are produced using a compound comprising a compostable or biobased polyester and a blowing agent. Additives including plasticizers and chain extenders are optionally included in the compostable or biobased composition.

Description

Foamed, method of manufacture and use thereof compost or based on biological
Technical field
Present invention relates in general to material compositions compost or based on biological, and relate to the novel method for generation of lightweight, compost or foamed based on biological, relate to particularly and utilize melt technology to mix material compost or based on biological and pore forming material to produce the method for foamed, in some particularly preferred embodiment, described pore forming material does not comprise any volatile organic component (VOC) as pentane.Described composition and method can be used for producing various products.
Background technology
Polymer foaming thing is included in the multiple spaces in polymeric matrix, also referred to as unit.By substituting solid plastic with space, for given volume, polymer foaming thing uses than solid plastic raw material still less.Therefore,, by replacing solid plastic with polymer foaming thing, in many application, can reduce material cost.In addition, foamed is extraordinary isolator, and it can seal building structure, to avoid the intrusion of air and moisture, saves charges for water and electricity (utility bills), and increases the intensity of building.
Than conventional polymer foamed, microporous foam thing has less cell size and the cell density of Geng Gao.In some cases, foaming process is by nucleator, and some of them are inorganic solid particles, adds polymer melt (in the course of processing).These reagent can have multiple combination thing, as talcum and calcium carbonate, and add in polymer melt, are commonly used to promote cell nucleation.In the even modular construction of formation, the dispersion of nucleator in polymeric blends is often crucial.
For the normally amorphous polymer of material of expandable polystyrene (EPS), it presents the second-order transition temperature of approximately 95 ℃ and the temperature of fusion of approximately 240 ℃.EPS resin is changed into three main phase of process need of the polystyrene foam product of expansion: pre-expansion, slaking and molded.The expandable bead that preparation is produced by polystyrene and pore forming material is then expanded by means of steam in pre-expander.The pre-object expanding is the foamed particle producing for the desired density of application-specific.Between the pre-phase of expansion, EPS bead is supplied in pre-expander container, it comprises agitator and controlled steam and air supply.Steam is introduced pre-expander can produce two kinds of effects: EPS bead is softening and pore forming material (it is dispersed in EPS bead, is generally pentane) is heated above to the temperature of its boiling point.Both of these case causes the volumetric expansion of EPS bead.The diameter of particle increases the density of resin simultaneously and reduces.The density of pre-expanded granular is about 1000kg/m 3, the density of expanded beads is 20 to 200kg/m 3; It depends on process, can realize 5 to 50 times of reductions of density.
Slaking has multiple object.Its allow the vacuum producing in the unit of foamed particle between the pre-phase of expansion with around barometric point reach balance.It allows the residual water-content of evaporation on foamed particle surface.And it provides the dissipation of excessive residual pore forming material.Curing time is depended on many factors, comprises the pore forming material content of original resin, pre-density on expansion and environmental factors.Suitably the pre-expanded beads of slaking is not responsive to physics and thermal shocking.Before slaking, the molded of described bead can cause that intragranular unit breaks, thereby produces undesirable molded foamed parts.
After the pre-expanded beads of slaking, they are transferred to moulding press, this moulding press comprises one or more cavitys, described cavity is for one or more desired molded foaming product moulding.Molded object is that foamed particle is fused into single foam unit together.The molded of EPS can be followed simple in-order: first fill molding cavity with pre-expanded beads; Carry out heating mould by introducing steam; Cooling molded foaming product in molding cavity; And from molding cavity, take out finished parts.Introduce the steam of moulding press and cause that bead is softening and even further expand, this is due to due to remaining pore forming material, as the CO of pentane or dipping 2.In closed cavities, the combination of these two kinds of effects allows individual particle to merge becomes single solid foamed thing parts.
Biodegradable for more and more needing for many plastics of packing, for example pallet in biscuit and candy wrapping.For some time, starch film has been proposed as biodegradable substitute.U.S. Patent number 3,949,145 have described PE/Starch alcohol/glycerin compositions as biodegradable agricultural mulching.
The common methods that is used for producing biodegradable product is to produce the composition of hydrolyzable degraded in conjunction with poly(lactic acid) (PLA) and starch.In production starch based polymers (especially passing through hot-melt extruded), meet difficulty.The molecular structure of starch is subject to as plasticized starch and makes it pass through the disadvantageous effect of the needed shear-stress of extrusion die and temperature condition.
Conventionally pore forming material is introduced to polymer materials to manufacture polymer foaming thing (one of in two ways).According to a kind of technology, make chemical foamer and mixed with polymers.In polymer materials, under the condition that polymkeric substance is melted therein conventionally, chemical foamer experience chemical reaction, thus cause that gas forms.Chemical foamer is low molecular weight organic compound normally, and it decomposes and discharges gas as nitrogen, carbonic acid gas or carbon monoxide under specified temp.According to another kind of technology, by physics pore forming material, under envrionment conditions, be the fluid of gas, inject molten polymer flow, to form mixture.Mixture withstanding pressure is reduced, thereby cause that pore forming material expands and forms bubble (unit) in polymkeric substance.Several patents and patent publications have been described some aspects of poromerics and micropore process.
The U.S. Patent number 6,593,384 that licenses to the people such as Anderson has been described and has been utilized widely polymer materials and the physics expandable hollow particles producing of bubbling.The U.S. Patent number 7,226,615 that licenses to the people such as Yuksel has been described inflatable foamed, and it is combined with supercarbonate pore forming material based on extensive disclosed biomaterial.U.S.'s publication application number 2006/0167122 of the people such as Haraguchi has been described expandable hollow particles, and it is derived from the combination of PLA, pore forming material and polyolefin-wax.U.S.'s publication application number 2010/0029793 of the people such as Witt has been described by using carbonic acid gas (CO 2) solvent impregnated resin bead produces the method for PLA foamed.
The U.S. Patent number 4,473,665 that licenses to the people such as Martini-Vvedensky has been described the method for the preparation of foamable polymer, and wherein said foamable polymer has the unit that diameter is less than approximately 100 microns.In described technology, with pore forming material saturated material precursor, material is placed under high pressure, then reduce rapidly pressure, so that pore forming material nucleation and permission forming unit.Then IQF material is to keep the desired distribution of micro unit.
The U.S. Patent number 5,158,986 that licenses to the people such as Cha has been described and has been utilized supercutical fluid to form capillary copolymer material as pore forming material.Utilize batch process, this patent has been described the whole bag of tricks for generation of nucleation site.
The U.S. Patent number 5,866,053 that licenses to the people such as Park has been described the continuation method that is used to form microporous foam thing.Pressure on a single phase soln of pore forming material and polymkeric substance is reduced so that material nucleation rapidly.Nucleation rate is enough high to form microvoid structure in final product.
The people's such as Burnham International Patent Publication No. WO 98/08667 provides the method and system for generation of poromerics and microporous article.In one approach, by following steps by the fluid of foamed polymer material precursor and pore forming material, a single phase soln continuous nucleation: stream is divided into independent part and makes respectively each unitary part nucleation, then these streams of recombine.The stream of recombine may be molded to desired form, for example, pass through forming mould.
Be generally accepted that in the art, in order to produce the enough nucleation sites for forming microporous foam thing, be used for producing enough pore forming materials of nucleation motivating force and the combination for the sufficiently high pressure power changing down of anti-stop element growth-dominated nucleation event.In the time that pore forming material level reduces, reduce for the motivating force of nucleation.But, although higher pore forming material level can cause less unit (in microporous foam thing field, conventionally desired result), but according to conventional idea, higher pore forming material level can also cause cell interconnection (according to definition, its increase cell size and may structural damage and other materials performance) and lower than best surface property (under higher gas level, impaired surface property may be due to pore forming material and diffuses out the aptitude of material).
In other words, generally believe, when change in capillary copolymer material pore forming material level time, between small unit size and best material property, exist compromise.
