CN85106316A - Foamed polymer, the method for its thermoformed shapes and moulding thereof - Google Patents
Foamed polymer, the method for its thermoformed shapes and moulding thereof Download PDFInfo
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- CN85106316A CN85106316A CN 85106316 CN85106316A CN85106316A CN 85106316 A CN85106316 A CN 85106316A CN 85106316 CN85106316 CN 85106316 CN 85106316 A CN85106316 A CN 85106316A CN 85106316 A CN85106316 A CN 85106316A
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Abstract
The invention provides density and be lower than 320.4kg/m
3Foam copolymer structure, also provide to comprise the polymer beads compound of lyosorption.The present invention has also disclosed the forming method and the thermoforming section bar thereof of this foamed polymer thus.
Description
The relevant foam of polymers of the present invention, its thermally molded article each and the method for preparing them.
In " modern plastics encyclopedia ", 1982-83,59 volumes on No, the 10A 275-278 page or leaf, disclose the method that some preparations are referred to as " structural foam " usually.This piece reference points out that the forming method of structural foam is similar to injection moulding method commonly used, and its dissimilarity is, needs to add whipping agent in this thermoplastic resin fusibleness, and when carrying out injection operation, not with the complete mold filling of mould.Formed the cortex of a non-foaming structure in abutting connection with the material of die surface, whipping agent expands to remaining material, thereby fills up mould and form the spumescence sandwich layer simultaneously.Under all situations that this piece reference is narrated, thermoplastic material and chemical foaming agent all melt under pressure outside mould and mix.After molten mixing,, then under the pressure of this formation system, fill up mould fully with the mixture that is suspended in the decomposed chemical foaming agent in this melt if adopt the high-pressure molding method.The melt material that contacts with mould forms the solid cortex of no abscess, then, impels the core chamber part of the heat of foaming outwards to foam and is full of mould.The goods of Sheng Chaning have slick finishing in this way.If adopt the low pressure molding method, then fill up the required volume of die cavity and in mould, inject resin melt and whipping agent to be less than.Because mould is not filled with, so the pressure that forms in die cavity because of injection operation and heat-processed just seldom has above 35kg/cm
2(500 pounds/inch
2).When pressure relief, foam material fills up mould with regard to expansion, and the result has just formed foam resin product, is characterized in having the uneven eddy flow pattern of color, and this just needs follow-up surface finish to handle to improve visual appearance.The important parameter of this method will be with pressure to preserve melt material before being included in injection always, and the control injection speed also comprises cast gate, runner and die venting hole that design is special.
Foamed polymer is widely used as insulating material and structured material on for example aircraft and electrical industry.Basic demand to foamed polymer is can be quite heat-resisting.Prior art has noticed when heating temperature reaches degradation temperature that foam material can be fire-retardant and the amount of being fuming is few, and the poison gas of discharging is few.
If have a kind of can be to be easy to control and structural foam be transformed into basically the method that the simple process of low density foam is uniformly produced the molded foam polymkeric substance, so this method is just superior than prior art.Moreover if these processing methodes are used to prepare the flame-retardant polymer foamy structure, that will further develop prior art.
It is 16.0kg/cm that the present invention can provide density
3(1 pound/English Foot
3) to 320.4kg/m
3(20 pounds/English Foot
3) to 320.4kg/m
3(20 pounds/English Foot
3) the foamy structure polymkeric substance.Foamable polymkeric substance comprises that those can suck the polymkeric substance of solvent, and object lesson comprises polyetherimide, the adulterant of polycarbonate and Arnox and polystyrene.The object lesson of solvent comprises methylene dichloride, chloroform, vinyl trichloride and composition thereof.
The present invention also provides and comprises and contain a kind of mixture of polymers of the discrete particles of lyosorption, and this absorption pellet is runny at least basically.
The present invention also provides the method for preparing the low density foam structure, comprising:
(a) soak into granular polymer with solvent;
(b) in the pressure extrusion device, evenly molten this particle and the solvent of mixing;
(c) such admixture is clamp-oned low pressure environment so that solvent evaporation, thereby produce foamy structure.
The present invention also provides the method for preparing the thermoforming polymer foam structure, comprising:
(a) allow density be lower than 320.4kg/m
3(20 pounds/English Foot
3) foamed polymer sheet stand to be enough to make first temperature of its distortion;
(b) under this temperature with this sheet forming; With
(c) reduce the temperature of this sheet material so that it forever when being in this second temperature or being lower than this second temperature keeps in type shape.
The present invention also provides preparation density to be lower than 320.4kg/m
3(20 pounds/English Foot
3) the method for forming polymer foamy structure, comprising:
(a) with solvent heat of emersion plastic polymer particle;
(b) particulate material that will soak into like this is heated to such temperature, and this temperature is enough to make particulate material to expand into density to be lower than former infiltration particulate degree widely; With
(c) this foaming granule material is inserted mould and heat this particle so that its fusing is in aggregates.
The present invention also provides preparation density to be lower than 320.4kg/m
3(20 pounds/English Foot
3) the method for molding thermoplastic foamy structure, comprising:
(a) flood the granular thermoplastic polymer with whipping agent, this polymkeric substance can lyosorption or whipping agent, and foaming agent consumption should reach during dipping is enough to make this swelling polymer to be lower than 320.4kg/m to density
3Degree, thereby be the compound material of free flowable basically particle at least;
(b) with the partially filled mould of this free flowable granular mixture;
(c) pressurizeing on this mould to prevent that whipping agent from evaporating away in a large number in follow-up polymer melt process;
(d) this polymer being heated into is flowable melt state at least;
(e) remove the pressure that is added on the mould, make above-mentioned flux foaming and allow the polymkeric substance of such foaming fill up mould fully; With
(f) allow the molded foam structure demoulding of making like this.
