DE2003111A1 - Process for making molded thermosetting articles - Google Patents

Description

"Process for the manufacture of molded heat-resistant b & rers

The priority of registration in the V.St.A. dated February 28, 1969 is used.

The present invention relates to a method of making shaped articles from thermosetting polydiene polymers or copolyraers. More particularly, this invention relates to an extended chain polydiene elastomer sheet or sheet which is formed into a rigid, hard resinous article by placing the sheet in a heated mold. The elastomer can be weighted down with various types of powdered filler materials, such as metals, Met «11-oxides, metal borides, metal carbides, metal leashes, asbestos,

009838/2069 BAD ORfGlNAt

Silica, talc, fluorocarbon hareen, polyesters and hydrocarbons or with various types of fiber Reinforcement materials, such as polyester, polyamides, glass and Netalle or both.

The thermosetting, cross-linked, eyclized polydiene resins belong to the family ▼ on Harren, which by cross-linked, linear-extended Chains characterized by cyclized aliphatic groups are discussed in the pending applications Serial No. 531 026, filed March 2, 1966; Serial No. 563 975, filed July 11, 1966; Serial No. 570 171, submitted on August 4, 1966; Serial No. 565,074, filed July 1st 1966. It is assumed that the polyether copolymers, the hydrocarbon copolymers and the internally plasticized Forms as described in these copending applications in the practice of the present invention as well as the chain extenders described and also the peroxide initiators listed therein can be used and incorporated therein by reference.

Thermoplastic material was used to manufacture Articles used in Ponowerkseugen. These objects were made by pying a plate in a mold with one another coordinated shapes and the object was formed by applying heat and pressure. The so

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manufactured objects had the inherent disadvantage because they are not in the event of subsequent exposure to heat were fora resistant.

When fillers or reinforcing materials were included, curable polymers could be used in molds with coordinated shapes, but special processing and storage conditions were required to prevent deterioration in product properties. The similar shape and QrUAe of the tools was boachrSnkt by schlechtan deformation characteristics of hitsehärtbaren harp. Manufactured parts often had widespread fluctuations in filler content from the edge to the center of the compact.

It has now been found that a Polydiane polymer resists can be, which results in a stable rubber-like plate, from which objects hardenable by means of process engineering alt Forawerkseugen can be produced with coordinated shapes. Thus the present Br- " findung de «Fmohaann to manufacture hitshardenable molded articles, old with a lightness and an expediency that has never been seen before in the treatment of hit-failures Materials were achieved together. Thermosetting resins of this invention can be dry, non-tacky Plates are processed which do not require special storage These panels can be made to fit easily

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Be clipped in the tool and show a regulated Flow during feeding, so that the fluctuations in filler concentrations ic of the molded article are eliminated, what BU Yerbeeserten Endelgensohaften leads.

The polydiene prepolymer as "for producing the thermosetting resin material of this invention are used should besitsen predominantly seitecständige vinyl groups which are lied on alternating carbon atoms of the Kohlenetoffhauptkette, and make up preferably at least bot olefinisehen unsaturation and preferably have a molecular weight of about 500 up to about 3000, although higher molecular weights can be used if viscosity is not a problem. The preferred polydiene is 1,2-polybutacliene, although 3, H-polyIsOPrSn is also suitable. Difunctional compounds characterized by terminal substitution are preferred, although other polyfunctional prepolymers containing more than one functional group near the opposite ends of the molecular chain, but not necessarily in the end pitches, may be used. In general, precautions against substituted prepolymers are the arboxy-substituted compounds, Diaaino-suketulerte compounds or other poly * ien-frtpolyers, which former functional groups have torsion in the bundles of MIy, are also used mti

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Punctures are preferred, but the recipe can be sur Adaptation to the use of prepolymers with a different number of functions can be set.

The selection of a suitable organic chain extender depends on the functional groups on the prepolymers. Where the functional groups are attached to the prepolymer hydroxyl groups, the chain extender from the group of diisocyanates, diacid halides, dianhydrides, dicarboxylic acids should be selected or d diester. Where the functional groups on the prepolymer are carboxyl groups, the chain extenders should be selected from diepoxides, diamines, diols and diaslridines. Functional amino groups on the prepolymer require chain extenders selected from diisocyanates, anhydrides, dianhydrides, carboxylic acids, diacid halides, diesters and diepoxides. The aliphatic or aromatic organic chain extenders are preferably difunctional; however, they may functionally contain groups in an amount in excess of 1 as the formulation can be adjusted to accommodate the use of such materials. It is believed that the properties of the elastomeric sheet can be changed by including compounds which induce specific cross-linking, such compounds being hydrocyanic compounds, polyisocyanates, polyamines, polyepoxides, polyaziridines and other compounds known in the art could be.