Summary of the invention
Therefore, an object of the present invention is to provide foamed compost or based on biological of avoiding prior art shortcoming.
An object of the present invention is to provide the composition of material, said composition comprises expanded bead compost or based on biological, and described bead has the modular construction of sealing substantially.Another object of the present invention is to provide expanded bead, and it further comprises pore forming material, and wherein pore forming material is physics pore forming material.Some preferred embodiment in, physics pore forming material is supercritical CO 2.In some embodiments, composition is the polymkeric substance of poly(lactic acid).In some embodiments, in polylactic acid polymer, the content of D-isomer is less than 6%.In other embodiments, in polylactic acid polymer, the content of D-isomer is less than 2%.In another embodiment, bead comprises nucleator and additive to improve melt rheological property energy and viscosity.Some preferred embodiment in, additive choosing is the group of following composition freely: antioxidant, photostabilizer, fiber, foaming additive, conductive additive, anti blocking agent, static inhibitor, thermo-stabilizer, impact modifying agent, biocide, expanding material, tackifier, tinting material, coupling agent and pigment.In another embodiment, expanded bead is by the material of more than 50% compost, the preferably material production of more than 80% compost.In other embodiments, expanded bead has the polymer composition based on biological that is greater than 50wt%, is preferably greater than the polymer composition based on biological of 80wt%.On the surface of extrusion die, after extrudate granulation, expanded bead has the modular construction of sealing substantially.Expanded bead has spherical or subglobular shape and the about 1mm diameter to about 10mm, and preferred about 2mm is to about 5mm, and more preferably from about 1mm to about 4mm.Expanded bead further has the 0.045g/cm of being less than 3density and the cell size diameter of 50 μ m to 150 μ m.
Another object of the present invention is to provide the method for utilizing melt technology to produce foamed compost or based on biological.A relevant object of the present invention is to provide the method for utilizing pore forming material to produce foamed compost or based on biological, and preferably described pore forming material does not comprise volatile organic component.Another relevant object of the present invention is to provide pore forming material that utilization preferably do not comprise pentane and produces the method for foamed compost or based on biological.
Another object of the present invention is to provide expanded bead compost or based on biological, and it can utilize conventional molding equipment to process.
Another object of the present invention is to provide expanded bead, and by compost, described expanded bead can become lower molecular weight material by chemical degradation.
Another object of the present invention is to provide expanded bead compost or based on biological, and it can make 3D shape.
By composition being provided and realizing these and other objects of the present invention by the method for polymkeric substance generation expanded bead compost or based on biological and the method for utilizing described bead to produce various article.In one embodiment, produce lightweight bead by polymkeric substance melt-processed compost or based on biological and pore forming material.In another embodiment, melt-processable composition comprises the other additive of the rheological characteristics of improving polymkeric substance compost or based on biological, makes it be more suitable for producing light-weight foam bead.Can utilize conventional molding equipment further to process expanded bead of the present invention, so that foaming product lightweight, compost or based on biological to be provided.Goods of the present invention can be applicable to use in the application of conventional expandable polystyrene (EPS) at present, comprise and relate to protective package, sound insulation and heat-insulating those application.
Polymer composition is widely used in many application, comprises automobile, building construction, electronics and consuming product.Polymkeric substance can be made up of the polymkeric substance based on biological or petroleum-type polymkeric substance.Polymkeric substance compost or based on biological is preferably used and is solved the environmental problem relevant to the processing of material (after they are not used further to their expection object), thereby the use of oil is down to minimum.But polymkeric substance must meet some physics and chemistry characteristic, so that they are suitable for the application of expection.In inflatable foamed, polymer composition must can be made 3D shape, and described 3D shape is tolerance or protection lightweight and that impact, sound and heat are provided.Disclosure of the invention described herein foamed compost or based on biological, it has to form and has the needed characteristic of product of these characteristics.
Accompanying drawing explanation
Illustrate in greater detail above-mentioned feature, aspect and advantage with other of the present invention with reference to the description of its embodiment shown in the following drawings, wherein:
Fig. 1 illustrates the general method schematic diagram by produce expanded bead according to extrusion foaming method of the present invention.
Fig. 2 illustrates the cross section of the expanded bead by producing according to the illustrative methods of one embodiment of the present invention.
Fig. 3 illustrates general flow chart, and it illustrates the technical process for the production of foaming product according to the present invention.
Embodiment
By describing with reference to following, can understand better invention above-outlined and that limit by the claim of enumerating.Being used for of below providing makes people can build and use the description of the embodiment of embodiment of the present invention not to be intended to limit the present invention, but as its specific embodiment.It will be understood by those skilled in the art that they can easily use disclosed conception and embodiment as being used for improving or being designed for the enforcement additive method of identical object of the present invention and the basis of system.Those skilled in the art it should further be appreciated that, such equivalence assembling without departing from the spirit and scope of the present invention (with its form the most widely).
For the purposes of the present invention, the following term definition using is in this application as follows:
" biodegradable " refers to and stands the compound that enzyme decomposes (as passed through microorganism), or its part stands the compound that enzyme decomposes (as passed through microorganism).In one case, for example, polymkeric substance, as poly(lactic acid) can be degraded to single lactic acid molecules by hydrolysis, by various microorganisms, carries out enzyme decomposition to it.Microorganism can consume conventionally to be had up to approximately 1000 dalton, and preferably up to the oligopolymer that comprises carboxylic acid of approximately 600 daltonian molecular weight, this depends on chemistry and the physical property of oligopolymer.
" biodegradable polymers " refers to polymer materials or resin, and it can become lower molecular weight material by chemical degradation.
" based on biology " refers to such material, and it is made up of biological product or reproducible Agricultural Materials fully or mostly, comprises plant, animal and marine organism material.Product based on biological is synthesized by biogenetic derivation and refers to such composition, and it for example, substitutes the oil using in preparation EPS by reducing the use in non-renewable source in conjunction with renewable composition as the surrogate of at least a portion material in product.Composition based on biological can not harm for many products their performance.
" chain extension agent " refers to such material, when together with polymkeric substance melt-processed, increases molecular weight by coupled chain end reactively.
" compost " refer to and can experience biological decomposition, make material be visually undistinguishable and resolve into carbonic acid gas, water, mineral compound and biomass.
" compost " is the bioprocess that by various microorganisms, organic waste is resolved into useful matter under oxygen exists.
" extrudate " is semi-solid material, by forcing material to be extruded by mould openings.
" melt-processable composition " refers to such preparation, conventionally at elevated temperatures, by means of conventional polymer processing technology picture for example extrude or injection-molded by its melt-processed.
" melt technology " refers to and extrudes, injection-molded, blown-moulding, rotational moulding are molded or batch mixing.
" nucleator " refers to such material, is incorporated as the crystal formation polymer melt that position is provided.For example, by adding nucleator, can obtain higher crystallinity and more uniform crystalline structure.
" softening agent " refers to such material, itself and polymer-compatible compost or based on biological after melt-processed.In polymkeric substance compost or based on biological, add softening agent and there is the effect that reduces film composite modulus.
The invention still further relates to the various products of being made by material compost or based on biological.Material compost or based on biological can comprise any of outside or inter-modification polymer composition or two kinds, those terms as described below.
Preferably, the polymkeric substance in current material is decomposed by compost.In current material, the degradation characteristic of polymkeric substance depends on the material type of preparing with polymkeric substance to a great extent.Therefore, polymkeric substance need to have suitable degradation characteristic, makes in the time processing and be produced into final material, and material does not experience remarkable degraded until after the validity period of material.
The feature of the polymkeric substance of material is also at present, is compost within a certain period of time, and the product of wherein being prepared by described material decomposes after using.Material of the present invention is degraded within the time of several weeks to several years, and similarly scale operation, nondegradable product needs decades to centuries natural decomposition conventionally.Some preferred embodiment in, the material of compost is degraded in less than 180 days.
