DE1494231A1 - Process for the production of molded plastic foams - Google Patents

Description

The invention relates to peat corrugations for the production of shaped, grooved “Fleet” , a special method for producing shaped, grooved “plastic” from finely divided, polymeric material

The state of the art knows a number of requirements Manufacture of suitable materials and polymeric materials For the fulfillment of the desired, connected Polynesians Russians dasei allgeweia expensive devices and strange ones Areelteveleen and procedural stages are applied

In the ÜSA-Futenteohrift 2 981 631 there is a process "to use a base old its" polymeric material under the assumption of a Wlreelecblohtteohnlk eeeohrleees laea "Use" TsrfsJsro · the su UeersleneMe base

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to a temperature above the melting point dee in the Wirbelsustand placed under polymer vorurhitzt and then entered into a fluidized bed deo Polymerioatee and blowing agent and dCRT _s held until dia of the fluidized bed of ^ eeetasten cursing the substrate in the desired thickness with the polymer bsw Deiss anechlieseend resulting foam Uber Absorbed Bind be "Se übarzugsdicken in the range of Ο? 25 to 1.9 mm reached wherein to achieve the etHrkeren coatings a multiple immersion in the V / irbeluchicht necessary is Gtenäea the patent, the Gröese the rorliegenden in the fluidized state polymer in the range 20-700 ρ lie ». :

Without being named su in the patent specification, iot die Use of a fluidized bed old specific? fixed framing and laughing parts connected, various of these Bsgrensungen and! Facht sils are in a younger perspective the teohnik of looking over with plastics using yon Edbelschlohten by P. V. Sherwood in "Plastics", Vol »25, Ir .. 278, Desembsr 1960, 3, 495 »« ufgensigt »to transferable * · ity Ib the economic situation should ·. B. Sin powder from TeHem exist, dsrsn gruses «such as about 95 and 500 μ and The dls are almost spherical in shape, also shown Moisture content and the electrostatic charge of the polymer these are for the Kritisoh, You have to be more critical of Orund this and others Factors for each author and each article to be treated:

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the above conditions added separately in the individual to which such conditions, the Ilaterialwahl ,, the steering Tenperatur _s analyzing the thermal properties of the material to be treated, the duration of stay in the coating layer ~>. the method of controlling preheating and post-treatment; and the method of handling the body to be treated itself

An older literature reference (US Pat. No. 2,844,409) mentions various other limitations of the fluidized bed process to be able to carry a Schneizen incident Polyraerteilchen piping difficulty can be by an additional treatment with the flame of a gas burner or in an oven in some cases Overcome but such treatment 1st in the filling, in which the polymer would be degraded in the heat special treatment zua part _r not applicability the reference also betönt the compulsion "with granular particles rather narrow particle size distribution (preferably about 50 to 300 Ji) to work and points out that, in each fluidized bed, the smaller particles are easily entrained by the <7irbelgaastron and thereby be Lost go

Ss is from serve Erwfigtingen out offeneichtlich _f that the method according to US Patent sealed "ift 2 98t 631 to the

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The application of extremely thin foamed coatings on those parts of relatively thick-walled substrates is drilled. ₈ the vortex can be used to create a smooth flow Polymer oversugosehioht would be subject to even more restrictions, if a similar method of operation is not possible, the inner flanks of a container with a relatively narrow opening on coatings or formed structures from solid material with a thickness τοη more than about 75 ρ also difficult if not impossible »(I get foamed overlay with a fluidized bed on the basis of a dry mixture of relatively coarse film that can be transferred to the swirling state and finely powdered bleaching agent bu n ,, because the bloat, the Ua peculiar melgung sioh from the Wlrbelsohioht away but and also "cook off"

The present invention provides shaped, hemmed pia- » made of solid, finely divided polymer materials are available, She has a history of making molded, molded parts Plastics available in which the special equipment or work stages of the known processes are not required * you will get molded, foamed polyolefin products,

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when using solid blowing agents, their properties are superior to the foamed products obtained according to the prior art Bind · It represents a direct and flexible process for the production of shaped »foamed polymer structures of various Sizes and shapes available o The invention continues eonly a new process for the shaping and formation of Made with foamed polymer materials available. "

These and other objects of the invention realizes _P by heating a finely divided polymer "that is mixed with a minor amount of a solid, feinteiIigen blowing agent or a blowing agent has been incorporated, enters in described below _β conventional molds ₉ to a sufficient for the foaming temperature, and the emerging? formed foam cools to a temperature at which it solidifies,

In general, any polymeric material is suitable for the purposes of the invention "its decomposition point etwus higher than its melting point and are thermoplastic in powder state can preserver = th ι These include polymers such as polyolefins _9» z. B »Polyethylene? Polypropylene Polybutene-1 and copolymers or devices of the same "Acrylic resins" ζ »Β Polymethyl methacrylate" Acrylic resins with high impact strength, "Cellulose-like substances" z. " B ₀ cellulose butyrate, cellulose acetate ₉ methyl cellulose and xthyloellulose »polystyrene and polystyrene with high sole tensile strength» vinyl resins _p ζ, Β polyvinyl chloride ,,