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Typical diisocyanate compounds that act as chain extenders used in the methods of the present invention can include:

Table Σ

1. 2, ^ - toluene lyocyanate

2. Hexamethylenediamooyanate

3. 2 _{tons of} 6-toluene diisocyanate

4. Dianisidine diisocyanate

5. 1,4-bensene diisocyanate

6. Ptp'-Dieooyanatdiphenylmethane

7. 1-chlorophenyl-2,1-diisocyanate

8. Trimethylene diocyanate

9. Pentaethylene diisocyanate

10. Butylene 1,2-dilocyanate

11. Butylene 1,4-diisoqyanate

12. Xylene diioocyanate

13. 2,4-cyclohexylene diisocyanate

14. 1,1-Oibutyl ether diisocyanate

15.!, E-Cyclopentanediisooyanate

16. 2, '; Indenediocyanate

17 Dipbenyl metal diisocyanate .S. 1,5-naphthalene diisocyanate 19 · triphenyl ethane cyanate

Typical, as chain extenders according to the present invention

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Usable acids and anhydrides are:

Table II

1. Adipic acid

2. Fumaric acid

3. 1,4-Cyelohexmndioarbonaäur ·

I, terephthalic acid

5. Malonic acid

6. Trieer Acid (Emery 316 2-D)

7. Diaeric acid (Enpol 102 2 and 1018) Empol Diiner Acids "

by Emery Industries.

8. Asttlaic acid 9 · sebacic acid Ιο. Isophthalic acid

II. Kndo-ois bicyolo (2.2.1) -5-hepten-2,> dicarboxylic dianhydride

12. Succinic anhydride 13 * Dodeoenyl succinic anhydride 1 * .. tetrahydrophthalic anhydride

15. Hexahydrophthalic anhyaride I

16. Maleic anhydride 17 · Phthalic anhydride

18. Glutaric anhydride

19. 1,4,5,6,7,7-Hexachlorobicyclo- [2.2.I] -5-hepten-2,3-dioarboic anhydride '

20. Tetra-chlorophthalic anhydride

Suitable dianhydride and polyanhydride chain links

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include the following:

Table III

1. 3 »3 ^? »4 ₍ 4 * -BenKophenontetracarbone & uredianhydrid

2. Polyamalainaturepolyahydride 3.

5. 1,2,3 "4-Cyβlopentant" traoarbonsSuredi enhydrid

Suitable diepoxyd chain extenders include the following T able IV

1. Epoxy NoYOlacs

2. Bia-epozydieyolopentyl ether of ethylene glycol

3. Kpiohlorhydrin / Biephenol-A type

4. 1-Epoxyethyl-3,4-epoxyoyolohexane 5 · Oloyolopentadlenioxyd

6. Liaonendlozyd

7. Bi- (2,3-epoxypropoxy) benzene

8. Vinyl cyclohexane dioxide

9. 3 "* - Epoxy-6-" -ethylcyclohexylmethyl-3, ^| I-epoxy-6-iBethyloyelohexanecarboirylate

10. Zeaxanthine diepoxide

11. o ^ lO-epoxy - ^ - hydroxyoctadecanoic acid, triester with Glycerol.

Unsuitable · Diiaine, Oiiaid and Trlinid Xette Extenders Include the following:

BATH ORIGINAL Table V

4. 1,6-hexane-H, N'-diethylenediamine, 1,6-hexane-N, N ^f -dipropyleniiain J. 1,7-heptane-M, M "-diethyleniol %. i, 7-heptane-M, M ^f -dipropylenimine

5. l, 8-Oeta "-M, ll" - <litthyleniÄiii

6. 1,8-Octane-S, M ^{f -dipropylenlaln}

7. i _> 3-Di- (carboxy-H-propyleni »id) -benzene

8. i, 3,5-tri- (carboxy-N-propylenimine) -benBol

9. i, 3-Di- (ethylene-H-i, 2-but7limine) benzene

By reacting the liquid polydienes with the chain extenders can an elastomeric material be obtained » which has a higher molecular weight. The chain lengthening reaction is Torsugweise at Uragebungs- or slightly elevated temperatures. The reaction temperature and the reaction times will vary according to the chain extenders used and it is to be understood da * the presence or absence of a catalyst has an influence on the chain elongation reaction will have on the reaction conditions. By suitable selection of the Kettemrerlangerer, volatile secondary checks can be made to «be limited to a minimum or avoided entirely, however can be a · degassing stage to remove any ·] * air, which Böglioherweiie introduced during the Hiach stage has been beneficial.