The invention describes expanded bead compost or based on biological that can be used for manufacturing foaming product.The compound that utilization comprises thermoplastic polymer compost or based on biological and pore forming material produces foamed of the present invention.In the structure of foaming product, by means of the expanded bead producing from fluoropolymer resin compost or based on biological, the thermoplastic, polymeric materials of this compost can be used for substituting expandable polystyrene (EPS).In the ideal case, can carry out substituted polystyrene with polymkeric substance compost or based on biological with same and physicals.
In composition compost or based on biological, comprise alternatively the additive that comprises softening agent and chain extension agent.Preferably, polymkeric substance has the content based on biological that is greater than 50%, is most preferably greater than 80% the content based on biological.Can utilize conventional melt technology, as single Screw Extrusion and twin screw extrusion, produce these foameds.In one embodiment, produce expanded bead by the surface cutting extrudate at extrusion die.By contacting with water, water vapour, air, carbonic acid gas or nitrogen, carry out cooling expanded bead alternatively subsequently.Cut bead on the surface of mould after, bead continues foaming, thereby forms the closed pore foaming structure with continuous surface layer, on the surface of bead, there is no the modular construction of exploitation.In one embodiment, the expanded bead compost of generation or based on biological has the 0.15g/cm of being less than 3density.In another embodiment, expanded bead compost or based on biological has and is preferably less than 0.075g/cm 3density, and be most preferably less than 0.05g/cm 3.In another embodiment, as determined according to ASTM D6400, be greater than the foamed of 50wt% by the material production of compost.One preferred embodiment in, foamed more than 80wt% is the material of compost.In the most preferred embodiment of one, the foamed that is greater than 95wt% is the material of compost.
By polymkeric substance melt-processed compost or based on biological and pore forming material and additive alternatively, produce polymkeric substance compost of the present invention or based on biological, the rheological property of polymkeric substance wherein said additive improved compost or based on biological, and comprise chain extension agent and softening agent.Polymkeric substance compost or based on biological can comprise conventionally by confessed those polymkeric substance of those of ordinary skills to resolve into the compound with lower molecular weight.The limiting examples that is applicable to implement polymkeric substance compost of the present invention or based on biological comprises polysaccharide, peptide, polyester, polyamino acid, polyvinyl alcohol, polymeric amide, polyalkylene glycol and their multipolymer.
In one aspect, polymkeric substance compost or based on biological is polyester.The limiting examples of polyester comprises random or stereospecific multipolymer and their derivative of poly(lactic acid), Poly-L-lactide (PLLA), poly--D-ALPHA-Hydroxypropionic acid (PDLA), Pfansteihl and D-ALPHA-Hydroxypropionic acid.Other limiting examples of polyester comprise pla-pcl, polyhydroxybutyrate, poly-hydroxypentanoic acid, polyethylene succinate, poly-succinic Aden ester, polybutylene adipate, polymalic acid, polyglycolic acid, poly-succinate, poly-barkite, polyglycolic acid Aden ester and poly-dioxy pimelinketone.
Comprise the material (for example, the biopolymerization resin of compost) of the known compost that is derived from biogenetic derivation for preferred polymeric resin of the present invention, can be by the synthetic polymer of compost but can also use.Biological polymer poly(lactic acid) (PLA) is most preferred example, this be due to its known compostability and from agricultural (for example corn) raw material the origin based on biological.Can use amorphous and semi-crystalline PLA polymkeric substance.The example of polymkeric substance compost or based on biological comprises Ingeo2002D and Ingeo4060D level plastics and Ingeo805ID level foamed (from Nature Works, LLC) and Cereplast Compostable5001.
In one embodiment of the invention, polymkeric substance and pore forming material melt-processed compost or based on biological, to produce light-weight foam bead.Pore forming material is such material, (for example can be added melt-processable composition, the premix of additive, polymeric matrix and/or optional filler, with melt or solid form), carry out generation unit by discharge gas at reasonable time in the course of processing.The amount of pore forming material and type can affect the density (by its modular construction) of finished product.Any suitable pore forming material can be used for producing foam material.
There is the pore forming material of two kinds of main Types: physics pore forming material and chemical foamer.It is volatile liquid or pressurized gas that physics pore forming material tends to, and during melt-processed, its change state is to form vesicular structure.One preferred embodiment in, physics pore forming material is carbonic acid gas.In most preferred embodiments, the physics pore forming material of carbonic acid gas under its supercritical state with Mixing of Polymer Melt.It is solid that chemical foamer tends to, and it decomposes (for example, with hot mode, reacting etc. with other products), to form gaseous decomposition product.Produce gas by fine distribution in melt-processable composition so that vesicular structure to be provided.
Chemical foamer can be divided into two main Types: organic pore forming material and inorganic pore forming material.Organic pore forming material can have various different chemical specieses, physical form and improved form, as for example Cellmic C 121.It is more limited that inorganic pore forming material tends to.Inorganic pore forming material can comprise that one or more carbonate are as sodium, calcium, potassium and/or magnesium carbonate.Preferably, use sodium bicarbonate, this is because its cheap and easy decomposition is to form carbon dioxide.In the time being heated higher than approximately 120 ℃, sodium bicarbonate progressively decomposes, and wherein between about 150 ℃ and 200 ℃, occurs significantly to decompose.Conventionally, temperature is higher, and sodium bicarbonate decomposes faster.Acid, as citric acid, can also be included in foaming additive, or adds respectively melt-processable composition, to promote pore forming material to decompose.Conventionally carry out providing chemical pore forming material with powder type or particle form.The concrete selection of pore forming material will be depended on cost, the desired desired performance of unit development, gas yield and foam material.
The suitable example of pore forming material comprises that water, carbonate and/or supercarbonate and other release of carbonate dioxide materials, diazonium compound and other nitrogen produce material, carbonic acid gas, decomposing polymer material if poly-(Tert-butyl Methacrylate) and polyacrylic acid, alkane and cycloalkanes gas are if pentane and butane, rare gas element are as nitrogen etc.Pore forming material can be hydrophilic or hydrophobic.In one embodiment, pore forming material can be solid pore forming material.In another embodiment, pore forming material can comprise that one or more carbonate and/or supercarbonate are as sodium, potassium, calcium and/or magnesium carbonate and/or supercarbonate.Pore forming material can also comprise sodium carbonate and sodium bicarbonate, or, alternatively, sodium bicarbonate individually.In another embodiment, pore forming material can be inorganic.
Although foaming agent composition can only comprise pore forming material, more typical situation is that wherein pore forming material comprises polymer support, and it is used for carrying or keeping pore forming material.This pore forming material enriched material can be dispersed in polymer support, for the object of transporting and/or processing.Polymer support can also be used to keep or carries and expect to add any other material or the additive in melt-processable composition.
In enriched material, pore forming material comprises level and can be very different.In some embodiments, foaming additive comprises the pore forming material at least about 2.5wt%, at least about the pore forming material of 5wt%, or, suitably, at least about the pore forming material of 10wt%.In other embodiments, foaming additive can comprise approximately 10 pore forming materials to 60wt%, approximately 15 pore forming materials to 50wt%, or, suitably, approximately 20 pore forming materials to 45wt%.In further embodiment, foaming additive can comprise approximately 0.05 pore forming material to 90wt%, approximately 0.1 pore forming material to 50wt%, or approximately 1 pore forming material to 26wt%.
As discussed previously, pore forming material enriched material can also comprise polymer support or material, it is used for keeping other additives to form single additive.Polymer support or component of polymer can be that any suitable polymer materials is as hydrocarbon polymer or nonhydrocarbon polymkeric substance.Polymer support should be able to be melted or melt-processed at the temperature of the activation temperature lower than pore forming material.But, in some cases, can use the component of polymer of fusing point higher than the activation temperature of pore forming material, as long as it is processed to retain appropriate active pore forming material fast enough.In one embodiment, the fusing point that polymer support has is no more than approximately 150 ℃, is no more than approximately 125 ℃, is no more than approximately 100 ℃, or, suitably, be no more than approximately 80 ℃.One preferred embodiment in, pore forming material enriched material comprises polymkeric substance compost or based on biological.