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Polyvinyl acetate and polyvinyl alcohol "Polyether _P a. B Polyethylene oxide s chlorinated polyethers, polyesters, ζ, B poly (ethylene adipate terephthalate polyamides, a B Polyethylene adiparide (nylon 6/6) and polyhexamethylene sebacumide (nylon 6/10), fluorocarbon resins and various copolymers or resins of the same thermosetting resins - The phenolic resins, epoxy resins "melamines _v polyurethanes, urea resins and the like" are also suitable

In the practice of the invention, suitable foams are generally only obtained when all or substantially all of the particles of the polymer mixture are no larger than about 2000 microns and have an average particle size of less than about 1000 microns in diameter. Larger particles tend to form of foams, which have an undesirably coarse and insignificant structure, and to an unnecessary expansion of the foaming capacity? In the above, the desired range satisfactory foams can be obtained regardless of the Teilchengrösee, particle shape and Teilchengrößeeenverteilung However, when foams _s are gewUnsoht with a particularly fine cell size one works preferably with a mixture whose average Teilchengrösee below 500 u _t, in particular less than 50 u is

A subdivision of the polymeric material with achievement The powdery state mentioned above can be used with a A number of methods familiar to the technique can be achieved.

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In such a process, a use of the polymer is used brewed with a suitable dissolver so that Polymeric acid precipitates in fine form. laugh at another technique the material is ground meohanieoh on a specially built device. Other working techniques are in one described in the literature *

Any substance can be used as a blowing agent "which can be distributed smoothly throughout the polymer mass without considerable decomposition and which, when heated to an elevated temperature, preferably to a temperature close to the value at which the polymer or resin reaches the plastic state", releases a gas able. Suitable agents include solid organic compounds, such as benzenesulfonylhydraside _β 4,4 * -oxy-bis- (benzenesulfonylhydraside) ₉ aodicarbonamide, 4,4 * -oxy-bis (benzenesulfonyl-seraicarbar-id),

N _P N ^S -einitroeo-

pentamethylenetetramine, 4,4 * -diphenyldiaulfonylazid _P 4-tert »- butylbenzolaeide, diasoaminobenssol« asohexahydrobenzonitrile and 2 ₉ 2 "" azoieobutyronitrile _v and solid, inorganic compounds ₉ such as ammonium oxalate, aomonium sulfamate ". Ammonium thiosulfate ₉ ammonium bicarbonate »sodium bicarbonate / sodium nitrate or combinations of inorganic compounds which react to form volatile substances when heated, s * Bu sodium nitride plus hydrated sodium acetate p sodium bicarbonate plufl sodium hydrogen tartrate and the like.

For a given polymer, the choice of blowing agent depends

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on the melting temperature of the polymer «the decomposition» range of blowing agent, the heating strength to be used during foaming, the desired properties of the foam, etc. In general, a blowing agent should be chosen whose decomposition temperature is above the melting temperature of the polymer but can also use blowing agents with lower decomposition temperatures in the event of rapid heating «The last determination preferred for a given polymer By means of simple experiments, the skilled worker is able to do this

The blowing agent is used in the amount that gives the desired degree of pouring. The amount required is generally between about 0.1 and 10 $> by total weight of the polymer .. At levels above about 10 1 "heating occurs to form a structure with large and ungleichmttsalgen pores and unnecessary pollution SohHume nit BlIUimittelrUckständen on · Quantities below. 0.1 £ found no effective foam formation, in general .. The i in the range of 0.1 to 10> amount to be used depends on the required properties of the final foams, Gröesere amounts in the range dieuem supply during foaming in an open mold lower SchHume specific gravity and in a closed form with more and smaller pore quantities at the lower end ('the critical area leads to foams with a higher specific gravity

Sa is the proportion of blowing agent in relation to the polymer

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is small, let a homogeneous distribution of the blowing agent in the Polymer for the quality of the resulting foam, in particular with regard to the pore size and uniformity of the pores distribution »critical. The polymer and blowing agent can be mixed using various techniques

According to one method, the finely divided polymer in solid, dry form is intimately smelled with a finely divided blowing agent. The blowing agent should accordingly have an average component ratio equal to the fineness of the polymer, so that ideally each polymer particle during foaming can be in intimate contact with one or more particles of the flower. The blowing agents suitable for practicing the invention are generally available in Trade in average grain sizes below about 40 u available and can therefore be used without size modification :. Satisfactory Miuchgrade of dry ingredients can be easily with simple, well-known mechanical means such as _p * obtained by circulating air movement ₉ and the like Trockenversprühen achieve * Bas mixture provides a homogeneous "is freiflleesendes powder.

In another method of mixing polymer and blowing agent, the blowing agent is first one of the usual ones Sohmla incorporation or plaeting techniques similar in the whole in the plastic state Dispersed polymer. Such techniques involve the use of devices such as heated

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Roller grinders; Banbury type mixers _; Mixing of the kneader type9 extrusion and the like. Geniuch obtained before Daa represents a uniform dispersion of the blowing agent in the polymer and is then pulverized according to one of the known techniques In other cases, the mixture can be mechanically ground directly to the required particle size.,

In another method of incorporating the blowing agent into the particulate polymer material, the polymer and the blooming agent dissolved in a common solvent. In this case it is important; the thermoplastic polymer to dissolve »while the blowing agent can also be easily dispersed in finely divided form. Subsequently to the full Dispersion or dissolution of the blowing agent in the polymer solution the solute is obtained by a variety of techniques such as (1) adding a nonsolvent to cause precipitation, (2) lowering the temperature of the solution, or (3) Removal of the solvent or a solvent component precipitated by distilling off. You can with one flolohen method the blowing agent in this v / eise evenly incorporate the polymer and the polymer by precipitation in a particularly finely divided and worthwhile form win>