Fig. 1 is for schematically expressing the side-view of the resin lyosorption device of being narrated among the embodiment 3.
Fig. 2 is for schematically expressing the side-view of the pre-expansion gear of being narrated among the embodiment 3.
Fig. 3 is for schematically expressing the side-view of the molded foam device of being narrated among the embodiment 3.
Fig. 4 is for schematically expressing the resin liquid sucking device side elevational view of being narrated among the embodiment 4.
Fig. 5 is for schematically expressing the side elevational view of the molded foam device described in the embodiment 4.
The relevant density of the present invention is lower than 320.4kg/m3(20 pounds/foot3) the foam-like polymer. Can imagine and use any such granular thermoplastic polymer, namely can be easy to Ground infiltrates or floods to produce those polymer of low density foam structure with suitable blowing agent or solvent. The object lesson of this polymer can be enumerated PEI, the admixture of Merlon and Arnox and polystyrene. The object lesson of solvent comprises carrene, chloroform, 1,1,2-trichloroethanes and composition thereof. Because the solvent here uses as blowing agent, so these two terms are used interchangeably in this manual.
But the preferred PEI of lyosoption those included materials that are the following chemical structure formula:
In the formula, Ar is divalent organic group, wherein contains 6-20 carbon atom, and R is selected from the divalent group that comprises following one group of group: aliphatic series, cyclic aliphatic, aromatics and group virtue generation aliphatic series, n is the integer greater than 1, such as 2,3,4 or bigger integer.
The Merlon that preferably can absorb the solvent of chatting has the following chemical structure formula:
Referring to " polymer science textbook ", second edition, not strong W Bi Ermiya Jr(Fred WBillmeyer, Jr) work, 1971, Willie-intermediate science (Wiley-Interscience), NY, NY, the 456th page. Suitable commercial polycarbonate is that the trade mark that General Electric Co. Limited (General Electric Company) sells is LEXAN
The Merlon of (Lexan).
The thermoplasticity admixture of preferred Arnox and polystyrene is poly-2,6-dimethyl The admixture of-Isosorbide-5-Nitrae-penylene oxygen and high impact property (high impact) polystyrene.
Every kind of composition all can reach 20 to 80 % by weight in this admixture. Here used " high impact property polystyrene " is to think briefly to refer to such two kinds of polymer, and namely from US Patent No 4,284,733 disclosed isomery Methylethyl benzol mixtures and rubber are derived and next high impact property copolymer like trunk polymer.
In preferred embodiments, foamed material of the present invention has and is lower than about 80.1kg/m3(5 pounds/foot3) density.
Main reference PEI of the present invention is described. Those skilled in the art can see that the explanation here equally also is suitable for suitable Merlon and Arnox-polystyrene blend composition.
It is known for some time to imagine this PEI of application by the present invention, but is made into foaming structure so that its density is lower than about 320.4kg/m3(20 pounds/English Foot3) the preparation method it is believed that to also not having so far. The PEI that the present invention imagines application is those polymer that can foam and process by solvent by method of the present invention, and used solvent is selected from following one group of compound, i.e. carrene, chloroform, 1,1,2-trichloroethanes and composition thereof. United States Patent(USP) Nos. 3,787,364 and 4,024, but 110 PEIs that disclose lyosoption and foamed and process by the inventive method. The PEI that preferably has above-mentioned chemical structural formula.
The PEI that is included in this structural formula scope can prepare by the described process of following document: " replacing polymerization process by nitro ... the PEI of preparation " of the work such as DM White (DMWhite) etc., polymer science magazine: polymer chemistry version, the 19th volume, 1635-1658 page or leaf (1981), copyright in 1981, John Willie (John Wiley) father and son Co., Ltd publishes. Concrete molecular weight (MW) with reference to speaking of on wherein 1653 pages is the preparation method of about 21,000 polymer " (18ip) ".
The commercially available polyetherimide resin corresponding with the above-mentioned chemical structural formula of quoting from is A Ertemu (Ultem
) 1000, by General Electric Co. Limited, plastics business department-number plastics approach, a MA(General Electric Company hereby, Plastics Operations, One Plastics Avenue, Pit-tsfield, MA.) sell. The vitrification point of this material (Tg) is 216 ℃ (421 °F), and can diameter be about 0.16-0.32cm(1/16-1/8 English Foot), length is 0.16-0.48cm(1/16-3/16 English Foot) granular form bought. Following table has described the related characteristics of this resin material in detail.
In order to prepare foamed polymer material of the present invention, infiltrate granular polymer with solvent or blowing agent earlier. Then, the polymer beads pressurization of this free flowable infiltration is molten mixed, subsequently it is clamp-oned environment under low pressure.
The polyetherimide of preferentially selecting for use is anhydrous, to avoid passing through H
2O forms the possibility of acidic component with combining of solvent.Any such acid product all can corrode extrusion apparatus and may make used polyetherimide or with the degraded of its foamy structure of making.Allow Ultem
1000 pellets stand about 4 hours of the heat-processed that temperature is about 149 ℃ (300), just can guarantee in the resin material it is anhydrous basically existence at least.