In another embodiment, softening agent can be added or is incorporated into composition to obtain the physical property of desired melt-processable composition.The limiting examples of softening agent comprises the abiogenous oil of polyalkylene glycol and functionalization.The limiting examples of polyalkylene glycol comprises the polyoxyethylene glycol of selling with Carbowax trade(brand)name (Dow Chemical Co., Midland, MI).The limiting examples of the abiogenous oil of functionalization comprises oxysuccinic acid esterification or epoxidation soybean, linseed oil or Trisun Oil R 80, and they are commercially available from Cargill Inc.
In another embodiment, composition compost or based on biological can comprise chain extension agent to increase the molecular weight of polymkeric substance compost or based on biological during melt-processed.This also has the melt viscosity of increasing and intensity effect, and it can improve the foaming power of polymkeric substance compost or based on biological.The example that can be used for chain extension agent of the present invention comprises those (from Clariant) that sell with CESA expansion trade(brand)name and those (BASF) that sell with Johncryl trade(brand)name.
In composition of the present invention, by adding nucleator, can improve mouldability.In polymeric blends, disperse nucleator to contribute to form even modular construction.The example of nucleator comprises that inorganic powder is as talcum, kaolin, mica, silica, calcium carbonate, barium sulfate, titanium oxide, aluminum oxide, clay, wilkinite and diatomite, and known chemical foamer is as azo two carbodiimides.Wherein, talcum is preferred, and this is because it contributes to control unit diameter.The content of nucleator depends on the type of nucleator and the element diameter of expection and changes.
In another aspect of the present invention, melt-processable composition compost or based on biological can comprise other additives.The limiting examples of additive comprises softening agent, chain extension agent, antioxidant, photostabilizer, fiber, pore forming material, foaming additive, anti blocking agent, thermo-stabilizer, impact modifying agent, biocide, expanding material, tackifier, tinting material, coupling agent, static inhibitor, conductive filler material and pigment.Can be with the form of powder, bead, particle, or can extrude form with any other, additive is added to melt-processable composition.The amount of the additive in melt-processable composition and type may be different, and it depends on the desired physicals of polymeric matrix and final product composition having.Technician in melt-processed field can select the suitable amount of additive and type with particular polymers matrix matching, thereby realize the desired physicals of finished product material.
In melt-processable, compost or foaming composition based on biological, the amount of composition may be different, and it depends on the end-use of expection.Polymkeric substance compost or based on biological can comprise approximately 40 final compositions to approximately 99 % by weight.Can be to comprise pore forming material up to the level of 20 % by weight.Softening agent compost or based on biological can comprise the final composition of approximately 1 to 50 % by weight, the preferably final composition of 1 to 20 % by weight.Chain extension agent can comprise the final composition of approximately 0.1 to 10 % by weight, preferably approximately 0.1 to 0.5 % by weight.Can comprise up to approximately 5 % by weight, be more preferably less than 1 % by weight, most preferably the nucleator of 0.5 % by weight (as talcum).
Early stage in forcing machine mixing process, physics pore forming material, as supercritical CO 2, be combined with melt.Then, in the time that mixture leaves forcing machine and is cut, supercritical CO 2expand to form expanded bead.The method of prior art need to cutting before quenching PLA.Therefore, the method for prior art does not produce expanded bead at forcing machine place but produces pearl, and it is with post-foaming, thereby causes physically dissimilar bead, and this bead need to be coated with to work in mold applications.Alternatively, in reexpansion process, heating bead allows material to expand to reduce density.
In some embodiments, can use alternatively gas pressurization expanded bead, in the molded operation of the finished product for desired, described gas will allow the other expansion of bead.Optional pressurization is used for making pressing and being greater than normal atmosphere in the unit in foamed.The fact that foamed has closed cell structure makes bead after impregnation steps can keep being greater than atmospheric interior pressure.When heat bead during molded time, this interior pressure allows expanded bead further to expand.Conventionally by means of gas as air, CO 2, N 2, hydrocarbon polymer etc. realizes this pressurization or the dipping of expanded bead.Then, bead is put into mould to form selected product.
In extrusion and foaming process, must control carefully the temperature curve of forcing machine to allow fusing and the mixing of solid, react with chain extension agent (optionally), for example, with pore forming material (supercritical CO 2) mix, and before extruding by mould cold fuse-element mixture.The temperature of initial cylindrical portions allows fusing and the mixing of solid, is included in dispersion nucleator in melt.Meanwhile, optional chain extension agent reacts with the chain end of polymkeric substance, thereby increases branch and molecular weight, the melt strength that this can increase the viscosity of melt and improve plastics.Before injection pore forming material, by careful design inner screw member, in forcing machine, produce melt sealant, leave opening for feed to prevent that pore forming material from flowing.Melt sealant maintains the pressure in forcing machine, is soluble thereby allow pore forming material to remain in molten plastic.After injection pore forming material, hybrid element is used for mixing pore forming material and melt.Solubility pore forming material in melt plastifies melt significantly, thereby greatly reduces its viscosity.Plastification allows cold fuse-element to the normal temperature of fusion lower than the polymkeric substance compost in the final section of forcing machine or based on biological.Cooling is the necessary viscosity with increase plasticizing melt, to allow to retain the modular construction of sealing during bubbling in mould.
Nucleator is as the nucleation site for pore forming material volatilization during bubbling.When there is step-down in mould time, be dissolved in pore forming material in plastic melt and leave solution and enter gas phase.By entering gas phase, the volume being occupied by pore forming material significantly increases, thereby produces foaming structure.By disperse nucleator in melt, between pressure reducing period, pore forming material will evaporate into its gaseous form from its solvable state in melt equably, thereby produces meticulous porous, expanded thing.In the case of the nucleation site that does not have suitably to disperse, foaming may be inhomogeneous, thereby produces larger space or open modular construction, and wherein cell-wall is ruptured and interconnects.Larger space and open modular construction produce more firmly, more crisp foamed.The very low-density foamed thing with closed cell structure can be described to sponge, and after significantly compressing, it has good elasticity recovery.
In the time that extrudate leaves mould and foams, the rotating blade of nodulizer cuts bead on the surface of mould.In the time of cutting, foamed is not yet fully set up.After bead is cut, bubbling process continues the structure of moulding bead.Pore forming material continues volatilization, thereby makes grain expansion.In the time of cutting, the crust of particle keeps rubber-like, thereby allows the surface flow of expanded bead and again form smooth solid surface.
Can be in several ways anyly prepare foaming composition melt-processable of the present invention, compost or based on biological.For example, can be by the mixing device that conventionally adopts in plastic industry any, as by means of mixing forcing machine, polymkeric substance compost or based on biological, pore forming material, nucleator and optional additive can be combined.For example, can use material with the form of powder, spherolite or particulate product.At the temperature of the fusing point higher than polymkeric substance or softening temperature, most convenient carries out married operation.Can the mixture mixed melting of generation be processed into expanded bead by the extrudate mixture of cutting polymer and pore forming material on the surface of extrusion die.By cut extrudate on the surface of extrusion die, before the complete expansion of foaming, form bead.After granulation, form expanded bead by the expansion (passing through pore forming material) of extrudate.By discharging pore forming material cooling expanded bead, but can be by contacting to apply subsequently cooling with water, water vapour, air, carbonic acid gas or nitrogen.Utilize the conventional equipment for molded expandable polystyrene, the expanded bead of generation can be molded as to three-dimensional part.In one embodiment, expanded bead comprise remaining pore forming material and can in molding process, carry out after expand.In another embodiment, before molded, with gas, as air or carbonic acid gas, carry out pressure expansion bead, during molded, expand allowing.
Conventionally to the temperature of 300 ℃, carry out melt-processed at approximately 80 ℃, although the selection of optimum operating temperature is fusing point, melt viscosity and the thermostability that depends on composition.Dissimilar melt-processed device, as forcing machine, can be used for processing melt-processable composition of the present invention.Be applicable to forcing machine of the present invention and be described in, for example, Rauwendaal, C, " Polymer Extrusion, " HansenPublishers, p.11-33,2001.
