DE1569292A1 - Process for the manufacture of a synthetic polymer material - Google Patents

Description

ng- linen weaver

asrmann _Λ

Munich 2, tantalum J 3 1.

Tel. 29 798Θ

Η · γγ Andre ", Albert, Jean PIVBIEAU

"Verfahr ·«, for the production of an Kunstpoiymerraaterials "

Priority Switzerland Rome March 31, 1964

The counterpart of the present invention is in the process for the Heratelluag a Kun8tpolyaermaterialB _{t then} generally has a cell structure and in a separate case is compact and cell-free.

Such material can namely according to the invention in harder and stiffer, or harder and more elastic, or softer and elastic form} in one as in both

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· »2 -

in other cases this material can be cellular and open cells or closed cells, or simultaneously have open and closed cells.

The invention also relates to the vegetables materials obtained from the aforementioned process and considered to be commercial products.

These materials can be made from a single mass or from consist of a composite mass created by the juxtaposition They are of a more nature, more firmly bound together Blementarmassen is formed from which at least one is obtained according to the invention. But preferably and apart of fittings forming elements (such as cardboard tubes stiffened by impregnation, various metallic elements), the different masses will be different, but all vegetables prepared according to the above procedure.

The bonding of the said compounds to one another can be obtained in any appropriate way, but preferably two adjacent layers * " contact one another are formed in the same way or one after the other, and in the latter case the hardening of the first layer is not complete when the second layer is formed.

Of course, the distribution of the aforementioned masses in the composite mass can be in any way be, and layer - or core materials, etc. correspond.

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The subject of the present invention is also the formation of τοη composite or non-composite Masses when guiding the hardening material onto a surface or in a corresponding container, for example in a mold (injection molding) or in an extruder (strands) or onto a surface (atomization, for example by means of a Syringe, simple sausaen, injection) or into the water (Construction of floating or non-floating dikes)

The formation of such coffers through this technique is one to the method according to the invention, since it is impossible to use the Final phase of planning and the geometrical conditions of this Separate hardening from the previous phase of the mixture.

The erfindungsgeaKsse process for the preparation of a Kunstpblymermaterlale features calibration namely that a reaction mass is formed from wsleliar since © ®r ~-mentioned material by curing due ier polymerization occurs by operating at a temperature of between 5 ⁸ C and 50 ^fl C a thermosetting Phenolhars or the like, of a low degree of polymerization and previously made into a liquid or viscous state, a polymerization catalyst, a polymerization inhibitor body are mixed and the proportions of the one of its mixture ingredients are controlled the same as the relative times of their introduction to obtain a material of a given density.

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Di · Anmtldtrin has found, §8 BtI possible, tin material ron gtgtbtntr density according to the invention Procedure see below, aueetrdta can nan ertntutll the duration Determine the polymerization, i.e. the duration of the hardening (from the moment of the introduction of the catalyst *, in some cases).

It is also possible to have a very wide diameter , sum example τοη 0.015 su 4 for the Hattrial manufactures through the combined or non-combined usage τοη Keep swelling agents and fillers clean.

If the cell material is cloudy, and this is the case is particularly taken into account by the Torlitgendt invention, becomes a sohwtlltndts means with the goal mentioned components (Hars, catalyst, Htmmungsmitttl) rermitoht.

For the exact setting of the polymerisation dtr is based on the procedure ι in the absence of a swelling agent for a Hars and a catalyst (and trtntutll an ortr mthrtrt filler) τοη gtgtbtntr type and Proportions (depending on the hair mentioned) The weight ratio is tints Htmmungsmitttls gtgtbtntr type depending on τοη dtr su obtained polymerization time certainly. For this purpose we use the example, based on experience built-up calculation tables btnutst, and each calculation table points, in dtn btsondtrtn existing conditions, to the su chooses Quantity ratio of the given means of ventilation as a function of τοη the desired polymerization time.

909831/1283 bath

Bs did clear »date the Diohte in absentia a · swelling agent cannot reach the lower part of the abovementioned net weight range, but one can in a low Na ·· through the wise choice of the type and the proportions of the resin and the catalyst on the one hand, and especially the tulle fabric on the other hand change these diohte, for example τοη 1.1 au 4.

In the presence of a trace of swelling Medium, the proportion of which is preferably below 25 It will be percent by weight of the mixture, it is quite different because the proportion of this swelling agent on the Porosity (and consequently on the dihths) of the material obtained has a strong effect.