Evenly melting in the process of batch mixing of preparation solvent or whipping agent and polyetherimide, if as the situation of for example handling polystyrene and iso-pentane, that is to say it is to make its molten mixing by the barrel of sending into extrusion machine together, in order to extrude the polyetherimide foams, it just will be necessary keeping high treatment temp and setting up refrigerating unit so.In this case, treatment temp just must maintain in the scope of about 343-371 ℃ (650-700) and also must adopt independent high voltage system when introducing the whipping agent of above-mentioned definition.So, in this system, just also need before extruded polymer, to adopt independent cooling apparatus or the cooling zone is set, otherwise will destroy the system that has foamed and form foamy structure inferior.
Appearance for fear of this phenomenon, have been found that, polyetherimide can absorb the above-mentioned whipping agent dipping of indicating at an easy rate, can carry out melt-processed being lower than about 260 ℃ (500 °F) and being low to moderate under the temperature of about 218 °～232 ℃ (425 °-450) through the resin particle after such imbibition.For example, in order to flood Ultem
1000 pellets just only need allow this raw material stand up to about 48 hours treating processes under room temperature in spissated whipping agent steam ambient.So just can access free flowable resin particle, wherein contain enough whipping agents to form low-density foamy structure.At 100 parts of Ultem
Can contain up to about 30 parts whipping agent in 1000 resin granular materials, and not have the danger adhered to one another of any particle.Preferred treatment process is that 100 parts by weight resin particles flood with 3-20 part whipping agent.If the Ultem that adopts whipping agent to cross
1000 resin granular materials just can correspondingly adopt lower treatment temp and fairly simple treatment facility, because whipping agent has been dispersed among the whole resinous substrates effectively.
Embodiment 2 has shown the production process that adopts extrusion process production foamed polymer.
As mentioned above, adopt chloroform, 1,1.2-trichloroethane or its mixture and the foamy structure that can both obtain being equal to methylene dichloride.Should be noted that and before extruding, also can in initial feed or melt, add additive commonly used, for example nucleator.
Foamed resin of the present invention can adopt thermoforming process to make any satisfactory shape.In general; thermoforming process comprises that preheating foamy structure sheet material reaches mold temperature with the temperature that little by little makes this foam board; then should be foam-formed by among following two kinds of moulds any; these two kinds of mating dies that mould is exactly former or formpiston and former should impose auxiliary force and could incite somebody to action remollescent foam pulling shaping with this mould when adopting former.
As object lesson, can adopt the embodiment 2 described resins of this specification sheets to make density and be lower than about 320.4kg/cm
3The foam-formed plate of polyetherimide, revised with annular slit die, this mould can make thickness and be approximately the 0.23cm(90 mil again) thin plate.This cystose can be heated to about 246 °-525 °F) temperature, and it is sent into formpiston and former gradually, these two kinds of moulds make the semi-circular crust of multilayer with resin board, and the two-layer external diameter that can be used as wherein is approximately 254cm(1 English inch) the insulation layer of pipeline.Form after this structure with cystose,, this profiled sheeting is taken out just with mold cools down, and with the structure of such compression moulding and the edge slit of resin board.
The also plastic one-tenth setting of this foamed polymer structure, according to the present invention, a kind of method of preparation amorphous polymer foamy structure comprises:
(a) soak into polyetherimide with solvent or whipping agent, the polymerization admixture pellet of polycarbonate or Arnox and polystyrene, solvent or whipping agent are selected from following one group of compound: methylene dichloride, and chloroform, vinyl trichloride and composition thereof,
(b) the above-mentioned imbibition particle of heating is to being enough to make these grain expansions to be lower than the temperature of imbibition pellet density widely to density,
(c) fill mould with this pellet of expansible, these pellets are heated to is enough to make it to be melted into whole temperature, allows its cooling to form the bonding foamy structure of setting then.
When carrying out this process, preferably also be to use anhydrous polymer, to avoid through H
2O combines with solvent or whipping agent and forms the possibility of acidic component.Any this acid product all can corrode molding device and may make polymkeric substance or lost efficacy with its foamy structure of making.Allow Ultem
1000 grains stand the heat-processed 4 hours that temperature for example is 149 ℃ (300), just can guarantee in the resin it is anhydrous basically existence at least.Polymkeric substance for other also can adopt corresponding drying conditions.
In order to make low density setting foam article of the present invention, at first allow selected polyetherimide resin absorb the above-mentioned solvent composition of indicating.This solvent, the methylene dichloride of Cai Yonging for example, should infiltrate or be inhaled in the resin, perhaps in other words, be lower than about 37.8 ℃ (100 °F), preferably under the room temperature, can be taken away by resin particle, the degree of resin particle imbibition is, when being heated to the temperature of 37.8 ℃ (100), can make said grain expansion follow-up.The polyetherimide particle that imagination is used just has the ability that absorbs the above-mentioned solvent of indicating at an easy rate under quite gentle condition, here said quite gentle condition for example refers to this resin granular material is placed roughly room temperature, and pressure is to last up to 48 hours under the condition of standard pressure.In this process, particle surface is come out fully to improve the specific absorption of solvent.Under such mild conditions, allow the resin lyosorption just can make and still such mixture can be packaged and be transported to distant further processing of place do.Granularity requirements to resin particle is not strict, as long as the segmentation resin particle can absorb selected solvent at an easy rate.Obviously, too big as fruit granule, just can not absorb the solvent of q.s at an easy rate, unless adopt other severe condition again.Antithesis, too little as fruit granule, will increase the danger that particle lumps prematurely.The relatively more suitable granularity of resin particle is for being less than about 0.08cm(1/32-1/8 English inch) or larger sized diameter and length.