During mixing of polymer and blowing agent through

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Dry mixing of the components in powdered Porra leads to adjacent and spaced-apart "dense particles" of the constituents, should mixing by plasticizing or dissolving lead to a mixture? in which each individual polymer particle includes part of the blowing agent. The Troekenmiseh technique is advantageous from the point of view of simplicity and equipment requirements. It also allows greater flexibility in the choice of the type and concentration of the blowing agent. On the other hand, plasticizing and dissolving leads to a mass _? that of a tendency of the particles of the blowing agent and polynerifiates _; eich & u tremie: · '., vn.e is free during shipping or other violent handling _{9 .} when to use one? shock-sensitive bloom is desired; one can mix the etc.-sensitive blowing agent and the polymer under carefully controlled conditions and the obtained? Must be sent safely to the processor that is insensitive to oil. Furthermore, the cell structure of foams _9, which are due to the mixture by plasticizing or dissolving, is relatively independent of the particle size of the foamable mass,

In order to obtain stable, molded foams from the above-mentioned powdered compositions, the compositions must first be grounded a temperature is heated at which a combination of the melting of the polymer and the decomposition of the blowing agent

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an extensive cellular «? The structure results Sehaumentwicklung is guided to the end of the foam or "hardened""is sufficiently long at a temperature above the Zersetzungetemperatur of the blowing agent to the decomposition of the _r holds Blfihmlttels substantially to lead to end ,, the temperature, however, by the initially developed SchauiR neither the decomposition temperature of the polymer nor that of the material forming the mold may exceed c The decomposition temperature of the mold material is of considerable importance; if the mold is made of a material or is coated on the inside with a material * whose melting point is only slightly above that of the foamed polymer? ζ B> in the formation of an enclosed in plastic foam A only moderately higher than the melting temperature of foamable polymer Sohäumunßs "and curing temperature is generally satisfied, a foaming and curing temperature from 35 to 150 higher than the melting temperature of the polymer echäumbaren is preferred. The total heating time necessary in the process of the invention to form a fully developed "molded foam" is unusually short; it is in the order of magnitude of 20 minutes or less and is often of a very short duration, such as about 6 minutes. Or less. The heat can be supplied in different _{ways P} such as by means of hot plates, conduction ovens, ultrared radiation, dielectric heating elements and the like,

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After reaching the desired degree of development the foam for stabilization is cooled to a temperature below the value at which there is no tendency for the foam » Cell walls for filling up occurs in general the foam is stabilized by bringing it to a temperature that is reasonably below the melting temperature of the polymer cools down, The cool down can be atosswelse or gradual take place

Before the abovementioned foaming is carried out, the compositions of the invention composed of polymer and blowing agent can be prepared by adding pigments; Dyes ^ \ ill materials ₉ Stabilizers »Modify plasticizers and the like.

The bemerkenswertesten advantages of the method of the invention lie in the gemäee ^ Rossen simplify the production of shaped structures made of polymer foams, and the versatility or _u adaptability of labor. You can, for example, B; use simple powder molding techniques, whereby the main appuratlve need is a thin metal mold (only the concave half of the mold is needed when working in the open mold) and a heat source. formed structure a form (Zo B, a metal sole) only filled with a mixture of f one-piece polymer and blowing agent to cover _{r to} cover ₉ to burn in an oven "until a foam is developed" and to cool to form a hollow body

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to fill a mold of the desired shape with the finely divided mixture, cover ₉ heat * to adjacent the mold inner surface of a molten layer is formed _k daa excess powder aua the shape distribute and form a foamed sleeve develop the molten polymer layer by further heating or "cure "ν Horizontal surfaces can be covered with foam" by simply applying an even layer of the powder mixture to the surface and burning it _;

The sluggish powder compositions according to the invention are shown in FIG in the same way accessible to the rotary casting or rotary molding techniques which are used to a large extent in vinyl plnstisoles Find, Here is a thin-walled, divisible hollow shape filled with a predetermined amount of the foamable genes and then closed. You move the closed one Form in two or more levels in circulation and heated at the same time »to the polymer to form a layer melt which is evenly distributed over the inner walls of the mold is One can during the circulation by further heating complete the foam development or transfer the mold to a separate oven and the foam with static Develop state of form. After the foam has developed, the mold is cooled and the molding is removed Technology is a large variety of shaped structures made of foamed Plast available

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Harzest der Formungsteohnik; Depending on the type and quantity of the blowing agent and the heating cycle, foam with a lot of crying, discrete cells (foams with closed cells or foams) or with relatively large, interconnected cells (foams with open cells or plastic sponges) produce piping whale ?! can generally be made on the basis of simple tests, but it seems> that a combination of a large quantity of a rapidly aeraeSzendsn blowing agent with a resin _s, which has a comparatively small Viseooität in the decomposition range of the blowing agent, a tendency to form foam with open cells results _P while when using relatively small amounts of a slowly decomposing blowing agent in combination with a Hers »which results in a relatively higher viscosity in the decomposition area of the blowing agent. there is a tendency for closed cell foams to form,