For the exact regulation of the density of the mentioned material Ia Dlohtenbereioh from 0.015 to 4, nan is only on the quantitative ratio of the swelling agent can act, but it is preferably proceeded in the following manner for a hair and a catalyst (and usually a filler ) of given types and proportions (depending on VOB named resin), depending on the choice of the diets to be obtained, those for the proportions of the swelling Pairs of value to be taken by means of and by means of the Heamunga means determined, it is assumed that the nature of both components is established. For this purpose, for example, empirical calculation tables are used, and each Calculator gives in the particular conditions considered

909831 / 12Ö3

The formerly named V "rtpa * r *. Self-reliantly leads to the determination of any one of the two quantity ratios was the determination of the other, and as a result, since the quantitative ratio of the inhibiting agent and all other factors are determined, the duration of the polymerization becomes known.

If, besides the density of the material, one dl duration As the polymerization progresses, it is not possible to determine the quantity ratios any more de swelling agent or de inhibiting agent arbitrarily, and the calculation table shows da ·· « Optionally select a value pair for the ·· quantity reserve ··· nut (iamer has a solution to the problem posed in this way and only one).

According to the invention are rorsugsveise or several fillers with the other components of the material mixed, because in the absence of any · filler · will be the Applications of such a material · limited {the · * fillers can nlalich colored pigaente, colored · liquids be, substances that alleviate the physical and mechanical properties of the material in a given direction, fabric dl the resistance to corrosion and chemicals, the resistance to hitting and increase fire resistance (fire-resistant substances such as trioresyl phosphate, potassium and aluminum nitrates), fabric for Sound density etc. ». ·; the material · geaa ·· of the invention

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are of course dielectric but this property can be increased by increasing the proportion of asbestos.

In general, the known phenoplasts cannot tolerate a temperature above 20020 {lose above this temperature their properties and dimensions; on the contrary, the material according to the invention can be used without deformation or change in shape tolerate much higher temperatures (namely if, how to do it Later we will see an asbestos used as a swelling agent) j this material can even have a temperature in the range of 800QC and even higher tolerated if special fillers Calcined mineral fillers (clay, magnesia) are used.

According to the method of the present invention, a so-called "thermosetting ⁿ phenolic resin or the like is used, which in the flÜBBigen, © the SiH © n state Ämreh which corresponding means is any offset toes M ··. ^ - to perform SSKM ^ {?. the basic resin is in polycondensate with a low degree of polymerization in relation to that of the final material} this polycondensate usually appears in a solid form, soluble in some solvents, which in principle is fusible, but gives an infusible material by further driven polymerization (therefore it becomes "thermosetting "named") | to bring this polycondensate to the desired liquid or acidic state (the state is in the aforementioned temperature range 5 ^a -508), one has to dissolve, for example, in an appropriate solvent and / or suspend it in a given liquid, or it with

• Into a certain amount of knowledge there is a quantity of ditetr Fl (Ieeigktit mixf in tints special pall can dltat liquid water eein.

The polycondensate, known as Yorgen, can also be made in liquid form Bars have a low degree of polymerization, which, by the way, is manommal In water or otherwise in alkaline solutions or in can be dissolved in the organic solvents.

Prevention must state the physical condition in which said polycondensate is brought to be mixed with the other constituents of the material according to the invention, see below oentipoises between 30,000 and 70,000 oentipoises due to a single viscosity when it is measured in the Niöie τοη 208C »and on favorable way (la case of a phenolic resin) «wipe 45,000 and 65,000 oentlpoises are marked.

Through phenol hares one can get any kind of hars, its at least one of the monomers is a compound which has a phthalate clone - this compound can have something in common Phenol or a polyphenol such as s.B. Resorcinol or a monophenol other than common phenol, e.g. Ortho ~ and / or Meta- and / or paracreeol, xylenol, butylphenol, etc.

As a monomer condensable with the Torgenanntan monomer compound, one will generally use a compound which has at least one aldehyde function, for example formaldehyde, acetaldehyde or furfural; one can also use a body from which one of the above ... _; Compound is created t this way you can use hexamethylenetetramine

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use, the formula also results from thermal decomposition this compound can act as a hardening accelerator and as a swelling agent.

According to one embodiment of the present invention, a phenolic resin of the "A" type is used, which corresponds to a first stage of condensation of the monomers under the influence of an alkaline catalyst (soda, potash, ammonia, etc.), since such a resin is generally used in solvents such as alcohol, acetone , Glycerin, etc. is meltable and soluble. In a special case, a resin of type A formed from the common phenol and formaldehyde will be used; these resins are sometimes called "Reeols" and oTsalWhum is a solid form which is brought into a liquid or viscous state using water as a carrier medium ( Case of those resins commonly found commercially); the physical form which you named resin will take will, as stated above, preferably have a viscosity between 45,000 and 65,000 centipoises, but, in this particular case, this viscosity will be favorable Way between 52,000 and 60,000 centipoists (measured near 20 ^ 0); its pH will preferably be between 4.5 and 5 ,? lie.