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The curing of the elastomer to produce a hard, hi-curable resin requires the inclusion of a free radical initiator, preferably a peroxide. This peroxide can be included in the initial mixture of the liquid polymer, or it can be ground into the elastomeric intermediate, where it is mainly dispersed in the unreacted state through the entire chain-extended elastomeric intermediate. After applying heat in the temperature range of between about 65.6 to about 204 ⁰ C (150 to about * »OO ° F) the peroxide is activated and causes a hardening of the elastomeric material for the production of a hardened, heat-hardened resin base mass, which has a Barool- Hardness of at least about 25 and good chemical resistance to nitrogen tetroxide, nitric acid, concentrated sulfuric acid, sodium hydroxide, acetic acid, halogenated hydrocarbons, acetone and hydrocarbon solvents.

To divide this harse, os is preferred, the polyfunct *. lelle polydiene with the polyfunctional organic "Attenverlängerer in approximately stoichiometric proportions to mix. Assume, however, that the purpose of using a chain extender is: "It is molecular weight of the prepolymer to the value which gives elastomeric properties. Materials which preferably have about three functional groups

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can be used in relatively smaller amounts, in order to vary the “lastier properties” further below. If also the approximately inconsistent proportions of polydiene and chain extenders are avoided, small amounts of organic chain extenders are used when polythese are used, which have a higher molecular weight of 15,000 and above In this way elastomers with a higher * hydrocarbon content are obtained. The amount of peroxide initiator used in these hardnesses will vary depending on the feroxide initiator and the polydiene used. In general, the amount of peroxide used will be in the range of about 0.5 to 10 Qew.-X of prepolymers and in particular within the range from ι * «a 2 to about $ 6. Examples of typical organic peroxides which can be used in dlesesi processes are shown in the following table.

Table VI

1. Di-tert-butyl peroxide

2. 2,5-DiBMthyl-2,5-bis- (tert-butylperoxy) -hexane

3. o-Buty1-4,4-bis- (tert-butylperoxy) -hexyne-3

H. 2,5-Dimethyl-2,5-bis- (tert-butylperoxy) -hexyne-3 5. tert-Butylperbeittdat

7 · methyl ethyl ketone peroxide

S. cumene hydroperoxide

9. Di-M-methyl-tert-butyl peroarbamate

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Table IV (continued)

10. Lauroyl peroxide

11. Ethyl perozide

12. Deeanoyl peroxide

13. tert-butyl peracetate

14. tert-butyl peroxylaobutyrate

The method of the present invention begins with the molding of the elastomeric sheet. The plate material can according to Any of the conventional methods, such as e.g. the removal of the plate from a rubber mill, from one Calender or elnfaoh by pouring the liquid polymer Mix on a flat surface. The elastomeric plates produced in one of these ways can be converted to a suitable Cut to size and stacked for later fabrication.

The final finishing is by placing the plate carried out in a heated mold. The mold is closed for a period of up to approximately 10 minutes, the time depending on the recipe.

Numerous variations can be made with those according to the present invention Invention produced panels are carried out. Fillers and foaming agents can be used to manufacture panels which have a wealth of properties for widely used

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different applications aside. In addition, others can polyfunctional polymers included in the initial Folymer Mieehung «to produce over-curable resins, which have slightly different characteristics.