The process according to the invention allows the production of shaped; foamed plastic products made of solid material, as well as in the form of a hollow body for a variety of applications, the wall thickness of such articles may be from about 1 _t 9 ram up to high values, such as 12 ₉ 3/4 cm? range, although a range of about 6 to 76 mm is also preferred. The foams combine properties such as low specific (jewel, high strength, elasticity * solvent and chemical resistance and low thermal and electrical conductivity). They are accordingly well suited

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for insulation purposes, ζ. B> Cooling room liningsK; "Seals for coolers uew ,, Polatermateriaxien _P ζ Β Mattresses, accident protection _{upholstery for motor vehicles P} Seat and furniture upholstery, carpet underlay material _s furniture _{parts t} , non-shock-absorbing fastenings, body protection pads, etc. * _P toys" z. B, dolls _P balls and the like ρ Sohwinm-compatible material for shipping and other articles ^ such as bowls (cups),. Korbflaschec, Troro ^ a and the like.

For most of the purposes of the plastic fiune, the foam is made of plastic for protection or decoration. Fabric or sheet metal including the above-mentioned Porraungstechniken in conjunction with the schHumbaren PulTermaesen according to the invention "ground there often appear zweckmrtssig blank _P the foam in a Plaatechicht einzuachlieseen ₉ with him su one unit is connected is Z * B" may be in the manufacture of arm - Pad or other foam-filled upholstery _{product, create a textured skin of a tough p} elastic plastic by forming a molten layer of such plastic on the inner surfaces of the mold, before the foamable powders according to the invention are introduced and peeled For the purposes of thermal or electrical insulation, a "sandwich" or layer structure is formed "in which the foam is sandwiched between layers of a rigid or flexible polymer coating, such as polyvinyl chloride, which has a hard surface"

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Polystyrene; Polypropylene and the like, or in a thin sheet of metal:

The following examples serve to illustrate certain issues guide forms of the invention

Example 1

A polyethylene resin with a melt index of 22 g / 10 i / lin is used. and a density of 0.915 g / cm ⁵ , which after pulverization has the following particle size distribution: 2.8 # <74 ρ, 21.0 $ -ς 149 ρ and 99 _S 2 # <297 Ji 58.2 parts of this powder are with 1.8 parts Azcd'ioarbcamid {"Ceicgen AZ") thoroughly dried The powder mixture is exposed in an oven for 10 minutes at a temperature of 210 ° C., during which a foam forms. The foam (thickness approximately 41 mm? Density 5.05 lbSo / cu.fto (0.0809 g / cm ')) has a predominantly open cell structure of medium fineness and is white and odorless and semi-flexible in nature>

Example 2

A polyethylene resin (Sohmelzindex 22 g / 10 IMn- ,, density 0.915 g / cm) is powdered to such a grain fineness that 86 > of the particles smaller than 50 microns and 97 smaller than 210 microns. A dry fragrance is made from 58.2 parts of this powder and 1.8 parts of p, p ^v -oxy-bis- (benzenesulfonylhydrazide) ("Gelogen"). The dry powder mixture will

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put in a mold and heated to ίόϋ C in a glass for 10 minutes · During this period; a foam about 6.1 cm thick develops; which has a very fine cell structure and a density of 0.056 g / W ⁵ (3.5 Ib3 / cu.ft )

Example 3

A cup-like body serving as a mold is filled with a dry mixture of polyethylene and azodicarboamide vegetables Example 1 ₉ covers it with a thin sheet of asbestos and heats the whole thing in an oven at 150 ° C for 1 min unmelted powder tipped out of the mold; leaving a skin of half-melted and half-expanded polymer adhering to the inner surface of the fora. The mold is heated again for 5 minutes to 210 ° G, during which the foam develops and stabilizes ο When the cup-like body is removed from the oven and cooled, a molded container with foamed sides of about 5 mm thickness is obtained

Example 4

48.0 parts of finely divided linear polyethylene (density 0.96 g / cra ⁵ ; cutting index 4.31 g / 10 min, at 190 ° C.; particle size range between 420 and 2000 u) are mixed dry with 2.0 parts of azodicar = boamid. J) as mixture is applied to an aluminum plate of 7.6 cm in width, 16.5 m in length and 5.72 cm deep

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and heated to 260 ° C. in an oven for 12 minutes rigid foam with a density of 0.7 4 * g / cnr

9 x

Examples 5 bio 7

After the Work way of Beiapiel 4 v / ground using the same aluminum trays ala Porη finely divided ethylene-butene llischpolymerisat, polypropylene and polybutene-1 in foams converted α Work values and properties of the foams obtained is called the Table I,

Tabel I. 6th 7th example 5 Polypro
pylen Poly
butene-1 Polymer 0.91 0p89 Art Ethylene
Butene
Mixed poly
merisat 6 _r 42 3.0 Density, g / oor O ρ 945 420-2000 420-2000 Melt index ? g / 10 min, *) 3.38 Grain size ρ u 420-2000 Barium azo Azodicarbo Blowing agent Art Barium azo "

Amount, i »

FLOATING CONDITIONS Temperature » ⁰ C
Krhltsungseeit, MIn _n

Foam density, g / cnr

(Ibο / cu, ft)

dicarb-dicarbamide oxylate oxylate

5 5 4

260

(5

0/1503 ^ 9.38)

280 15

_0s 1698

(10.6)

260 15

0.1698 (10.6)