Of course, any resin other than phenol resin becomes the thermosetting resin type according to the method of the invention is used if it only meets the aforementioned characteristics. If it is a phenol type resin

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an acid catalyst is preferably used, but est is clear that every other type of catalyst depending on the nature of the monomers and the final polymer, i.e. of the one in finished material can be used.

It is known that sometimes in the case of phenolic resins the increase in temperature is sufficient to cause polymerization and the desired hardening, but in the case of phenolic resins this temperature can sometimes be excessive, and the properties (homogeneity for example) of the final material and damage the reproducibility of the results; geaäss the present invention must never be a temperature of 13Οβσ to be exceeded, but it will always be in the presence of one Catalyst worked. Also, if you do it continuously works, the mixture is preferably more stable at practical Temperature run, and, in general, everything will ordered in such a way that the curve showing the temperature of the mixture as a function of the duration (up to the moment the hardening) indicates, in advance it is determined 1st.

Before introducing the catalyst, the mass formed by the constituents of the mixture is preferably kept at a temperature between 15 ⁹ and 40 ^ 0? After the introduction of the catalyst, it may be necessary, due to the exothermic nature of the polymerization reactions of the aforementioned type, to provide a system which would bring about a cooling of controllable strength {the establishment of a reheating or

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BATHROOM OBlGiNAL

adjustable cooling can also be provided »um the course of the aforementioned curve must be observed {of course the same regulation is possible, which is also the type of resin used in the context of the present invention.

Except for the catalyst, they are practically preferred all ingredients of the mixture are introduced at the same time, and the mixture is then homogenized, usually by kneading, then the catalyst is introduced, which the initial polymerization causes (in this way you can extend the pawn, which the time since the mixing of all Components outside of the catalyst starts from the time as the hardening occurs, it separates without the polymerization time to change, which can be interesting because, for example, the distance between the point where the mix is going on (e.g. in a kneader) and de? Replace the BF3t - ?, rs? TtaagC swm Example in a form) can be very changeable.

If you notice, as in the previous paragraph that the inhibitor is introduced before the catalyst, which allows, simply by changing the proportion inhibitor polymerisation builders to change, but to trigger them at the desired time, by simultaneously using the same quantitative ratio of the catalyst admits. It must be noted that the inhibitor either previously in the resin alone, or on independent Way can be introduced.

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The use of a constant in practice Catalyst (»for example expressed as a function of the resin consists of a preferred implementation of the method of the present invention.

This narrow catalyst will preferably be between 2 * ^f and 15 "* (by weight, depending on the resin) in the case of a phenol hare and an acidic catalyst; The acid used will usually be a strong, inorganic or organic acid, and especially hydrochloric acid and / or sulfuric acid, a certain amount of organic acid is preferably added to these acids, which makes the resin sensitive to the action of the inorganic acid, for example paratoluenesulfonic acid in one Quantity ratio which is at most equal to 2/5 of that of the mineral acid.

As a non-acidic catalyst one can use in case of feces such a catalyst as ethyl dioxide (more difficult to handle) or a mixture of propyl ether and fluorobenzene (fairly expensive).

The inhibitor used in the method of the present invention is preferred among the following substances selected t water, salty Vaaaerb'sung, oil, Fettstoff, Glyoerin, etc. «. W. The applicant has noted that c salty water solutions (non-alkaline line) Showed that seawater could be used for this purpose; it was also found that it is better

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the lake water with ordinary water up to about 2 to 4 Times to dilute its initial volume.

In general, the proportion of the inhibiting agent can preferably be between 0 and 5% by weight, depending on the resin.

The proportion of swelling agent useful in the process of the present invention is vegetable preferably between $ 0 and $ 25 depending on weight from the resin, because these proportions allow the very to achieve the previously specified density scale.

This swelling agent can be of various types, and, for example, among the carbonates (ammonium carbonate, sodium carbonate, etc.) hydrocarbons (toluene, jet fuel, Benzene, etc.), but is preferred used as a swelling agent a substance chosen from the group formed by asbestos, such as, for example, asbestos usually used as a filler for paint (PuI-vergestein ) ·

To ice the material according to the invention make (hard and elastic or soft and elastic) will be in the aforementioned mixture in a known manner one or more auxiliaries (plasticizers), such as the one under the name "Thiakhol" known, a higher quantity ratio catalyst and / or filler allowed then, gradually of white and elastic Masses (forums of roughly the same size) too hard and elastic masses (irregular pores due to onion

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emergence) to pass.