Any system of being convenient to handle that can allow resin particle be exposed under the selected solvent environment all can use.No matter when, preparation has absorbed the still free flowable resin granular material of group of solvents of q.s so that produce the premix expansion pellet that has satisfied density requirements to greatest extent in subsequent handling if desired, just only need are exposed to the surface of resin particle in the vaporous solvent system equably fully, just can control above-mentioned imbibition process well.With imbibition to greatest extent, but still free flowable resin granular material just can be produced the extremely low pre-expansion pellet of density after foaming, and for example, density is low to moderate 16kg/m
3The pellet of (every cubic feet 1 pound).On the other hand, the polymeric aggregate Bi Jing with the liquid absorption much less also can make the approaching roughly 320.4kg/m of density
3(20 pounds/English Foot
3) pre-expansion pellet.
When allowing the particle imbibition, also can be placed on the screen cloth of suitable mesh, solvent vapo(u)r is in roughly passing through this pellet layer under the room temperature, till the imbibition degree reaches requirement.On the other hand, can get pellet again sends at leisure and has one or resemble in the container of whipping appts so that the pellet particle surface is exposed among the vaporous solvent fully.Adopt this all processing method, 100 parts of resin granular materials are just used about 5-15 part at an easy rate, and preferably 10 parts selected solvent floods.The pellet of imbibition expands in advance in former state, and is final, such expansible pellet sent in the suitable mould and with it be molded as the quite low part of density.
The pellet of such imbibition sent in certain environmental system just it can be expanded in advance, in this system, pellet can be exposed in the heating systems equably, and along with the temperature of pellet and imbibition solvent raises, heating environment will make each granule foaming.Although only pellet foaming, preferable methods are still pellet is exposed to and allow its foaming among the heated mixt of rare gas element and the selected solvent of vaporous with heating condition.For example, available methylene dichloride and carbonic acid gas are with the mixed mixture of about 30: 70 to 70: 30 volume ratio.Preferably, allow the mixture of 50/50 volume ratio pass through the pellet of imbibition.The temperature range of said system is about 163 ℃ to 260 ℃ (325 °-500 °F).Along with pellet particulate volume increases, these particles will be entrained in the gaseous mixture and be delivered to bleeding point away from this heating systems through heating systems.Only need these particulate residence time of monitoring,, thereby make the pellet density scope after such expansion reach roughly 16kg/m with regard to its pre-expansible degree of may command
3To 320.4kg/m
3(every cubic feet per Foot 1 pound to about every cubic feet per Foot 20 pounds).Operating process is made the final densities that such control has also roughly indicated the foam pieces finished product.
After the particle of absorption liquid expand into satisfactory degree in advance, the pellet that just these can be expanded was then sent into the molded and shaped recycle system.This molded and shaped recycle system comprises with pellet fills mould, and pre-separately expanded granular is welded mutually, and cooling die makes the above-mentioned molded and shaped goods demoulding at last.Can adopt in the prior art any easy to operate molded and shaped system and adopt known processing method to put forward heat passage efficient and can adopt known means to impel molded part and mould to separate.For instance, the aluminium-making mould that can adopt the surface to scribble tetrafluoroethylene (Tef-lon) reaches high thermal conductivity and molded part is opened with mold separation at an easy rate.
The pre-expansible situation of pellet is the same with making, and the method that only adopts heating and keep malleation just can be made finished product with fused foam pellet in a suitable manner.But preferable methods is, adopts heating and evaporating solvent, and for example the method for methylene dichloride impels particle to be welding together mutually.In order to control better, preferable methods is that the gaseous mixture of adopting solvent and rare gas element such as carbonic acid gas impels particle to be welding together mutually.After particle is heated like this, and in system, all keep about 0.141 Anywhere to 2.11kg/cm
2Under the condition of (every square of English inch 2-30 pound) malleation,, subsequently it is released from mould the molded product cooling.In making particle fusion bonded process, temperature can remain on about 163 ℃ to 26 260 ℃ (325 °-500) further specifying of this method and see embodiment 3.
When adopting the mixture of chloroform or trichloroethane or itself and methylene dichloride or its mixture that does not mix methylene dichloride to implement method of the present invention, equal results that can obtain being equal to.The disclosed polymkeric substance with the ability that sucks solvent also can be made into the splendid molded component of foam reticulated structure as long as its liquid absorption is limited within the scope described herein.
Another kind of preparation density is lower than 320.4kg/m
3(20 pounds/English Foot
3) the method for molded and shaped thermoplastic foam structure comprise:
(a) flood the granular thermoplastic polymer with whipping agent, used polymkeric substance can suck solvent or whipping agent, and the consumption of whipping agent should be enough to make polymers impregnated to expand into density to be lower than 320.4kg/m
3Degree, thereby can to produce be free flowable basically granular mixture at least;
(b) with the partially filled mould of this free flowable granular mixture;
(c) in the process of follow-up polymerization adhere, do any substantial evaporation to the mould pressurization to stop whipping agent;
(d) this polymkeric substance being heated to is flowable basically molten state at least;
(e) remove the pressure be added on the mould so that flux foaming and allow the polymkeric substance that has foamed fill up entire die; And
(f) make the molded and shaped like this foamy structure demoulding.
Have found that, when initial material during for the granular thermoplastic polymer of the whipping agent that sucked the amount of meeting the requirements, just can be than the processable polymer scope of broad.When polymer beads being processed into the free flowable granular formation of surface drying, just can carry out processing treatment in the following order: (1) can inject the satisfactory mould of shape with this granular polymer that has sucked whipping agent, (2) substantially from polymkeric substance, evaporate for this mold system pressurization to stop whipping agent, (3) whipping agent has been evenly dispersed in the polymkeric substance basically, make this polymer melted, and the pressure on (4) releasing pressurizing mold, thereby form the splendid polymer foam structure of performance with mold shape.