*) at 19O ^W C, with the exception of polypropylene, which is ventilated at 230 C

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EXAMPLE 8

A polypropylene resin (density 0.91 g / cm, melt index 6.42 g / 10 min> at 230 ° C.) is reduced in size to a powder with a grain size distribution: 6.1 # < 210 u, 29 ₉ 6 9 * <297 u and 100 ° < 420 μ One would like 40 ropes of the powder dry with 2.0 parts of azodiciboanide and pour the mixture onto a tray. Example 4 If the powder is heated to 280 ° C for 12 minutes, an extremely rigid shoe with medium-fine ropes and a density of 0.285 β / ο * ⁵ (7.8 lb- / cuoft) is obtained,

Beiapi & l 9

As a result of the working technique of Example 4, samples of powdered polyethylenes with a grain size of less than 100 ρ were trooken with blowing agent and transferred to foam In this case, a closed Zelletruktur tested Stigt eioh _c that nan by corresponding Y / ahl Hare, BlHhmittel and work conditions can be obtained with Sei.Hume / oroffener or closed Zeilstruktur

Polyethylene blowing agent foaming fraction of the

ίο ____ »-_— ,, -» —_ — _ conditions open cells

Dioht · 0.915 ^R 3 * p, p ^v ~ Oxy ~ 14 min · ,, 0.65 oo bie- (benaol- 155 C

ο eulfoaylhydra-

in aid)

ο Density O »9i6 ^b ""0.31

£ Density Op915 ^a 2.7 £ Asodi- i2 min., · 0.80 O ₀ carboumid 20 £ C

Density 0.933 ° 2.5 # Azodi- 9 min .., 234 ° GO _P 44

carboamide

Sciimeizinaex: a = 22 _r ,,,

b - 70, r - 3 ,, o BAD CfrW & INAt.

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Belnlil 10

^ one-part, chlorinated polyethylene (chlorine content 15 £ »Sehmels index 20 g / 10 min., particle size 100 * κ 53 μ) is mixed with 5 * (ppH) p, p'-oxy-bi * - (b« nsolsulfonylhydra8id) trooken * 40 g of the Genieohes are firmly filled into a 17.8 χ 7.6 χ 5.1 om form and heated to 165 ° C for 10 minutes Weü * roe 0.066 n / m? (4.1 lb./od.ft.).

Beiepjel 11

Fine, urgent polystyrene ("Monsanto"900; particles / p »öeee 6.1 $ < 210 μ ₉ 29.6 $ <297 u, 100 % < 420 u) will oit 5 i> (pph) p, p" - Oxy-bie- (benzenesulfonyl eenicarbasid) ("Gelogen" BIl) trookengeaisohto 20 g of this smell are entered in a 8.9 χ 7.6 χ 5.1 om form and 14 minutes at 210 ° C, whereupon The polymerizate has expanded to a 2.5 mm thick foam with a thickness of 0.1137 g / ce ⁵ (7.09 lbo / o) ··.

Example 12

Feint «iliffee poly methyl methaorylate (red ram” plexiglass Y8 100 ") of the same grain size as in Example 11

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nit 5 i » (pph) asodicurboamide dry smoked, 20 g of the mixture« ground in the same way «as treated in example 11», however, only an increase of 12 hours to 210 ° C is required. The resulting »white, solid foam has a thickness of 53 mm and a density of 0.0402 g / osr (2.5 lb./ou,ft) and has a fine to medium-sized cell texture.

Example 13

Powdered polyvinylchloride ("Bakelite Vinylite VAOH"; partial size <100 u) is smeared with 5 pounds (pph) of dinitroeopenteiaethylene tetroAln ("Unicel HD"), 20 g of dee Geuiüohes "ground in an 8.9 x 7.6 χ 5" 1 om Fora 6 minutes, to 175 ° C, whereupon Bioh has formed a 2 oa thick, very fine Sohaua with a density of 0.1383 β / o » ³ (8.626 lb./ou.ft)

BfiBDiel U

Finely divided cellulose butyrate ("Tenite Cellulose Butyrate", Pormsorte) feilohengrttsee 100 % < 210 μ) is with 5 % (pph) Asodioarboamld trookenceaieoht. 10 g of this mixture are added to an 8.9 x 7.6 x 5.1 cm for ”and increases to 6 min. to 200 ° C. The resulting fine-rope, semi-rigid,“ eieee Schawrn het tine diameter of about 3 om and a density of 0.0431 g / oer (2.69 lbVou.ft ”).

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Fine polyamide (KyIon, ¹¹ Su Pont Zytel 63 ") of the same size as in Example 11 is dry-mixed with b f> (pph) p _t p * -Oxybie- (ben £ oyisulfOfi] rl" Seiilearbagld). MaIi gives 20 i of this Oeaisohos in a β »9 x 7,6 χ 5,1 se form and« rnli with 15 Hin. to 200 ° C, whereupon a rigid, wei & e «r _f * V medium, Uger SSoH * u · oit" liier density of 0.1708 & / CVR (10,65 ftc) vorliegtο

7t · above examples erlUutern the Einsäte of sohftu "- t rnn powdered Kaseen that d by simply Trockennieohen * get" grounded r polymers and blowing agents, in the following examples, the blowing agents are lmetifluierunoa- the Polyntrieaten by / or incorporated LUseteohnik and from the • With respect to masses, thin-celled or powdered Uaterlallen are