The elasticity and / or flexibility of the material The ε smock can be made of powdered, vulcanized Gum, isinglass, rosin, vegetable oils, glycerine, etc. v. beetehon.

The use of such aids embraces production smoother, for example consisting of nehroren layers Filmoiateriale that are particularly good for packaging fit.

Rs was noticed that the work in the presence of air and light acted on the results obtained and changes in the conditions of exposure to air and in the Lighting conditions changes in (? En corresponding calculation tables caused, and the results are not ec ßenprecisely reproducible was.

As a result, the invention is a manufacturing process preferably carried out under light and air protection.

Surface active · lüttel can be entered in the Tinchunf * but this is not absolutely necessary. If the Catalyst included in the mixture is preferred this hardening mixture can be fed onto a surface or into a container (mold or extruder), i.e. into the Make yourself where § ± bhärtet and at the same time the achieved Final form is obtained by fee muse, it is noticed that this form somehow which may be, and the mass of material thus obtained just as well

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in limited as well as in very large »even meter-high dimensions be generated knows E.b. in the case of dikes), and the · in homogeneous quality.

This cash register can also provide a Kusaamengesetiste through the deposit of different types (feat anelnanderg «- bound masses that form an undissociable whole

be

resulting mass, and each elementary mass is preferably homogeneous; at least some of the Elemontarmaoses mentioned (and

at least one) are then according to the method of the invention obtained, and each of these masses is specific by one Composition marked (which incidentally the same for two or more of these non-contact maseta. can be).

Vgrsugswelee betsit & t jeäeefe complete & n & lg such a composite cash register made of Bleßentaraassenesaas "? Aoi'v :: m '/ ^ q ^ emlias the method of the present invention is shown, except for the stiffening or the mechanical properties of the suspension mass-increasing elements (metallic tube, Tubes made of stiffened cardboard, woven or non-woven fibers, made of textile, metal or plastic, etc. In this way, every Eleaentaroaese can be represented from a very homogeneous composition, which corresponds to the desired one; in addition, since the various elemental compositions are of the same type, bind them intimately to one another, the cohesion of the united masses is separated and not a division

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let nSglioh.If »an erslelt, the« «in · dtr» tarmaeaen sellfrei vird (sub example fall ei · a 'crust ¹ · ie «in · outside form sues), however, we know it to be recommended, in dl · Mixture, which is shown as a small amount of swelling putty (because it may have a few widely spaced pieces in the knee above), which does not prevent the surface from rolling smoothly and fully su received.

In addition, let the cabbage lettuce as much as possible nooh improved when the hachbareaesen at the same time Touch old one another »or harden one after the other, whereby the Hardening of the "wide cash register" when touching the harvested crop * shhah, eodaee the curvature of the first named pintuck taraas- • e nooh nloht let roll when the mixture forming the svelte hatred comes into contact with the first mentioned nose. braoht 1st

In general, the above el-entarse them Form layers of a so-tight wetness, sohlohtveise or as susassiengesetste mass old Xwiebeletstruktur (Schiohten, die eioh rereohlieesen) enters, but it will assumed that this each desired forest and distribution can have, susi example, let taraaa β en in the form τοη

Inside
a «or« more separate / learn or τοη one or

■ honorable interior elements.

A particularly interesting structure is shown in the example τοη exhibited a «sues — narrowest material that

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has two filamentary masses according to the present invention , one of which in the shape of one of one actually cell-free material of high density existing Stusseren layer or "crust" occurs, this location with one with the called crust forming a monoblock structure, internal stiffening element is possibly connected, and its Composition can be the same as that of the crust, while the other elemental mass is in the form of a material of low density appears (row of cells), which denotes the occupies limited space by said crust, or lies between this crust and the stiffening element.

It has been observed that the curing time is that obtained in accordance with the method of the present invention Materials., Usually, between 1 and 30 seconds, lay, arber that they are between 2 and 7 seconds, in most cases could «In the most extreme cases, in the conventional Conditions of industrial application of manufacturing processes and shaping of plastic materials are less interesting , this duration can reach many hours (through a corresponding regulation of the relative quantity ratios from Henua agent and catalyst).

It was also noted that it is necessary to set the temperature ■ to be checked as indicated above, otherwise the depth of reaction is the polymerisation to be achieved and so on, because side reactions occur and in some cases destroy reagents and products can.