In one embodiment, the expanded bead compost of generation or based on biological has the 0.15g/cm of being less than 3proportion.In another embodiment, expanded bead compost or based on biological has and is preferably less than 0.075g/cm 3proportion, and be most preferably less than 0.05g/cm 3.
Preferably, there is the content based on biological that is greater than 50% for the preparation of the polymkeric substance of expanded bead, be most preferably greater than the content based on biological of 80wt%.In one embodiment, as determined according to ASTM D6400, the foamed that is greater than 50wt% is compost.One preferred embodiment in, the foamed that is greater than 80wt% is compost.In the most preferred embodiment of one, the foamed that is greater than 95wt% is compost.
First three embodiment adopts the PLA resin of single type below.But known, the degree of crystallinity of PLA is subject to two basic sides controls: the firstth, form, and second is process.PLA polymkeric substance is made up of lactic acid monomer, but has the lactic acid monomer of two types.Although be made up of identical element, functional group and chemical bond, the stereochemistry of monomer is different.Described two kinds of isomer of lactic acid, so-called l and d-isomer, have different three-dimensional ' chirality '.Result is that the type of isomer can affect the position of side along the pendant methyl of the main chain of PLA polymer chain.100% by 1 or the PLA chain that forms of d-isomer will be highly crystalline, this is because polymer chain can closely be filled each other.By introducing compared with other isomer of small concentration, degree of crystallinity starts to reduce, this be because the position of pendant methyl start to destroy degree of crystallinity compared with higher structure.Have 1 and the PLA that approaches 50/50 mixture of d-isomer cause complete amorphous polymer.The 1-isomer of lactic acid is the main natural form of lactic acid, so most semi-crystalline PLA is mainly made up of 1-isomer, and has the random impurity of d-isomer.From 100%1 or d-isomer to produce PLA be very difficult, so all semi-crystalline materials that can obtain in a large number will comprise less d-content of isomer.805ID resin has approximately 3.7 to 4.6% d-content of isomer, and 4032D resin has the d-content of isomer (1.2 to 1.6%) that is less than 2%.
In PLA, the second aspect of thermostability is process and the thermal history (thermal history) of plastics.The slow crystallization of PLA.Although d-content of isomer can be in suitable scope to support degree of crystallinity, if cooling material too soon, this must not occur.When heating of plastic is during higher than its fusing point, all degree of crystallinity can be lost, thereby needs thermal annealing slowly to carry out induced crystallization.Filler, as high-performance talcum, through being commonly used to promote more rapid crystallization, extrudes but wish to utilize for the great majority of the high-crystallinity of thermostability the annealing steps that application need to be between 100 ℃ to 130 ℃, with sufficient crystallising PLA.But, in the application of extrusion foaming thing, during generating foamed, there is enough shearings and unit elongation, to induce the degree of crystallinity in the very thin plastic film of closed pores that separates foamed.In addition, between foaming processing period, be used for promoting to be dissolved in CO in melt 2dispersion and the nucleator of nucleation also improve kinetics of crystallization.Therefore, the rapid crystallization of extrusion foaming thing process induction PLA.From the angle of thermostability, this is unexpected, because do not need annealing steps.
Fig. 1 illustrates the process schematic diagram of producing bead by extrusion foaming method.In following examples, be that Leistritz ZSE27MAXX corotation turns twin screw extruder for the forcing machine of mixing process, it has ten segmentations in cylinder.The cylinder of forcing machine is equipped with filling orifice with by supercritical co (CO 2) be supplied to the plastic melt in the 4th cylindrical portions.By the liquid CO from pressurized cylinder with the pressurization of TharSFC P-50 high-pressure pump 2to 27.6MPa(4000psi) pressure produce the CO of supercritical state 2.All forcing pipes have chuck, are that the ethylene glycol-water mixture of 2 ℃ (35 °F) is in addition cooling with setting point.
In another aspect of the present invention, the improvement of the production of light-weight foam bead is described.In improved method, during extrusion, in conjunction with physics pore forming material and chemical foamer, to produce light-weight foam bead.Coming in production lightweight bead process by extruding the granulation with hot side, physics pore forming material, preferably supercritical CO 2, as the main source of pore forming material.By chemical foamer is added to extrusion, make during extruding chemical foamer not degradable, the lightweight bead of generation will retain some chemical foamers in their composition.
Can add secondary pore forming material in one of three kinds of modes.In the first situation, secondary pore forming material can be added to the upstream of a pore forming material.In the second situation, secondary pore forming material can be added to the downstream of a pore forming material.And, in the third situation, can add secondary pore forming material with a pore forming material simultaneously.Preferably, in all cases, a pore forming material is that physics pore forming material is as supercritical CO 2.A this pore forming material is used for providing most expansion to produce expanded bead during extruding.During extruding and forming with expanded bead, the object of secondary pore forming material is to a great extent still in dormant state, thereby it can be triggered so that further expanded beads in the course of processing subsequently of expanded bead.Carefully design method of the present invention, makes not completely consumed secondary pore forming material in extrusion and foaming process.Method of the present invention allows secondary pore forming material in extrusion foaming thing process to remain intact to a great extent, thereby allows secondary pore forming material to add expanded bead.
It is contemplated that, chemical foamer is suitable as secondary pore forming material most.For the first and the second situation, pore forming material is injected before melt or after, chemical foamer is added to the polymer melt of forcing machine.Due to the temperature that melt raises, possible is that chemical foamer decomposes starting and gas is provided, and it can foamable polymer.By controlling temperature and the residence time of polymkeric substance/pore forming material mixture in forcing machine of melt, can control the degree of decomposition of pore forming material.Can there is to discharge gas in some decomposition, but as long as some pore forming materials are retained in extrudate, expanded bead will comprise it.
For the third situation, secondary pore forming material mixes and while injection of polymer melt with a pore forming material.It is contemplated that supercritical CO 2that pore forming material and chemical foamer are as secondary pore forming material.Chemical foamer can be liquid or solid.One preferred embodiment in, supercritical CO 2 can as carrier come mutually soluble chemistry pore forming material with form mixture.Then the cylinder that mixture is injected to forcing machine with Mixing of Polymer Melt.It is contemplated that, some preferred embodiment in, in expanded bead, secondary foaming agent concentration is approximately 0.5 to about 5wt%.
Embodiment #1
The blend that is dry mixed that produces plastics, it is made up of the following: the multifunctional oligopolymer reactant of Clariant CESA-extend OMAN698498 Styrene And Chloroalkyl Acrylates of the Nature Works Ingeo805ID poly(lactic acid) (PLA) of about 97 % by weight, about 2 % by weight and the Cereplast ECA-023 talcum masterbatch of about 1 % by weight.Particle dry mixture is supplied to the opening for feed part of twin screw extruder according to gravity method.The feeding rate of solid is set as 3.5kg/hr(7.7lbs/hr), and under 40rpm rotary screw.With 10g/ minute, by supercritical co (CO 2) be injected into the 4th plastic melt in part.The S.C. bundle mould bolt with 3mm opening is connected to the end of forcing machine.
Originally, use the smooth temperature curve of 210 ℃.After starting, extrudate temperature exceedes 200 ℃; But under this high temperature, extrudate foaming is poor, shows low melt strength, and lacks the viscosity remaining on pore forming material.Modular construction is due to CO 2convenient in rapid escape leaves open modular construction and collapses fast, only has less density and reduces.To leave the temperature curve on 10 cylindrical portions and systematically regulate to realize 210 ℃, 199 ℃, 177 ℃, 155 ℃, 122 ℃, 111 ℃, 100 ℃, 102 ℃, 101 ℃ and 85 ℃ across forcing machine from being fed to.Under these conditions, be 11.7MPa(1700psi at the melt pressure at mould place).Extrudate is foamed to being less than 0.04g/cm 3(2.5lb/ft 3) density, and there is the modular construction of sealing.The surface temperature of bundle conductor extrudate is less than 40 ℃.