Beleplel 16

Polylth / ltn (Sohaelslndtx 22 g / 10 min at 190 ° C; density 0 »915 g / o) wlr € on a mixer of the Banbury type 15 minο at 10 * ° C» it 3.5 $ biasoaminobenzene ("Yuloaoel AN" ) Duroh-machined and subsequently powder-coated on a Vile / Mill type grinder. The powder (75 gi particle size, i.e. 6.1 t <210 ji, 29.6 5i <297 ji and 100 * <420 tt) becomes

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entered in a single 20.3 x 10.8 χ 7.0 on font and 20 min. «uf 155 ° O heated. The received ·, approximately 32 mm thick · foam «• Let a fine 1) 18 medium cell structure contain 65» 8 pounds open cells, has a density of 0.1035 g / oa '(6.46 lb, / ou «ft) «Ad let semi-flexible,

Beleplel 17

Due above powder (75 β) with a TellohenerQeftenbereleh of 420 ble 2000 u In the same manner as discussed in Beleplel · The Sohaum welet a etwae conquer Z # 11struktur to "f contains 77.8> open cells, and has a density of 0 .0907 g / c * ³ (5.66 lb, / ou, ft,)>

Beleplele 16 ble 22

Samples of polypropylene (density 0.905 g / em'i eohmelilnd · * 3 »4 β / 10 min. At 290 ° 0) and lineorpolyHthylen (Dlohte 0.96 e / om ³ l Botaalal index 0.9 i / 10 min« at 190 ° 0) are ground on a laataehuk grinder for 10 minutes at 150 ° 0 with the following elnaelnen blowing agents

a) 3 Jt Slasoamlnobenaol ("Vuleaoel Al-)

b) 3 + barlumasodloarboxylate ("Bxpandex 177") o) J ft Atodlaarbomamld (-CeIo «en AS")

Each PUetmaeee is powdered after cooling, la

3.2 s 3.8 ι 8t5 m forms entered wad received. 01a ermal-

$ emea SaaltaMt. tlad la faball · Π beaehrlebaa.

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B e i »a i · 1 Π

Polybutene-1 (density 0.89 ft / oe ³ ; Sohmeli index 2.0 g / 10 min. At 190 ° O) is placed on a Kautaohuk grinder for 10 min. At 100 ° C ■ it 5 5 * pp ^f -03qr * bie- (b * n »oleulfonylhydraeid) aufettieeht, The raw material is then granulated and powdered on a“ Pallaann grinder, A 50 g sample of powder (¥ cll «eheagrö ··· la Bereioh under 297 ia ) is placed in a flat metal container of 15 »2 χ 7ti x 5.1 ob CtrBs ·· and heated to 150 ° O for 20 minutes. 6 Ib / ou ^ t,) obtained, the al
semi-flexible renewal let

- 25 -

§01105 / 0141

m0 / S08606

hurry II blooms

Scfattuaung ! «Tor daa Sehn—

Art

You »- 8etaaalate, , latex.

"

■

lornjjröaae,

Art

♦)

ge, £ parahittur _f sung, O «in7

See- ZaII- stare- ** te,, «roebait ^w

Polypropylene 0.905 3.14

· 0.905 3.14

-1500

Diaaoai benzene

11 ti ο—

0.7 * * 105 Bariuaaso-3.4 f < 210 dlearbttc-6.1 % < 297 ylat 19.6 % * 420
34.5 ί < 500
100 Jt <150O

0.905 3.14 as at

Asodicarbonaadd

0.905 3.14

Polyethylene 0.96 0.3

1 «96 % < 105 Azodiear-9.8 % <20 boaaaid

17.64 Ιί <297

56.85) l <420 i $

0.7 1>

3.4 *

6.1 ^

19t6 *

34.5 ί

100

< 105 Bariuaazo-

<210 dioarbcnc-

<297 ylat

* <Ιί <

* O

300 320

300 230

350

7 9

4 9

f / cm-Ib. /

aa

ou. ft,

0.2099 conquered etarr (13.1)

0.1938 old etarr (12.1) tel

0.2425 «it- rigid (15.14) tel

0.1961 fine (12.24)

0.3268 ait-etarr (20.4) tal

Mi lytr c. aoaeeaoeaaa aai lOAJjropylen, aal walohai the Wtwttmimg at WO * C takes place

149 * 231

g-52281

Belaplel 24

Small amounts of a polyethylene (Dlohte 0.92 β / c "⁵; Schaela index 5.0 g / 10 min. at 290 ° C.) and polyisobutylene (molecular weight 120,000) are processed on a Kauteohuk grinder under aneohlieeeender Bugab · of 3 »0 Jf H,! F'-Diaethyl-ll _f K · - dlnitroeoterephthalumld gealecht, The cold plastic Ha ··· is granulated, mixed with drying egg · and then brought into a finely divided state by means of a Wiley grinder. The finely divided powder (partial size in the range from 297 to 1000 yx) is placed in a fluffy metal tray and boiled in an oven at 125 ° C for 15 minutes. You get a flexible foam with medium cell tea and good elasticity .