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"The one used for the application of the present procedure Equipment can be of the same type as that of the patent application "Equipment for the manufacture of Resin materials, especially in a continuous manner ", which am the same day as this was requested by the applicant.

It is not necessary to use such equipment, although it was designed for continuous work and works for both continuous and discontinuous work.

T) the method according to the present invention can continuous and discontinuous, but it is clear that it is especially good for continuous Production fits in terms of the mixing phase and hardening phase (possibly with an expansion hardness associated with polymerisation): in this case the constituents of the material are introduced and continuously mixed (for example in a kneader -'- 'isher apparatus) and the extinction obtained is continuously transferred to the host transferred (for example into a mold or an extruder or on a surface or into the water), where either a mass of continuous structure (which is in pieces may or may not be cut up, for example as a material having a continuous wall or a continuous Pile forms), or a series of tills (those in the Time and space are separate) occurs.

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Trap a mold for molding by curing dee Object is needed, a fuel molding must be carried out be (at least one injection for each of the elemental masses of the vegetable included in the method of the invention composite cash register); these shapes can be continuous be carried out by means of an open, fixed or adjustable mold, which delivers shaped mass on the outside, the stimulation given by the mixture or mixtures being injected is sufficient to produce the already hardened mixture in most cases Part to advance.

Of course, it may be necessary for this shaping to use a skeleton to burn two neighboring elementary masses; this guiding device is necessary if two neighboring elementary masses arise at the same time, the end of this guiding device in relative motion to these hates in correlation with The relative displacement of the hardness limit is that the limit (across the g ^ | i "sE-iieis ~ Mass6ffi ^; f ^{; 1} Ää # 'dlViron hardened zones of

^{Äiίt O} sö "i never put the master device in

f the formation with continuous, 'other strands of a simple or iueaa aengese -; isju: «n-lISBBe ^ auiäh an extrusion in this way one can get a ^ o ^^ t ^ a ^ i & i, that is perpendicular to the strand direction "<Atltr ^ l% proves different kinds of hatred To clarify the matter, imagine two masses, one of them

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one cylindrical shape, while the other an outer one Forms a layer of uniform density {both can For example, they can be formed at the same time when «on upwards on the extruder an Ejlindrisches eur opening of the extruder sets up coaxial guide device, and this guide is at a certain distance ron the opening of the extruder interrupted, since the masses have hardened enough, well without a guide device keep their respectful distant jgu (the Solidarity between the two masses who have come together can then absolutely secured by the fact that the named masses can be of the same kind in a favorable way, their more critical Polymerization point (critical hardening) in the same Moment lies for each of the two masses (in a transverse section to the axis of the extruder), the temperature control can be carried out precisely (the durohsatas quantities are nlmlioh lower in the extrusion press than in injection molding in a continuous way, on velohes a continuous extraction from the Form follows), and the outlet opening of the extrusion press is best dimensioned; it is also possible to run the two rorgen Forming masses one after the other, for example, when bending Burst of the hardening of the heart upward in despair Oflation of the extrusion press (possible use of a guide device ), then this man, preferably in front of a roll stand Hardening, clay surrounding the outer layer (the guide device is no longer necessary), which then harden, so that both masses at the moment they are the. Drain opening of the extruder happen, hardened and in solidarity.

909831/1283 _iAD original

According to one characteristic of the invention, it is possible in the course of the production of a composite mass with a translucent and unbroken "crust" under the crust under light to insert a thin photosensitive film, the photosensitive components of which are, for example, a thin mixed constituent such as phenolic resin. Gelatin to be p-etra ^ sn. Since all processes have already taken place under light protection, it is then possible to expose the photosensitive film by simultaneous exposure under a strong light, and this exposure occurs when the entire composite mass has assumed its final hardened form, with the aforementioned crust in front or may be formed after this exposure. The image results either from the direct exposure of a photosensitive, discontinuous film, the surface distribution of which corresponds to the image or the desired pattern, or from the exposure of a photosensitive continuous film with a layer (between the light source and the composite mass) of a protective material with a reproduction of a pattern , or an image trimmed from a glass plate or a transparent plastic film to reproduce this image or this pattern on the aforementioned photosensitive film; the fixing of the images can be carried out according to the conventional photographic dry or momentary methods. The · «· characteristic offers the particular advantage that one is available upon request

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the surfaces of the generated measurements can, and it there is no risk of misalignment of this decoration. These decorations can either be in black and white, or monochrome, or multicolored by using a photosensitive film of the same kind.

Eb is also possible the masses obtained according to the process of the present invention by introducing to decorate pre-embossed cloth or paper boards which the desired patterns or images are displayed.