Processing method whereby, just can control the density of foamed polymer, only need to inject in the control formation system mould and with a certain amount of granular resin compound density of foaming agent and put on pressure in the airtight forming mould system, just can get the structure of density.Moulding process is carried out such control, just can obtain a series of foamy structures of foams smaller from the structural foam to density, structural foam just has the foams of the gauge control upper layer that do not foam within the specific limits, and the smaller foams of density just do not have the not foams of the upper layer of foaming fully.
When preparation meets the typing foam article of requirement of the present invention, at first allow selected resin suck suitable whipping agent.At the employing polyetherimide, during the admixture of polycarbonate and Arnox-polystyrene, can adopt those can suck methylene dichloride, chloroform, the polymkeric substance of vinyl trichloride or its mixture.Selected solvent, methylene dichloride for example, should be infiltrated or be absorbed or otherwise be taken away by used polyetherimide pellet, said polymkeric substance is under the condition of gentleness, just be lower than about 38 ℃ (100 °F) in temperature, preferably under room temperature and the standard pressure, and suck solvent in about 48 hours time in being less than, the soakage of solvent should be able to be impelled polymer foaming subsequently.In this technical process, the polymer beads surface come out fully and can improve the specific absorption of solvent.Under such mild conditions, suck solvent just after the whipping agent, just can make still free flowable granular or granular composition.According to the present invention, such composition can be wired up and is transported to place far away further to process.The granularity of used thermoplastic resin there is not strict requirement, just available as long as the resin raw material of thin choosing can suck selected solvent easily.Obviously, if resin particle is too big, just can not make these particles fully suck solvent at an easy rate, unless adopt other operational condition again.If resin particle is too little, will increase the danger that these particles lump prematurely with solvent antithesis.
Any easy to operate system that resin particle is exposed in the selected solvent system all can adopt.All be exposed to all surface of resin particle in the vaporish solvent system equably, the residence time of resin particle in solvent must be satisfied such condition, promptly can the free flowing granule aggregate with short can the generation still of the foaming dosage that sucks with the resin granular material that produces the satisfactory foams of density to greatest extent, by such working method, can carry out better controlled to the imbibition process of resin.With imbibition group to greatest extent still can free-pouring resin granular material just can to make density extremely low, for example be low to moderate less than 16kg/m
3The foamed polymer of (1 pound of every cubic feet per Foot).On the other hand, just can make density near 320.4kg/m with the quite few resin granular material of having taken in of quantity of solvent
3(20 pounds/English Foot
3) or bigger foams.
When allowing the resin granular material lyosorption, these pellets can be placed above the screen cloth of appropriate size and allow solvent or whipping agent steam be roughly the pellet layer that penetrates such formation under the condition of room temperature, till reaching satisfactory solvent suction degree.Equally, also can lentamente resin granular material be sent in the solvent or whipping agent that in the container that one or more whipping appts is housed so that resin particle surface is exposed to steam condition fully.Adopt such processing method, just can be at an easy rate with about 5-15 part, the resin granular material of 10 parts of selected solvent impregnated 100 parts (weight) preferably.The resin particle that has sucked solvent just can inject the satisfactory mould of shape with such form.
When sending into these resin granular materials that sucked solvent in the selected mould, allow these resin granular materials only occupy a part of volume of mould.The size of the mold volumes that resin granular material is occupied depends on the performance of the desired foamy structure that obtains.If fill mould to greatest extent with the granular resin that sucks solvent, this volume of quite a few mould that will account for obviously, and when these resin fusions, just can not significantly expand, will be quite big and operate the density of the foamy structure that obtains like this.On the other hand, if the volumetric ratio that accounts for when filling mould with resin is less, the density of the so final foamy structure that forms is just smaller comparatively speaking.
Will be understood that when heating forming mould of the present invention system, some has infiltrated the whipping agent that goes in the resin granular material and can be evaporated, and can help like this molded and shaped system pressurization.For the whipping agent that guarantees q.s is dissolved in or is scattered among the resin melt, thereby make the satisfactory foamy structure of density, just must consider that whipping agent is evaporated to the amount among this compression space above melt in the heat-processed of resin granular material and before pressure relief from resin melt.As long as the whipping agent of steam condition is added compression space and makes its a part of dividing potential drop that occupies this system, just can effectively control to the density of foamy structure.Those of ordinary skill in the present technique field can calculate at an easy rate and enter any spatial quantity that may exist in any selected mould after the whipping agent that infiltrates in the resin granular material is evaporated from this heating pellet, can adopt its equivalent or its any component in pressure process.If the composition series in the selected compression system is from being entirely the mixture of rare gas element to the suitable proportion of rare gas element and whipping agent steam, so just can making a series of foam structures of density from big variable density to little density.
For example, use 15 parts (weight) of resin granular material Ul-tem for the whipping agent of absorption
1000 is raw material, is 6.35cm(25 English inch with diameter), length is 2.54cm(1 English inch) garden cylindrical mould moulding, wherein contain about 30 grams and used solvent impregnated resin, and be 21kg/cm with pressure
2(300 pounds/English inch
2) CO
2Pressurization so just can make the quite high foams of density, and its density can reach about 320.4kg/m
3(20 pounds/English Foot
3).As use identical resin-whipping agent mixture, only weight consumption is 25 grams, but used garden cylindrical mould diameter is a 6.35(2.5 English inch), length is 38.7cm(6 English inch), and be 40: 60 methylene dichloride steam and CO with weight ratio
2Mixture under the temperature of 204 ℃ (400), be pressurized to 42kg/cm
2(600 pounds/English inch
2), by such method, just can make density is about 48.06kg/m
3(3 pounds/English Foot
3) garden cylindrical foam structure forming body.This processing method has been described in detail in embodiment 4.