Fillers which suitable for inclusion in the Platt erial Ensat of the present invention, may be selected from metals such as eB powders, whiskers or turnings from iron, Volfraa, nickel, vanadium, copper, magnesium, aluminum% minium. Zircon, tantalum, zinc, cadmium, chromium, niobium, and others which may be suitable; Carbides, nitrides, borides, oxides and silicates of metals, where the metals can be selected from titanium, tungsten, magnesium, aluminum, copper, zinc, cadmium, niobium, tin, lead, uranium, molybdenum, iron and others, which may be suitable; inorganic minerals such as talc, silica, asbestos, glass and clay; polymeric materials such as sB particles or fibers of polyamides, polyesters, polyacrylonitriles, polyolefins, epoxies, phenol-formaldehyde λ Kondensationeprodukten and melanins; and inorganic salts, such as halides, chromates, and carbonates clay, sodium, potassium, calcium, magnesium, barium, else, aluminum, silicon, and zinc. Although a wide variety of

Materials as fillers or reinforcing materials

1, it is obvious that those Fillers, which degrade at higher temperatures or react with the polymers under the process conditions, do not

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are suitable for purposes of this invention. The particle size of the filler materialB is used by the application the plate is intended to depend on. Although no particular range of particle sizes is preferred, it is to understand that the particle size should not be so small as to cause excessive dusting and oolite as well the particle sizes should not be so large that they cause clogging the processing equipment leads. The filler and reinforcing materials can be used in amounts up to 80% by weight of the total mass are used and still produce panels which have excellent stability and machinability own.

The fillers can be processed in one of two stages be admitted; while mixing »de * ™ polymeric liquid initially or by sin-milling into the elastomeric intermediate stage. In general, the choice in this matter depends on the type of processing equipment that is available is.

For certain uses, molded articles are made from molded Hars plates, is desirable. Panels off Schäuaten elastomers can by introducing a foaming agent made in the initial end of the polymer will. Blowing or foaming agents that have been found suitable are the following:

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Table VII water

propane

Peatan

Triehlorfluonsethane Diolordlfluo methane

1,2-dichlorotetrafluorotthane ™

1,1-difluoro-1-chloroethane

Dinltrosopentaaethylene tetraBine Oxybia (bensol sulfone hydraside)

2,2-Aeobisieobutyronitrile

AasraniuBoarbonate Aiodloarbonaald

Once the mixture of the flflsaice poljaere Reaktionsteoperatur In the area nriaenen 23 and 9O ⁰ C is subjected to the BlIh- or Johau-Ittel sJctiriert, while check forms the elastoaere material. The plates of the layered elastomeric material can be plaolert the heated fonwerkaaug and hardened afterwards.

Bia other «means for the production of hit-hit bars · Sobluae follows the same procedure as described above, take into account, however, the temperature of the chain extension

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reaction and the foaming agent selected, so that forauag the elastic plate does not foam. Be accordingly the foaming or blowing agents in the elaetoaeren material in a la substantial unreacted state and the foam or blowing agent is distributed as soon as the plate in the received Verkseog is placed, activated, sur making a Foam, which then turns into a hard, hit-hardened hair is hardened.

Once the use of a resin with a modified specification Required can be polyether, polyester, or Hydrocarbon Harse into the initial polymeric mixture be incorporated. So that the polymers participate in the Eettenverllngervagsreaktion can participate, it is desirable to use polymers which have the same polyfunctional parts Groups have how tie in dea polydia are present. Venn hence the polydiene hydroxyl groups as functional groups desirably, the modifying polymer becomes Have hydroxyl groups and the like applies to the carboxyl and amnogrupp »as functional groups. The correlation these functional groups on the modifying polymers with the kind of polydiene it enables connections, old the glelo ^ ien lettenverlängerer χα react.

Several long-chain polyfunctional polyethers are for one Suitable for use as a modifying agent in this Hars system.

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Choose from a wide range of polyfunctional ones PolyAthers should have the intended properties the end product can be regulated. In general, all of this invention can be substituted or unsubstituted Polyoxyalkylene poly oils can be used. Typical ge « suitable · Polylther are ».B. following·!

τ a b · ι ι '· viii

1. Polyoxypropylene glycol

2. Polyozypropylenetriol ™

3. Polyocyte ethylene glycol
4 · polyoxybutylene glycol

5. polyoxybutylenetriol '

€ . Polyethylenoxyethylene glycol

7 · Polyethylene ethylene oxide riol

8 "polyoxyethylene glycol

9. Polyoxylethylene triol.

Diethylene polyfunktion "cases hydrocarbon polymers which (hydroxy wad carboxyl groups as functional groups which are ffthig" old functional Qruppen of XettenT "rläng · - vr * react su b + sitsen can τοη using

Butadiene polyaires and polyesters are produced.