Eb is noted that when working according to the procedure of the invention, changes in temperature or in the proportion of an ingredient, in general work in the following way (assuming that the other factors are immutable):

a) Increase in temperature! Increase in the rate of polymerization, reduced Density;

b) Increase in the amount of inhibitor: decrease in the polymer ion rate, decrease in expansion rate, slight decrease in density;

c) Increase in the amount of catalyst: increase in expansion speed, increase the polymerization rate j the density can be higher;

d) Increase in the amount of swelling agent: decrease in the rate of expansion, stronger expansion, weaker Density;

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e) Increase in the amount of filler {generally higher Density.

Eb it is noticed that one can be achieved both by shaping and by Strangen Maasen with a well-finished surface (borrowed very smooth contact skin).

The invention is being used with great accuracy the following examples and the calculation table on Figure 1 explained.

EXAMPLE I One takes a resin ^H A "(common phenol resin formula,

of type "A", obtained by alkaline catalysis) of the following additives

1) water ι 14 g

2) Polycondensate Phenol-Forsei s TS Q-

3) residue of free phenol ι 8 g

This polycondensate was made from 75 parts by weight phenols and 140 parts by weight of formols, duroh alkaline catalysis (Use of a sodium hydroxide solution) shown; in absence from water and from residual unpolymerized phenol appears this polycondensate in a doughy state.

The viscosity of this resin at 202C is 56,000 centipoises (tough state) (the temperature of the said Haraes is slowly brought to 34 ⁹ C; its viscosity then reaches about 10,000 centipoises.

The parts given above are given by weight.

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Be is mixed strongly and very raw (in 25 seconds for example) under air and light ohms, and the 100 parts of the yorgen called Harsea, 1? Parts washed and dry kieaelerdhaltigen Saude · (Qranulometrie 25/16), 2 parts · asbestos and 0.1 part of sea water, said components rersohiedenen Torher au a temperature τοη) is ^a C 54 brought about by the way 6 parts of hydrochloric acid with 1 part konsentrierter concentrated oleic acid rermisoht, and this catalyst is re-prepared with the stony mass just obtained, the qanse is then poured into a metallic and shiny, absolutely dry pore (it is a question of discontinuous forestry), where it expands for about a minute becomes) the temperature of the mass rises • it expands to about 12OtC | the mass hardens in seconds after the expansion (the finished material can be easily stripped off the pore) it emerges as a hard and stiff, homogeneous mass with a fine, very smooth contact skin (its thickness is 0.285.

BBISPIBL 2

You drive as in Example I, but you have to use 4 parts live instead of 2. A hard and stiff, homogeneous mass with a fine, very smooth contact skin is obtained Product is 0.135 i.e. riel lower than the diohte of Product in the previous example.

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EXAMPLE 3

Proceed as in example Z? but m & m uses 0 ₉ 4 healthy sea water instead of 0.1 {the finished product has the same kisser appearance as in examples 1 and 2; the density 0.265 is somewhat lower than that of the product iaa Example I; the product obtained is less than that in the example

EXAMPLE 4

You seduce as in example 1 »but you use 1 part Sea water instead of 0.1 j the finished product has the same external appearance Look like those in examples 1 to 3 - the view this material is 0.235, while the curing time is longer is than in example 1.

EXAMPLE 5

.MAN verfäihrt as in Example 1, but the various ingredients at a temperature of about 4Q ^fi C instead of 34 * 0 vermischtjdas finished product, its density is 0.225, has the same appearance on Kussere as in Examples 1 to. 4

EXAMPLE 6

One seduces as in Example 1, but one uses 45 parts of silica-containing sand instead of 15; the finished product has the same appearance as in Examples 1 to _5f and its density is 0.350.

EXAMPLE 7

in the same way as in example 1, but 5 parts are used 909831/1283

BATH ORIGINAL

concentrated hydrochloric acid instead of 6; the product obtained has a density of 0.205.

Figure 1 represents one according to the method of the present Invention usable calculator.

This calculation table corresponds to the case τοη 15 parts neutral pullstoffee (gravel containing sand) and 100 parts Resin "A" (that in Example 1) and a catalyst from a mixture τοη 6 parts of hydrochloric acid, in the concentrated

consists th state, and 1 part concentrated sulfuric acid; this Table applies to the temperatures of Example 1. The straight lines (I) (II) (III) and (17) correspond to, respectively Examples 1, 2, 3 and 4.

This calculation table comprises 3 ABC scales. The A scale indicates the density of the material obtained. The C scale indicates the number of parts of the inhibitor (Seevaaser) for 100 parts of the aforementioned resin. The B scale shows the number of parts of asbestos _{f is} always for 100 parts of resin.