The present invention will be further described with following embodiment.
Embodiment 1
Present embodiment explanation preparation is used for the method for polyetherimide of the present invention.
Contain 2.855 part 1 in the raw mix, two (the 4-phenoxy group phthaloyl imino-) benzene of 3-, 1.180 parts of dihydroxyphenyl propanes, 0.081 part of 0-phenyl phenol (O-phenyl-phenol) sodium salt and 20 parts of N-Methyl pyrrolidone are filling reflux under the nitrogen condition with this mixture.Heat-processed continues 1 hour, during this period of time, distills out total amount and is approximately 10 parts liquid.With pouring in about 300 parts methyl alcohol after this reaction mixture cooling, methyl alcohol is stirred in a mixing tank while add mixture, the polymer precipitation with regard to adularescent comes out subsequently.The polymer filtration that obtains is like this come out and wash, under vacuum condition, carry out drying then.This polymkeric substance is the polyetherimide with above-mentioned defined structure, and wherein the predecessor of Ar is a dihydroxyphenyl propane, and R is a penylene.
Embodiment 2
Present embodiment has illustrated and has adopted pressing method to form the process of foamed polymer.
With anhydrous Ultem
1000 particles are in being exposed under the room temperature condition in the methylene dichloride environment, the time length be about 48 hours to make the still free flowable pellet of methylene dichloride group that contains have an appointment 15 parts (weight) in per 100 parts of resin granular materials.The pellet that obtains is like this sent into the opening for feed of single multiple screw extruder, and length one diameter of this extruding machine is 24: 1 than (L/D), and its extrusion screw diameter is a 3.2cm(1.25 English inch).Again this pellet that has been full of solvent is added hot melt equably under the temperature of 232.2 ℃ (450) and mix, then it is delivered directly to the forming area of this extrusion molding system.Allow so even resin melt extrude from capillary type mouth mould, the diameter of tubule is a 0.203cm(0.08 English inch in this mouthful mould), and its length one diameter is 16.1 than (L/D).The product density of extruding like this is about 40kg/cm
3(2.5 pounds/English Foot
3), wherein have meticulous closed chamber structure.Have found that within the short period of time (being approximately 2 hours) after extruding, methylene dichloride is actually all and has overflowed from the meticulous air chamber of this foamy, thereby made extremely excellent froth product.Such foamed resin has kept used anti-combustion that original copolymer had with the low smokiness energy.
Embodiment 3
This embodiment has illustrated the pre-expansion of the polymer beads that has sucked solvent among the present invention and molded and shaped process subsequently thereof.
Selected polyetherimide resin particulate granularity is about 0.16 to 0.32cm(1/16-1/8 English inch) (diameter and length), (this resin is that General Electric Corporation is with registered trademark A Ertemu (Ultem
) 1000 products of selling, can be from General Electric Corporation, a plastics approach of plastics business department, now a MA(General Electric Company, Plastics Operation, 1 Plas-tics Avenue, Pittsfield, MA) obtain), soak into these resins with methylene dichloride with the ratio of 10 parts of methylene dichloride of per 100 parts of resins then.Referring now to accompanying drawing 1, this process is finished so as can be seen, promptly is being roughly under the condition of room temperature, will be 5.08cm(2 English inch originally) resin particle layer 10 place on the support screen 12 and allow resin particle be exposed to 14 li of methylene dichloride steam.After 24 hours, the solvent that resin particle sucks has promptly reached above indicated degree.At this moment keep still can free-pouring state for particle, and can be transported to the higher apsis in this operating point packing back shipment and go to finish its course of processing.
Referring now to accompanying drawing 2, only need can make these particles expand in advance among the above-mentioned pellet that has sucked solvent is sent into vertical vessel 16, are mounted with the Z-axis 18 of CD-ROM drive motor in the container 16, and horizontal agitator arm 20 is housed on this axle.When stirring these particles that suck solvent, allow volumetric mixture ratio be 50/50 carbonic acid gas mixture mixture 22 upwards by and under the temperature of about 204 ℃ (400), make mixed gas walk around each particle, the flow velocity of this mixed gas should be enough to carry secretly away expansible particle.This can cause the increase of single resin particle volume and it is finally carried away by the mixed gas at upper reaches.So pre-expansible pellet 24 is discharged from container, after the discharge it is collected usefulness in order to follow-up molded and shaped process.As long as select suitable operational condition, just can make density is about 160.2kg/m
3(10 pounds/English Foot
3) pre-swollen resin pellet.Referring now to accompanying drawing 3, then above-mentioned pre-expanded granular is sent in the mould 26, this mould is of a size of 30.5 * 30.5 * 1.3cm(12 * 12 * 0.5 English inch).Allow the volume ratio be that 50/50 the carbonic acid gas and the mixture 28 of methylene dichloride are 232 ℃ (450 °F) in temperature, gauge pressure is 0.14kg/cm
2(2 pounds/English inch
2(gauge pressure)) condition under by above-mentioned expansion pellet.After the cooling, allow the finished product demoulding, this finished product density is about 80.1kg/m
3(5 pounds of every cubic feet per Foot), (beam strength) is splendid for its tensile strength.
This finished product have unmodified resin and have good flame retardant resistance and low-smoke performance.
Embodiment 4
Present embodiment has illustrated the another kind of working method of the row that belong to the scope of the invention, wherein, will take in the polymer beads of solvent earlier and send into mould, pressurize then, heat, subsequently with regard to pressure relief so that its foaming.