liliDltl 2S

Bin · sample pole / etyrol ( "Do" ßtyron 666m ^F, Mar »pts generally · f" riMndung) is combined on a Miecher the type Banbury with S OEW. ^ Aiodioarbonamid. If ta · blowing agent U the polymer ieat volletandig the per If Ut ₉ , al · hvi · «« Sohmelae are cooled and make a 3.2 mm oranges. The granules are then pulverized duroh meohaai- • before · grinding and sieved in »white samples« f «lna« rt "llteit fmlyityr ·! · * (1)" it "intr feilohangre ··· killed by al mmmlgst · ί97 m and (2) with a eoloa 's mis" h "n TF7 mmi 1000 m _v" samples both dleeer «Pulvejr

909I0S / 094I

S-52281

separately for themselves on trays aufgegeuen _F which one I Sicherstelluns a good "pack" of the particles shakes, The "" samples in an oven at 200 ° C blown case both samples stretch au an acting "out, with due finer Pulrer the role The size of the coarser sample (after 11 to 13 minutes) is approximately 2 1/2 inches thick. (5 lb- / cuft and a fine to medium line structure -

B i κ β i β 1 26

As in Example 25, a sample of high-carbon polystyrene ("Monsanto Luetrex Hi-Teet 88 * ^ e significantly higher Z kisteit!, iie mainly in a orhähten Beetftndigteit against granulating during handling of the foam during a Zeitrasücs tvm Auadruek ksaant

Boiepiel 27

PoljiMtlsylatethacrylat (injection molding, »Plexiglas YS **) is by working on a rubber grinder nit £ 4 PfP'-Gzy-bis-ibensolBulfonyl-aefcicerbutid) thickened A «ft Atsrch a & ttohlleefteod ·· Granulating and PulTsrinating er» holding powder rlrd sin «traction kit of a particle aereae

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909805 / 09A8

BATH

3-52281

<r42O j * won by seven; this powder is heated in a stainless steel beaker in an oven 10 up to 215 ° C, whereupon the volume has increased to 6 to 7 times and a free, rigid view with a medium to coarse cell tractor is in front ) The density of Sohauac is 0.13 g / cer (B.

Beleplel 28

Bine Prob "polyamide" manufactured sue hexamethylenediamine and, la Hoiverhftltnis ron 50: 50, adipic acid and Äthyleuberoneilure, a bit VleooeitHtszahl determined in AsieiaeneÄttre, clay is dispersed in 1.6 959fleem Xthunol, d "m to Dinitrceopentsjiethjlentetramin (" HD Unioil ^W) in an amount of $ 3, lied to the polyanide, »ueetit Daa gelörte Gut is then precipitated by adding Wseser and the powder is dried and sieved to a size smaller than 420 u brewed Si ···· Powder is in a flat The metal bowl is fired to 225 ° C, with a further coloration and a green cell structure, the foam is extremely solid and extremely firm and goes far beyond the above-mentioned SohHuae,

Example 29

On a Kautuohuk clearing mill, a sample of a * Cular Polyrlnylohlorld-Vlnylaoetat-IIlsohpolynerisatea

- 29 909805/0948 _{BAD 0RIGINAL}

3-52231

("Saugatuck Marvinal VH-60 *) with 2? I ana epoxidized

("Paraplex" G-62), 1 f- Cadwlua-bariualaurat unrt 5 36 i # <- (lj0n3olaulfonylbydr8SitÄj wiped up Dae hoatög »a # Geniech is cooled, granulated _t pulverized and sieved to a particle size» smaller t * la 210 ρ? Daa Powder is covered in a seed-cup-like body "the" on the old of an Aebsstplatt ", 1 Hin, burned at 180 ° C. Thereupon" Uberechüaeig "powder from the body _?

a geeehnolzener coating surüclcblelbt ^ D # r ■ coating in dam Bekälter 3 is U ± n, again in oven eio ^ sgabertc vvobei calibrating a auegedahnt "Zellutrulitur from about 6 aa Tfanddick" escape disgusted _f which the Innenfcrm of the container to "EIET> This shape is removed from the container after cooling *, among other things, it turns out to be ul »a« hr »ufrefe- *

30th

A sample of XthyXoelluloae ( ^w Dow Etbooal 855 *) is opened up with 2 * 4,4 ^ -Biphenyldivulfenylasid all blowing agents the Sohaum which is approximately IJ is thick sua, bee it st a "density τοπ 0.24 β / ο" ³ (15 Ibe / cu ft} and "eist a 'attraktIre rigidity ρ strength and toughness,

- 30 -.
909805/184 8

U94231

Vie the above description and examples show. The present invention provides a single and simple VerTabrea for the formation of an unlimited variety of cefor types, chested articles of various foroes and 3 sizes made of polymeric material. The method requires only simple devices, mainly aur β la fora and a heat source, by making minor changes to the heakrtiona variable, the line type is mainly open and predominantly varying in size, and can be rigidly flexible or flexible

In contrast to this, the fluidized bed process not only requires more complicated devices and a more complex mode of operation, but these processes are also limited to the application in the formation of relatively thinner over and above the exposed surfaces according to the process of the Ü3A-P "tentechrift 2 961 6?" Is a. 3 A vortex layer heating device is necessary via a hooking device, whereas only one heating device is required in the present invention. Äteoh der Pctoctechrirt tons of tHnigJip HeV 1m «ltter ttL« fce Me * »· 1.9 μ» d 1 » ttmme Kelei can only be achieved with multiple immersion treatments, while wttee the yorlleceeden Brfindttag Dicker ittn gef oretea SohatOMS bl« su several customs ( one inch ^ verifiable about 2 1/2 cm) in a ArlMlteevtuf "recoverable bar are ^ ΓΙβ übersugedioke H% in de" method of the Ba, further teirtschrift by ti "ability of the * Interleaving beschrttnlct" the WCn "aulcunebUHai