If one determines the diet to be obtained, e.g. O, 40, the quantities of asbestos and salt water to be taken are obtained in the following way: leave some straight line of orientation , for example the straight line Δ. on the Division 0.40 of the Sgala At the overlap with the division scale B indicates the amount of asbestos, i.e. hler 1 Part ι the overlap with the C scale indicates the amount Inhibitor, i.e. here about 0.1 part. Of course

909831/1283 BADORiGlNAI.

if one looks at another line instead of the straight line but also through the same point on the scale IA ran β if one had a different working pair for the sets swelling coat and inhibitor, and this pair would have * incidentally corresponded to a different value for the duration of the polymerization.

Since the duration of polymerization is essentially dependent on the quantity ratio of the inhibitor (if the other factors assumed to be permanent for the construction of the table mentioned are real), the determination of this duration allows the stated quantity ratio to be determined; in these conditions, if has further determined the su-sustaining Biehtf ordered only the possibility of einsigen g®ra ~ the line, and the übereete & eldUsüß this straight line with the scale B has the au gebrnmeheiid © KSSG '^ vmfeBlvpts asbestos.

EXAMPLE β

The procedure is as in Example 1, but 3 parts of sulfuric acid and 1 part of paratoluenesulfonic acid are used as the catalyst.
EXAMPLE 9

Kan procedure described in Example l but nan _t benutet instead kieselerdhaltigen sand a group consisting of 60 parts of kaolin filler.
EXAMPLE 10

Proceed as in Example 1, but instead of the

909831/1283 ^ßAD

For sand containing silica, a filler consisting of 35 parts of clay is used.
BBISPIBL U

The procedure is as in Example 1, but a filler is used which consists of 10 parts of carborundum, 10 parts of barium sulfate and 10 parts of silica. EXAMPLE 12

A lot is shown in Example 1, but two different ones Mixtures are produced (one is similar to that in Example 1, but consists of 0.5 part asbestos and 45 parts silica containing Sand, while the other is similar to that of Example 1, except that it contains 6 parts of asbestos * contains); these thoughts become separate but equilateral in the same fixed, open, for the production of ron Walls made up form injected into it (the rolletäfidige section the compounded mass hardening in the form is shaped as a rectangle)! ror hardening rerhurt that the first mixture (which will form the 'crust' of the Vand) mixes with the wide mixture (which will form the Hers of the wall, τοη lower density), by means of a fixed one Parallelepiped guide device, its upward side slightly above the ftrenssone is where at least one of the has just hardened and taken on its band shape.

BBI8PHL 13

You get the same procedure as in example 12, but you go through it

Impregnation of stiffened cardboard into the mass, sur time 909831/1283

BATH ORIGINAL

the injection into the mold 3 these tubes are introduced into the zone of the mold that delimits the heart of the wall to be obtained.
EXAMPLE 14

The procedure is as in Example 1, but the lake water is replaced by spring water.

EXAMPLE 1 5

You seduce as in example 1, but you use one Phenol-Formol type resin in solution in an organic Solvent; the curing time is much longer.

EXAMPLE 1 6

The procedure is as in Example 1, but using a resin with a low degree of polymerization, which is initially in powder form is, and is transferred into a liquid.

The present® invention is of course not of limited to the embodiments described above, which have only been given as examples.

90983 1/1283

Claims (1)