Embodiment #2
According to also improve the method for describing in embodiment #1, to be included in the granulation operation on die surface.By off-axis, double blade nodulizer is mounted to forcing machine and die assembly.On the surface of mould, be used in the nodulizer cutting expanded bead operating under 1500rpm.Expanded bead unrestricted flow and not sticking together.The surface of expanded bead is complete and does not present open or damaged unit.The density of expanded bead is less than 0.04g/cm 3(2.5lb/ft 3), and bead diameter is approximately 10mm.
Embodiment #3
Improve the method for describing to substitute 3mm plain conductor bundle mould (use has the octal mould of 0.8mm mould openings) in embodiment #1.New die comprises adapter part, and it added a heating zone before mould.Granulating system is changed over to coaxial double blade diced system (operating under 2500rpm).The feeding rate of the dry blend of resin, chain extension agent and talcum masterbatch is reduced to 2.3kg/hr(5lbs/hr).By the final processing temperature curve adjustment at low-density foamed thing production period to across 210 ℃, 199 ℃, 177 ℃, 155 ℃, 115 ℃, 115 ℃, 115 ℃, 115 ℃, 115 ℃, 130 ℃ and 135 ℃, forcing machine and mould.Under 25rpm, operate extruder screw.At about 10.3MPa(1500psi) pressure under, supercritical CO 2feeding rate be 7.0g/ minute.The operating period of forcing machine melt pressure be, about 15.8MPa(2300psi after mould).The expanded bead producing has the diameter of 2mm to 5mm, and density is less than 0.045g/cm3(2.8lb/ft3).Fig. 2 shows the Photomicrograph of the wedge-shaped cross-section of the expanded bead obtaining by scanning electron microscopy, and it illustrates that cell size is the modular construction of the sealing of 50 to 150 μ m.
Embodiment #4
Improving the method described in embodiment #3 has compared with beads diameter with from the expanded bead of different compositions to produce.With the alternative described mould of 12 punch dies with 0.6mm mould openings.Use and turn twin screw extruder from the 38mm SHJ-38 corotation with 180 ℃ of smooth temperature curves of Lantai Plastics Machinery Company and carry out pre-mixing feed composition.For this operation, dry blend mixture is prepared by the following: the multifunctional oligopolymer reactant of Clariant CESA-extend OMAN698498 Styrene And Chloroalkyl Acrylates of the NatureWorks Ingeo4032D PLA of the NatureWorks Ingeo805ID PLA of about 87 % by weight, about 10 % by weight, about 2 % by weight and the Cereplast ECA-023 talcum masterbatch of about 1 % by weight.Subsequently with 2.3kg/hr(5.0lbs/hr), the preparation of mixing is sent into the opening for feed of Leistritz ZSE27MAXX forcing machine, screw speed is 25rpm.Supercritical CO 2feeding rate be 7g/ minute, and temperature curve is 210 ℃, 199 ℃, 177 ℃, 155 ℃, 115 ℃, 115 ℃, 115 ℃, 115 ℃, 115 ℃, 150 ℃ and 150 ℃.Under 1920rpm, operate nodulizer, on the surface of extrusion die, cut extrudate.Melt pressure after mould is about 15.2MPa(2200psi).Produce expanded bead there is the diameter of 1mm to4mm, and be less than 0.045g/cm3(2.8lb/ft3) density.For relative thermostability, the expanded bead relatively producing by this method and the expanded bead producing in embodiment #3.Placed side by sidely on hot plate and under the temperature ramp increasing, heat, and compare from the expanded bead of embodiment #3, this expanded bead is softening at higher temperature.
Embodiment #5
At 0.45MPa(65psi) under, in sealed vessel, pressurization continues to be less than 30 minutes from the expanded bead of embodiment #4.Carry out the reduction of blood pressure in high-speed of container to remove bead.The surface of tightening bead by superatmospheric interior pressure.Bead vacuum is sent into the cavity of the molded press of steam tank (Hirsch HS1400D), and from pressurized vessel, taken out in 1 minute.During filling, original moulded cavity temperature is approximately 25 ℃.Use the conventional aluminium-making mould for expandable polystyrene (EPS) of box-shape.With the next molded final product of four step processes.The removing cycle is set as 1 second, under 0.55 bar vapor pressure and 30% valve open.First intersects steam course is set as 20 seconds, under 0.55 bar vapor pressure and 90% valve open.Under the vapor pressure of 0.65 bar and 90% valve open, use second to intersect steam course (with vapour stream opposite direction) and continue 20 seconds.Apply water coolant 15 seconds in mould both sides, then under 4 bar pressures, apply cooling air 30 seconds.After cooling air, apply 5 seconds vacuum.Remove mold cassettes from press.Clearly illustrate that the reexpansion of expanded bead in mould in the molded shape of bead later.Be copied to the surface of goods from the surface depression of molding cavity and texture.Weight based on box and geometrical shape, the density of moulded product is less than 0.03g/cm 3(2.0lb/ft 3).
Invention described herein allows the existing EPS of transformation manufacturing works to produce the foaming product based on polymkeric substance compost or based on biological.Fig. 3 illustrates that composition that utilization is described in the above-described embodiments and method produce the gathering of step of finished product.First, mix the raw material of PLA polymkeric substance, nucleator and other additives.In some embodiments, described at embodiment #4, can in independent forcing machine, mix these raw materials.Then, by pore forming material, preferably supercritical CO 2, add mixture.The foamed bundle conductor of extruding by hot side granulation on extruding machine mold face produces less light-weight foam bead.In some embodiments, can utilize water-bath or other appropriate means to carry out cooling expanded bead.Then pressure expansion bead is to promote the reexpansion at the mould of the finished product for desired.Conventionally by means of gas as air, CO 2, N 2, hydrocarbon polymer etc., complete this pressurization of expanded bead.Then, bead is put into mould to form selected product.Described at embodiment #5, steam press can be used for molded.Bead expands to produce finished product in mould.
Early stage in forcing machine mixing process, by physics pore forming material, as supercritical CO 2, be combined with melt.In one embodiment, after physics pore forming material, and in the relatively cold part of forcing machine, add chemical foamer.In another embodiment, before physics pore forming material, again, in the relatively cold part of forcing machine, add chemical foamer.Then, when mixture leaves forcing machine and when cut, supercritical CO 2expand to form initial bead.Be different from method in the prior art, mixture, without quenching, or prevents expansion (in the time that it leaves forcing machine) before cut.These beads have and in extrusion, have been immersed in chemical foamer wherein.Control carefully described process so that not completely consumed of secondary pore forming material during extrusion and foaming process.Due to the lesser temps using at interpolation chemical foamer place in extrusion, in extrusion, it can keep dormant state.Subsequently, in reexpansion process, heating bead will discharge gas (by the thermolysis of chemical foamer), therefore, when in the time being combined for the correct temperature of softening plastics, allow material to expand to reduce density.During molded, for example, bead heated so that they are melted in together and chemical foamer is activated, thereby cause reexpansion., during molded, thereby thereby the thermal destruction that can trigger pore forming material can be carried out bead fusion or traditional pre-expansive working further reduces density.