The granularity of selected polyetherimide resin pellet, just its diameter and length range are about 0.16 to 0.32cm(1/16-1/8 English inch), this resin is that General Electric Corporation is with registered trademark A Ertemu (Ultem
) 1000 products of selling, can be from General Electric Corporation, an approach of plastics business department, now a MA(General Electric Company, Plastics operation, 1Plas-tics Avenue, Pittsfield, MA) obtain, use methylene dichloride to soak into this resin then with 15 parts of methylene dichloride ratios of per 100 parts of (weight) resins.Referring now to accompanying drawing 4, this process is finished so as can be seen, is about to thick in 5.08cm(2 English inch) the resin particle bed of material 30 place on the support screen 32, and allow resin particle be exposed among the methylene dichloride steam 34 that temperature is roughly room temperature.After 48 hours, the solvent that resin particle sucks has promptly reached above indicated degree, and at this moment particle keeps still free flowable state.Referring now to accompanying drawing 5.Mould 36 is the garden tubular, and its internal diameter is a 6.35cm(2.5 English inch), the resin granular material 38 that has sucked solvent with 30 grams is filled this mould.Mould is closed, and adopts the heated mixt of methylene dichloride and carbonic acid gas, mould inner pressure is brought up to 42kg/cm by pressurizing device 40
2(600 pounds/English inch
2), the ratio of mixture of methylene dichloride and carbonic acid gas is 40 to 60 weight % in the mixture.By heating unit 42 mould will be heated to the temperature of 204 ℃ (400) then.Finish when becoming molten state at resin granular material, adopt pressure relief device 44 promptly to remove above-mentioned inflation pressure again, so that the foaming of the pellet in the mould.Then with mold cools down, allow the foam article demoulding.The final foamy structure that forms has the shape and size of this mould, and all is distributed with uniform basically meticulous sealed gas chamber structure in whole goods, and this extrudate density is about 64.08kg/m
3(4 pounds/English Foot
3).This foamy structure has all good anti-combustion and low-smoke performances that unmodified resin has.
Claims (33)
1, density is lower than 320.4kg/m
2The spumescence polymkeric substance, this polymkeric substance be for can sucking the polyetherimide of solvent, the admixture of polycarbonate or Arnox and polystyrene, and said solvent is a methylene dichloride, chloroform, vinyl trichloride or its mixture.
2, according to claim 1 described spumescence polymkeric substance, wherein, the structural formula of said polyetherimide is as follows:
In the formula, n is a positive integer, and Ar is the divalent group that contains 6 to 20 carbon atoms, R be selected from aliphatic series, cyclic aliphatic, aromatics with the divalent group of virtue for aliphatic group.
3, according to claim 2 described spumescence polymkeric substance, wherein, the predecessor of Ar is a dihydroxyphenyl propane, and R is a penylene.
4, the composition that comprises the loose polymer beads that sucks solvent, wherein, the soakage of solvent should be enough to make this polymer foaming to be lower than 320.4kg/m to density
3Degree, said polymkeric substance is a polyetherimide, the polymeric blend of polycarbonate or polyphenylene oxide and polystyrene, and said solvent is a methylene dichloride, chloroform, vinyl trichloride or its mixture.
5,, wherein, contain solvent in per 100 parts of polymkeric substance up to 30 parts according to claim 4 described compositions.
6, the method for preparing the low density foam polymkeric substance, comprising:
(a) soak into granular polymer with solvent;
(b) pressurization melts these particles and solvent to mix equably; And
(c) melt that such blending is got up is clamp-oned low pressure environment so that solvent evaporation is come out, thereby formation foamy structure, said polymkeric substance is a polyetherimide, the admixture of polycarbonate or Arnox and polystyrene, and said solvent is a methylene dichloride, chloroform, 1,1,2-trichloroethane or its mixture.
7, according to claim 6 described methods, wherein, polymkeric substance is the polyetherimide with following structural formula:
In the formula, n is a positive integer, and Ar is the divalent group that comprises 6 to 20 carbon atoms, R be selected from aliphatic series, cyclic aliphatic, aromatics with the divalent group of virtue for aliphatic group.
8, according to claim 7 described methods, wherein, the quantity of solvent that polymkeric substance sucks should be enough to make this polymer foaming to be lower than 320.4kg/m to density
3Degree.
9, the thermoforming structure that makes with foamed polymer, its preparation method comprises:
(a) density is lower than 320.4kg/m
3The foamy structure plate be heated to first temperature, this temperature is enough to form the modular construction that will play a role at cystose;
(b) under this first temperature, in cystose, form modular construction;
(c) this foamy structure plate is cooled to second temperature, so that can or being lower than under the condition of second temperature in second temperature, the modular construction in the plate permanently remains, said foamed polymer is foamed polyetherimide, foamed polycarbonate or Arnox and polystyrene foam shape admixture.
10, according to claim 9 described thermoforming structures, wherein, said polymkeric substance is a polyetherimide, and its structure is as follows:
In the formula, n is a positive integer, and Ar is the divalent group that comprises 6 to 20 carbon atoms, R be selected from aliphatic series, cyclic aliphatic, aromatics with the divalent group of virtue for aliphatic group.
11, the forming method of styling polymer foamy structure, comprising:
(a) soak into polymkeric substance with solvent, said polymkeric substance is a polyetherimide, the polymeric blend of polycarbonate or Arnox and polystyrene, and said solvent is selected from methylene dichloride, chloroform, vinyl trichloride or its mixture.