EXPECTATIONS 1- production method sur daduroh in a Kunstpolymermateriali that it consists in forming a reaction Btasse su from which by curing due to polymerization of said material is formed by reacting at a temperature between 5 and 50 C ⁹ "C a previously into a liquid or acidic state and thermosetting phenolic resin or the like of low degree of polymerization, a catalyst of polymerization, a polymerization inhibitor, and by regulating the proportions of the various components of the mixture and the relative times of their introduction, to obtain a material of a given density see below obtain. 2- process vegetables according to claim!, Characterized in that that you can evenly use the aforementioned ingredients a swelling agent mixed, the proportion of which is regulated so that the given density of the material can be between 0.015 and 4 « 3-method according to claim 2, characterized in that that one for a Hars and a catalyst of given types and proportions (depending on the named Hars) and for a swelling agent and an inhibiting agent of given kinds, and means in the given conditions experience-based calculation tables, and duroh 909331/1283 ORIGINAL the choice of the density to be obtained, that for the proportions of the swelling agent and the inhibitor EU taking value pairs determines, veil the quantity ratio of one of these last two components influences that of the other, as can be seen from the calculation tables. 4 - Method according to claim 3, characterized in that that one also chooses the duration of the polymerization, whatever the proportions of the swelling agent and inhibitor leads to a single pair of values. 5 - The method according to claim 2, characterized in that one acts only on the quantity ratio of the oil-rolling coat in order to regulate the density. 6 - Method according to claim 2, characterized in that that the aforementioned swelling agent is a substance belonging to the asbestos group. 7 - The method according to claim 2, characterized in that that the quantity ratio of the swelling agent is between 0 and 25 * depending on the weight. 8- method according to claim 1, characterized in that that one or more fillers are evenly mixed with the aforementioned ingredients. 9 - The method according to claim 8, characterized in that that the aforementioned filler is a silicon substance is. 909831/1283 10- method according to claim 8, characterized in that that the aforementioned filler is a calcined mineral substance. 11- method according to claim 1, characterized in that the aforementioned, in liquid or seeds State transferred? Resin from a solid, in a corresponding liquid medium dissolved or suspended poly-condensate consists" 12 - method according to claim ll, characterized by that the form under which the aforementioned resin is mixed with the other components of the mixture, has a viscosity corresponding to a viscosity measured near 20 & C between 30,000 and 70,000 centipoises is equivalent to. 13 "* Method according to claim 12, characterized in that that the aforementioned resin is of the phenotype. 14- method according to claim 13, characterized in that that the aforementioned viscosity, measured near 2OSC, is between 45,000 and 65,000 centipoises. 15- method according to claim 14, characterized in that that the aforementioned resin is in alkaline catalysis is preserved. 16 - The method according to claim 11, characterized in that that »the resin is made up of a compound which has at least one phenol function and of one Compound which has at least one aldehyde function. 9 0 HB 3 1/1 2 8 3 17- method according to claim 1, characterized in that The aforementioned resin is made of ordinary Phenol and formaldehyde are shown 1st. 18 «Method according to claims 14 and 17, daduxjh characterized daas the polycondensate from which said Resin is obtained in alkaline catalysis, and that the aforementioned liquid medium eats water. 19- method according to claim 18, characterized in that daos the mentioned viscosity, close to 20 * C measured, is between 52,000 and 60,000 centipoises, where daa pH. is between 4.5 and 5.3. 20- method according to claim 1, characterized in that that the aforementioned catalyst is an acidic catalyst. 21- method according to claim 20, characterized in that that the aforementioned acid catalyst reads a strong, mineral or organic acid, 22- Process according to claims 13 and 20, characterized in that the proportion of acidic catalyst, depending on the resin, is between 2? and 15 'is weight. 23 * Method according to claim 22, characterized in that that the aforementioned strong acid is concentrated hydrochloric acid and / or sulfuric acid. BATH 9 0 9 8 3 1/12 8 3 24 method according to claim 23 »characterized paratoluene sulfonic acid is added to the aforementioned acid or acidic solution. 25- Process vegetable claim 1, characterized in that that the inhibitor is made from a non-alkaline saline solution consists. 26 method according to claim 1, characterized in that that the inhibitor consists of water. 27 method according to claim 1, characterized in that that the inhibitor consists of seawater. 28 method according to claim 1, characterized in that that the quantity ratio of the inhibitor, depending on the resin, is at most 5 # by weight. 29 method according to claim 1, characterized that one only acts on the quantity ratio of the inhibitor, to regulate the polymerization time. 30- method according to claim 1, characterized in that that you can use the aforementioned jstandteila. under . Air protection mixed. 31- method according to claim 1, characterized in that that one mixes the aforementioned ingredients under protection from light. 32- The method according to claim 1, characterized in that a plasticizer is used with the aforementioned ingredients mixes evenly. 909831/1283 33- method according to claim 1, characterized in that that you get powder-like with the previously mentioned bedding parts vulcanized rubber mixed. 34- The method according to claim 3 ?, characterized in that the softener ^{n is} thiakhol ⁿ . 35 - The method according to claim 1, characterized in that that you work continuously. 36- method according to claim 1, characterized in that that the mixture is carried out continuously, that it is continuously transferred into the hardening medium, unless that Shape, the extruder or tthnlioh.es, and the hardened material is continuously out of shape and fihnl. drawn _ '. 37 method according to claim 1, characterized that the mixture is carried out continuously, and that one they continuously point to an inventively fixed point Surface transferred, capable of receiving the hardened material. 38-process vegetables according to claim 1, characterized in that that finally the catalyst is added to the mixture of the other ingredients and mixed. 39 method according to claim 33, characterized in that that before the introduction of the catalyst, the temperature of the mixture between 15 and 403C. BATH ORIGINAL 9098 3 1/128 3 L e e τ s e i t e