One preferred embodiment in, chemical foamer is added and injects the extrusion in downstream and mix physics pore forming material.But, as described above, can in the melt of injection upstream, add secondary pore forming material, and mix physics pore forming material, or mix with physics pore forming material simultaneously.Conventionally, leaving before mould, needing cooling extruded mixture, to keep enough melt strengths and can obtain the modular construction that foamed is good.By forcing machine compared with cold-zone in add chemical foamer, the heat energy of chemical decomposition pore forming material is less, and has reduced the resonance time of material in forcing machine.Can be with, for example, the form of powder, spherolite or particulate product, is used these materials (biodegradable polymers, pore forming material, biodegradable softening agent and optional additive).At the temperature of the fusing point higher than polymkeric substance or softening temperature, carry out married operation most convenient.The melting blended mixture obtaining can be processed into lightweight bundle conductor and utilize subsequently bundle conductor nodulizer to cut into bead.In another embodiment, produce expanded bead by cut foamed bundle conductor on the surface of extrusion die.By cut extrudate on the surface of extrusion die, occurring before the complete expansion of foamed, form bead.After granulation, expanded bead is formed by the expansion (by physics pore forming material) of extrudate.By discharging pore forming material cooling expanded bead, but can be by contacting with water, water vapour, air, carbonic acid gas or nitrogen, apply subsequently cooling.Can utilize the conventional equipment adopting in molded expandable polystyrene that the bead obtaining is molded as to three-dimensional part.The object of secondary pore forming material is to keep to a great extent dormant state, thereby it can be triggered so that further expanded beads in the course of processing subsequently of expanded bead.Preferably, expanded bead comprise residue chemistry pore forming material and can in molding process, carry out after expand.
In one embodiment, as determined according to ASTM D6400, the material that foamed more than 50wt% comprises compost.One preferred embodiment in, the material that foamed more than 80wt% comprises compost.In the most preferred embodiment of one, the material that foamed more than 95wt% comprises compost.
The compound that utilization comprises polyester compost or based on biological and pore forming material produces the expandable bead of one aspect of the present invention.In composition compost or based on biological, comprise alternatively the additive that comprises softening agent and chain extension agent.Can utilize conventional melt technology, as single Screw Extrusion and twin screw extrusion, produce expandable bead.In one embodiment, by melt-processed, make polymkeric substance compost or based on biological mix to produce particle with hydrophobic additive.Then flood these particles with preparation expandable bead with pore forming material.Then heat expandable bead to bubble, thereby produce expanded bead.Then expanded bead is molded as to goods.In another embodiment, melt-processed is used for mixing polymkeric substance, hydrophobic additive and pore forming material compost or based on biological, directly to operate to produce expandable bead by melt-processed.In this case, must the fast cooling extrudate from mould to be locked in pore forming material, make it not escape and not bubble.Be desirable to, in pre-expander operation, bubble in the controlled time by heating expandable bead, to produce expanded bead.Then molded expanded bead.Preferably, the expanded bead obtaining has the 0.15g/cm of being less than 3density.More preferably, expanded bead has the 0.075g/cm of being less than 3density, and be most preferably less than 0.05g/cm 3.One preferred embodiment in, as according to ASTM D6400 determine, foamed more than 50wt% is compost.More preferably, more than 80% foamed is compost.In the most preferred embodiment of one, more than 95% foamed is compost.
In some embodiments, as required, interested plastics preparation can be mixed into the homogeneous material for extruding.In suitable situation, for example, by a plastics granulation and grind alternatively and be categorized into the particle with predetermined size, 0.25mm diameter.Then polymer beads can be added the stirring pressure-pot with water to produce slurry.Can add solution stabilizer, as tensio-active agent or salt, to suppress particle coagulation and to promote hydrocarbon polymer pore forming material to diffuse into polymer beads.In some embodiments, will be added into slurry as the hydrocarbon polymer pore forming material of liquid.Preferably, add the amount of hydrocarbon polymer pore forming material of system by scheduled, its desired degree based on hydrocarbon polymer pore forming material in expandable bead.Pressure-pot can be temperature controlled, for example, by cycling hot water-bath.In some embodiments, by pressure-pot mechanical seal and utilize pressurized gas (as nitrogen) to pressurize.
It is contemplated that, the present invention can substitute the EPS material in the existing installation of production plant.Can use the raw material being formed by expandable bead compost or based on biological to substitute EPS raw material.Hydrocarbon polymer pore forming material is envisioned for pore forming material, and this is because they are manufactured for EPS, and exists several different methods catch and burn as the volatile hydrocarbon of fuel.Expect to be down to minimum by being used for that existing factory is transformed into the required cost of material new compost or based on biological by EPS.
A critical aspects of an embodiment of the invention is, in the time using, to add polymkeric substance compost or based on biological as the ability in the matrix of PLA the hydrocarbon polymer pore forming material of q.s.For example, PLA do not show that polystyrene presents for adsorbing the avidity of pentane, produce EPS.At room temperature, pentane be easy to absorb enter solid polystyrene, but PLA this thing happens.Therefore be necessary to produce the composition of polymkeric substance compost or based on biological, it allows impregnated carbon hydrogen compound pore forming material.In order to accomplish this point, amphipathic or hydrophobic additive are added to preparation, although not all amphipathic or hydrophobic additive is all favourable.Amphipathic or the hydrophobic additive with lower wetting ability-lipophilic balance (HLB) value is preferred.The example of lower HLB value hydrophobic additive comprises Span60(sorbitan monostearate, HLB=4.7), Span80(sorbitanic oleic acid ester, HLB=4) and Span85(Span 85, HLB=1.8).Segmented copolymer nonionic emulsifier can also be as hydrophobic additive to improve hydrocarbon polymer pore forming material solvability.The example of suitable nonionic emulsifier is the Unithox420 ethoxylate (HLB=4) from Baker Petrolite, and it is the lower molecular weight segmented copolymer of polyethylene and polyoxyethylene glycol.The oil of biogenetic derivation, as soya-bean oil or acetylizad direactive glyceride (it is derived from hydrogenated castor oil), can be used for contributing to hydrocarbon polymer pore forming material solvability in addition.
By using conventional softening agent, chain extension agent, linking agent, and with the blend of other thermoplasticss, the additionally composition of polymer formulation product modification compost or based on biological, to improve the processing characteristics of resin and other aspects of latherability.
For example, utilize melt-processed to pass through twin-screw extrusion, be created in material compositions listed in following table 1.Polymkeric substance NatureWorks2002D poly(lactic acid) (PLA), compost and based on biological is the main component of all preparations.Other starting material comprise citrate (CitroflexA-2, Vertellus Performance Materials), copolyester elastomer (Neostar FN007, Eastman Chemical), stearic acid surface-treated calcium carbonate (Omyacarb FT, Omya North America), sorbitan monostearate (Span60, Sigma-Aldrich), polyoxyethylene glycol (Carbowax8000, Dow Chemical), be derived from the acetylated monoglyceride (Soft-N-Safe of hydrogenated castor oil Grindsted, Danisco), dicumyl peroxide (Sigma-Aldrich), ethoxylated non-ionic type emulsifying agent (Unithox450, Baker Petrolite) and the PLA of own toxilic acid esterification.In forcing machine, utilize the constant temp curve of 180oC, by melt-processed by mass 3% maleic anhydride, by mass 0.5% dicumyl peroxide and by mass 96.5% Nature Works2002D PLA produce the PLA of toxilic acid esterification, as the precursor of preparation.
Figure BDA0000474435040000241
Table 1. composition and after dipping the degree of pentane
Starting material are sent into 26mm, corotation and are turned the opening for feed of twin screw extruder (model LTF26-40, from LabTech Engineering Company, LTD).Use the steady temperature curve of 180oC.Make extrudate pass mould to produce bundle conductor, by water or in addition cooling by air, then granulation.For with pentane pore forming material dip composition, the sample of weighing in advance of particle is sealed in pressurized vessel and with liquid pentane and contacts (at room temperature).Heated sample container to 80 ℃ is submerged in water-bath 2 hours simultaneously.After two hours, take out sample and allow cooling.Take out particle, blot to remove any top coat of liquid pentane, then weigh.Calculate dipping by the difference of final quality and initial mass and enter the pentane quality of particle, and be expressed as the per-cent (in table 1) of sample quality.Comprise that the control sample of Nature Works2002D PLA and toxilic acid esterification PLA is as reference.After dipping, record control sample and comprise and be less than by mass 2.5% pentane, the material that comprises hydrophobic additive increases the pentane quality by steeping process combination widely.By heating on hot plate, material listed in table 1 is expanded to produce expanded beads subsequently, thereby allow to discharge pentane pore forming material to gas phase.