909895/0948 * ™ **

3-52231

The bodies used according to the patent with strong heat absorption capacity in the form of thick metal tubes and rods require preheating temperatures that are about 55 1/2 ° C or more above the softening temperature of the polymer are, among other things, to achieve coatings with a thickness of less than 75 U. Thicker coatings can therefore not be achieved without ο following the decomposition peratur of the polymers © * The WirfcalBGhicht method remains even with the coating of smaller materials 'mi'aM ^ ojEühcü ^ ΒΣΊ & 15 ^ ua _t like the teehniucui very gabräuchl

g «ivaiiiüch cder by spraying on before» Hatali J? <QYui, & t aline % ®aen Ki-fcl ^. That Verfahr ^ a 'vorIi jgvna en Inventuü ^ arideiereoits ■ iöt von uqt ami «iirffifcaaj.'Rehffi"4Vt;i'a ^ göii d ^ r Porm au ^ aeentli ^ l

UlI «

is, <. \ # uel diä i-erra the outer area of the finished object and it pictureot., ^v

In fluidized bed technology, particles can »their oröeee im

about 1üO u o carries, not

Man k ^ rüi ätiaeu & apreaheaä ά *. * Intiig «Natux · dex * Hisohttng vca Fo ^ yüneriSE« o ^ d Bl ^ ümi.tt «ix, di * r lui the process goadee" ^^ i ^ uxci.üur idt, b * i ν, βΙοηβΛ 'feilohen fiiit one

Jr ds be voa weisd ^ isr ale 50 u si oh leicht

, V:, üiL, ,,>. 4 ^ i. · ■. -Ay ^ fal ti:.:. ^

let use »do not achieve« Dae vortex method

909 8 0 5/0948 "^ ^

S-52281

gΓ: does not allow forner to use simple, dry-mixed Gemengenν there such mixtures in the rapidly flowing Gaeetron of the fluidized bed show a tendency to secrete Particles of the blowing agent would be easily produced get lost during hit trips or be calibrated by hitting them prematurely decompose the hot surface of the base *

Another "clear advantage of the process of the invention is that" the " tmn kit of a given amount of a given solid blowing agent can achieve polymerizates formed with a considerably lower density than otherwise with previously known processes - for example, Strangyrees processes in which one "Thermoplastic polymer 3 to 5 pounds" a """solid sheet leaflets are incorporated" Sdhaumdichten down to about 0.52 g / cer (20 lb "/ cu; fiOf while" old the process according to the present invention and sit the same binding means - * «rog · dieaten in the range of 0.08 g / cm * (5 lbVoo.ft) erslelen kanu« The genes of the Brfindang received aeohitiae and desentopreobend la relation to the amount of the in the sight »remaining» undeserved BlätiBittel-BüokstSiade entepreohend improved,

Above are various embodiments of the invention described · »» but the boats of the invention have further variations and amendments ^ are important e uerkaal of the invention lies in the use of a finely divided Plaetaaterialsi aan can easily form PlaeteohHu ·· »without doing special ~ app * ratur # n and combined working conditions take effect on

909805/0948 ~ 33 * BAD OWGlNAU

, "1 * 94231

S-52281

nuts Me Verwandung of f unitary P'taatmaterial _{v f} as polyethylene ixa mixture Rait feinte 11 _r strength fenteia Bliihiaittel will stall a particular preferred manner of carrying out the invention <Jar Such * Arbeitegeoiach has tuf due to its Wirtechaftlichkeit and Anpaesungafähigketlt for dec Her-.atelier how the foreman had an excellent value for his mercy.

909605/0948 ~ ³⁴ "* BAD ORIGINAL

Claims (1)

Claims 3 «tby gekexmzol suspects that mfin In a cffano odti & $ hle33 "IAEE Fona a schaumblldende Habse üiafuhrS ;, felntelllgee which solid plastic material having an average Teilohengr & sse of less than about 0 _# l to 10 ttew · ^ to the felntelllgen solid blowing agent contains, and then the mass heated to a temperature _# the etna 35 bio 150 ⁰ C is above the Sohnelspuckt of the plastic material "do BlMhmifctel ru decompose the _e Flaetsaterlal without 2>» rsetsung xu aofanelsen and horeuateilen on serving ^ 'tfeica the Plostsohauffl. 2 · Procedure naoh Anapruoh 1, marked by «that one fointeiligea, plastic material with a d-w-jhsohnittlichen Partial height from Keniger than about 500 μ used. - · Method according to claim 1 or 2, thereby that Mn da · BlMbodttel in a kenee in the range of about A-52 2 blah 6 pounds of total weight of plastic material used. 4. Method according to one of Claims 1 to 3, characterized in that that «an blowing agent is used whose decomposition temperature is above the melting point of the plastic Material lies » 5. The method according to claim 1, characterized in that the temperature is maintained for a time sufficient to decompose essentially all of the blowing agent. 6. Method according to one of Claims 1 to 5, characterized in that that one works with an open or closed, form-giving zone. - 36 0980 S / na / o BATH ORIGINAL