(b) polymeric aggregate that will suck solvent is heated to such temperature, promptly is enough to make pellet to expand into the temperature that density is lower than the density of the pellet that sucks solvent widely; And
(c) with above-mentioned expansion pellet filling mould and to this pellet heating, its degree of heat should be enough to make these particles to be welding together mutually, and forms the adhesive foam structure of typing when cooling.
12, according to claim 11 described forming methods, wherein, said polymkeric substance is the polyetherimide with following chemical structural formula:
In the formula, n is a positive integer, and Ar is the divalent group that comprises 6 to 20 carbon atoms, and R is the divalent group that is selected from the following radicals group: aliphatic series, cyclic aliphatic, aromatics with virtue for aliphatic group.
13, according to claim 12 described forming methods, wherein, polymeric aggregate stands 0.141 to 2.1kg/cm in its molded and shaped process
2Pressure.
14, according to claim 13 described forming methods, wherein, the polymeric aggregate that sucks solvent in the operation steps (a) is basically can free-pouring and not expansion significantly at least.
15, according to claim 14 described forming methods, wherein, the soakage of solvent is the solvent that has in per 100 parts of (weight) polymkeric substance up to 30 parts.
16, according to claim 15 described forming methods, wherein, the amount of solvent composition is in per 100 parts of (weight) resins 0.5 to 20 part of solvent to be arranged.
17, according to claim 14 described forming methods, wherein, the particle that has sucked solvent expands in heated air stream, and to allow air-flow that particle entrainment is walked, the expansible particle collects subsequently.
18, according to claim 17 described forming methods, wherein, the temperature range of heated air can just can cause that particle carries out in a way obvious expansible temperature to the maximum processing temperature that particle is lumpd up to being unlikely of can reaching.
19, according to claim 18 described forming methods, wherein, temperature range is about 163 ℃ to 260 ℃.
20, according to claim 17 described forming methods, wherein, heated air is the mixture of solvent composition and rare gas element.
21,, wherein, reach the desired temperature of step (c) by the method that hot gas is contacted with polymer beads according to claim 11 described forming methods.
22,, wherein, contain gasiform solvent composition in the hot gas according to claim 21 described forming methods.
23, according to claim 22 described forming methods, wherein, contain rare gas element in the said heated air.
24, the styling polymer foamy structure that makes with any one the described forming method in the claim 11 to 23.
25, the preparation method of molded and shaped thermoplastic foam structure, comprising:
(a) use solvent impregnated granular thermoplastic polymer, this polymkeric substance can lyosorption, and said solvent load should be enough to make this swelling polymer to be lower than about 320.4kg/m to density
3Degree, be free flowable basically granular mixture at least thereby make;
(b) partly fill mould with above-mentioned free flowable granular mixture;
(c) among follow-up melting process, be evaporated to stop solvent to the mould pressurization a great deal of;
(d) heated polymerizable thing makes it become molten state at least;
(e) remove pressure on the pressurizing mold, allow molten mass foaming and the polymkeric substance that has foamed is expanded in mould; And
(f) make the molded and shaped like this foamy structure demoulding.
26, according to claim 25 described preparation methods, wherein, said polymkeric substance is selected from the polyetherimide that can suck solvent, the polymerization admixture of polycarbonate and Arnox and polystyrene.
27, according to claim 26 described preparation methods, wherein, said solvent is selected from methylene dichloride, chloroform, vinyl trichloride and composition thereof.
28, according to claim 27 described preparation methods, wherein, said polyetherimide is the polymkeric substance with following chemical structural formula:
In the formula, n is a positive integer, and Ar is the divalent group that contains 6 to 20 carbon atoms, R be selected from aliphatic series, cyclic aliphatic, aromatics with the divalent group of virtue for aliphatic group.
29, according to claim 28 described preparation methods, wherein, the amount of solvent in polymeric aggregate is the solvent that has in the polymkeric substance of per 100 parts (weight) up to 30 parts.
30, according to claim 25 described preparation methods, wherein, the amount of solvent in polymeric aggregate is in the polymkeric substance of per 100 parts (weight) 0.5 to 20 part solvent to be arranged.
31, according to claim 25 described preparation methods, wherein, mould is with comprising that the gaseous state system of rare gas element is forced into 21 to 105kg/m
2
32, according to claim 31 described preparation methods, wherein, the gaseous state system comprises the mixture of rare gas element and the independent vaporous solvent with certain dividing potential drop that adds.
33, the molded and shaped polymer foam structure that makes with any one the described preparation method in the claim 25 to 32.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85106316 CN85106316A (en) | 1983-12-12 | 1985-07-28 | Foamed polymer, the method for its thermoformed shapes and moulding thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/560,641 US4535100A (en) | 1983-12-12 | 1983-12-12 | Polymer foam, thermoformed shapes thereof and methods of forming same |
| CN 85106316 CN85106316A (en) | 1983-12-12 | 1985-07-28 | Foamed polymer, the method for its thermoformed shapes and moulding thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85106316A true CN85106316A (en) | 1987-02-04 |
Family
ID=25741977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85106316 Pending CN85106316A (en) | 1983-12-12 | 1985-07-28 | Foamed polymer, the method for its thermoformed shapes and moulding thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85106316A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104540756A (en) * | 2012-06-06 | 2015-04-22 | 巴斯夫欧洲公司 | Method for transporting expanded thermoplastic polymer particles |
-
1985
- 1985-07-28 CN CN 85106316 patent/CN85106316A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104540756A (en) * | 2012-06-06 | 2015-04-22 | 巴斯夫欧洲公司 | Method for transporting expanded thermoplastic polymer particles |
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