With reference to embodiment, the present invention is described.Although, in order to describe the object of concept of the present invention, concrete numerical value, relation, material and step are provided, but what it will be understood by those skilled in the art that is, can to as in disclosed embodiment illustrated the present invention carry out many variations and/or change, and do not depart from the spirit or scope of broadly described key concept of the present invention and principle of operation.Will be appreciated that, under the inspiration of above-mentioned instruction, those skilled in the art can improve those details and not depart from the invention of instruction herein.Some embodiment and the change of the concept that forms basis of the present invention are now very full on, after being familiar with described key concept, to those skilled in the art, various other embodiments and illustrating herein and the potential variation of the embodiment described and to change will be apparent.It is intended to comprise all such changes, replacement scheme and other embodiments, as long as they within the scope of the invention.Therefore, should be appreciated that and can implement the present invention with being different from other modes of specifically illustrating herein.Therefore, embodiments of the present invention are considered to illustrative and not restrictive in all respects.
Industrial applicibility
The present invention relates to manufacture and the use of expanded bead compost or based on biological.Expanded bead of the present invention is for being manufactured the industry of container and other goods by material compost or based on biological.

Claims (48)

1. a composition for material, comprises:
Expanded bead compost or based on biological, described expanded bead has the modular construction of sealing substantially.
2. composition according to claim 1, further comprises pore forming material.
3. composition according to claim 1, wherein, described pore forming material comprises physics pore forming material.
4. composition according to claim 1, wherein, described pore forming material comprises supercritical CO 2.
5. composition according to claim 1, the polymkeric substance of described compost comprises the polymkeric substance of poly(lactic acid).
6. composition according to claim 5, wherein, in described polylactic acid polymer, the content of D-isomer is less than 6%.
7. composition according to claim 5, wherein, in described polylactic acid polymer, the content of D-isomer is less than 2%.
8. composition according to claim 1, further comprises nucleator.
9. composition according to claim 1, further comprises additive to improve melt rheological property energy and viscosity.
10. composition according to claim 1, further comprises the additive in the group forming below choosing freely: antioxidant, photostabilizer, fiber, foaming additive, conductive additive, anti blocking agent, static inhibitor, thermo-stabilizer, impact modifying agent, biocide, expanding material, tackifier, tinting material, coupling agent and pigment.
11. compositions according to claim 1, wherein, described composition is by the compost material production more than 50%.
12. compositions according to claim 1, wherein, described composition is by the compost material production more than 80%.
13. compositions according to claim 1, wherein, described polymkeric substance more than 50% ground based on biology.
14. compositions according to claim 1, wherein, described polymkeric substance more than 80% ground based on biology.
15. compositions according to claim 1, wherein, on the surface of extrusion die, after by extrudate granulation, described expanded bead has the modular construction of sealing substantially.
16. compositions according to claim 1, wherein, described expanded bead has spherical or subglobular shape.
17. compositions according to claim 1, wherein, described expanded bead has the diameter of about 1mm to about 10mm, and preferred about 2mm is to about 5mm, and more preferably from about 1mm is to about 4mm.
18. compositions according to claim 1, wherein, described expanded bead has the 0.045g/cm of being less than 3density.
19. compositions according to claim 1, wherein, described expanded bead has the cell size diameter of 50 μ m to 150 μ m.
The composition of 20. 1 kinds of materials, comprises:
Polymkeric substance compost or based on biological, described polymkeric substance is together with at least one pore forming material melt-processed resulting mixture, described mixture forms has the expanded bead of the modular construction of sealing substantially, wherein, in the time that described foaming extrudate leaves forcing machine, on the face of mould, form described expanded bead.
21. compositions according to claim 20, wherein, described pore forming material comprises physics pore forming material.
22. compositions according to claim 20, wherein, described pore forming material comprises supercritical CO 2.
23. compositions according to claim 20, the polymkeric substance of described compost comprises the polymkeric substance of poly(lactic acid).
24. compositions according to claim 20, wherein, described bead has spherical or subglobular shape.
25. compositions according to claim 20, wherein, described bead can keep internal gas pressure to exceed envrionment conditions in the modular construction of the described sealing of foamed.
26. compositions according to claim 20, wherein, described bead has the diameter of about 1mm to about 10mm, and preferred about 2mm is to about 5mm, and more preferably from about 1mm is to about 4mm.
27. compositions according to claim 20, wherein, described expanded bead has the 0.045g/cm of being less than 3density.
28. compositions according to claim 20, wherein, described expanded bead has the cell size diameter of approximately 50 μ m to approximately 150 μ m.
29. 1 kinds of methods, comprising:
In forcing machine, melt-processed comprises polymkeric substance compost or based on biological and the composition of pore forming material, to form extrudate; Wherein said extrudate comprises the bead of the modular construction of sealing substantially, and described bead is formed has the expanded bead of closed cell substantially.
30. methods according to claim 29, described composition further comprises nucleator.
31. methods according to claim 29, further comprise, by being connected in the nozzle mould of described forcing machine end, extrude described extrudate.
32. methods according to claim 31 wherein, in the time that described extrudate leaves described mould, form described expanded bead on the surface of described mould.
33. methods according to claim 31, further comprise and cut described extrudate with the rotating blade of front-end surface of the described nozzle mould of contact, allow described extrudate to foam to produce expanded bead simultaneously.
, wherein, before the complete expansion of foaming extrudate, on the surface of described extrusion die, there is the granulation of described extrudate in 34. methods according to claim 33.
35. methods according to claim 29, wherein, described composition further comprises additive.
36. methods according to claim 29, wherein, described pore forming material comprises physics pore forming material.
37. methods according to claim 29, wherein, described pore forming material comprises supercritical CO 2.
38. methods according to claim 29, the polymkeric substance of described compost comprises polylactic acid polymer.
39. methods according to claim 29, further comprise by liquid or the gas pore forming material described bead that pressurizes.
40. methods according to claim 33, wherein, described gas selects free air, CO 2, N 2, and the group of hydrocarbon polymer composition.
, wherein, after the granulation of the described extrudate mixture of polymkeric substance and pore forming material, there is the foaming of described pearl in 41. methods according to claim 33.
42. methods according to claim 29, further comprise: described bead is moved into mould; And by applying heat, in described mould, further expand and merge described bead.
43. methods according to claim 29, wherein, described bead can remain on the interior pressure in the modular construction of described sealing, thereby the volumetric expansion of described expanded bead is provided in heat-processed.
44. 1 kinds of methods for generation of foaming moulded product, comprise the following steps:
Method according to claim 29 produces expanded bead;
Make described expanded bead under temperature and pressure condition with obtain foaming moulded product.
45. according to the method described in claim 44, and wherein, described method promotes the fusion of described expanded bead by heated air.
46. according to the method described in claim 45, and wherein, described method is used steam.
47. according to the method described in claim 40, and wherein, described method is used the mixture of air or air and steam.
48. methods according to claim 35, wherein, described additive selects the group of free the following composition: antioxidant, photostabilizer, fiber, pore forming material, foaming additive, anti blocking agent, thermo-stabilizer, impact modifying agent, biocide, expanding material, tackifier, tinting material, coupling agent, static inhibitor, conductive filler material and pigment.
CN201280043807.2A 2011-07-07 2012-07-06 Compostable or biobased foams, method of manufacture and use Pending CN103890066A (en)

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US13/178,293 US20120009420A1 (en) 2010-07-07 2011-07-07 Compostable or Biobased Foams
US13/178,272 US20120010307A1 (en) 2010-07-07 2011-07-07 Expandable Beads of a Compostable or Biobased Thermoplastic Polymer
US13/178,293 2011-07-07
US13/178,300 2011-07-07
US13/178,300 US20120007267A1 (en) 2010-07-07 2011-07-07 Method of Producing Compostable or Biobased Foams
US13/178,272 2011-07-07
US13/230,158 2011-09-12
US13/230,158 US8962706B2 (en) 2010-09-10 2011-09-12 Process for enabling secondary expansion of expandable beads
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