♦. · ■

see polyfunctional hydrocarbons, which are called

Modifying agents are suitable »are s.B. the following:

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Table II

1. 1,4-polybutadiene diol Hoeopolyrmeree

2. Dihydroxy - !, 4-polybutadieastyrene copolymer

3. Dihydroxy-1,4-polybutadiene acrylonitrile copolymer

4. Hydrogen-saturated 1,4-polybutadiene diol honeopolymer

5. Hydrogen-saturated dihydroxy-1,4-polybutadiene styrene copolymer

6. Hydrogen-saturated dihydroxy-1, Ί-polybutadiene aoryl nitrile copolymer «8

7. Waeeeretoff saturated · 1,2-polybutadiene homopolymer

8. Polyieobutylandiol Hoeopolyaeree

9 · Di carboxy-1 _t 4-polybutadiene-HoKopolya «s * e8

10. Dicarboxy-1-4 polybatadieaetyrene copolymer

11. Dioarboxy-1.M-polybutadiene acrylonitrile

Dl · ·· Poly »» r »n kOnn * n duroh Polyaerisatlor naoh methods gMriUI dm state-of-the-art; unsaturated Kohlemraaeretoffe, vie κ.B. Ieoprene, butadiene, isobutylene, Styrene and acrylonitrile can chemise their polymerization old Have terminated compounds selected to yield the intended functional groups.

Polyfunctional polyesters can be selected from a wide range of clay miscible or immiscible compounds are, which hydroxyl or carboxy groups act as functional groups that are able to with the functional Groups on the chain extender react accordingly.

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Typisoh for dl · polyfunctional polyester, which as modiflsiendttel can be used are the following:

OO
HO - R ¹ 4 - O - C - R ² - C - O - R ¹ * _Λ OH

or

OO OO

HO -C- R ^ + CO- R ¹ - 0 - C - IT 4 - _m C - OH

wherein R represents radicals selected from the group consisting of made of phenylene, tetramethylene, pentamethylene, decamethylene, Xethylene, propylene and F> itylene; R means chemical Staaa parts from the group consisting of adipin, sebaein, Terephthal, isoterephthal, oxal, olutar, amber, Aselalic and malonic acid and ■ represents a number which sufficient, a molecular weight of preferably in the range Lend from 500 to $ 000 tu.

The following specific embodiment is aimed at this invention explain further, although no restriction is intended is.

example

The connection for the prefi plate was made in the following manner manufactured:

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100.0 Qev. parts of a 1,2-polybutadiene-Harses (approximate molecular weight 2000) (150 ⁰ F) to 65.6 vorerhitit ⁰ C and 1.0 parts Qew. Triaethylolpropan (TMP) Eugegeben. This solution was stirred until the TMP was dissolved. 9 * 9 parts by weight of 2,4-Toluoldilsocyaaat were added to the mixture and stirred until homogeneous. The mixture obtained (at 65.6 ⁰ C (150 ⁰ P)) was poured into a polyethylene bag and the shutter closed Bit an adhesive strip. The bag was then placed in a Luftsirkulationsofen for 16 hours at 65.6 ⁰ C (150 ⁰ F), where a rubbery composition was formed.

The Ound. was separated from the polyethylene bag and two-walsen-StandardguBoaiaühle banded on a vorerhitsten (F) 65.6 ⁰ C (150 ^0). The following ingredients were ansohlieAend at 65.6 ⁰ C (150 ⁰ F) below the belt in the order in which geseigt, sugegeben:

H ₉ 5 parts by weight methaorohoxypropyltrlaethoxysilane

6.6 ow. Parts Diouay! Peroxide
450.0 parts by weight 0.062 sai (250 aesh) silica powder 4.5 parts by weight calcium stearate

There was enough time to mix in each ingredient la gated the tape in a homogeneous way. Ia AnsöhluA the completed connection from the Ousnia mill was removed from the mixing process as a single sheet of material.

The plate was cooled to 23.9 ° C (75 ° F) and it was frozen

009836/2069 - 21 -

posed, daft ti · dry, tack-free and guami-like. A one-quarter piece approximately 1.27 x 12.70 χ 0.64 ob (1/2 5 χ 1/4-inoh) was cut from the plate. The stack was pre-heated to tine (177 ⁰ C (35O ⁰ F)) fully positive pre-afore (1.27 cm wide χ 12.70 ο »long (1/2-inch 5-inohes)) before producing a test piece of the dimensions 1.27 x 12.70 χ 0.64 oh (1/2 χ 5 xi / 4-inohes) abandoned. A steady pressure of 98.4 kg / cm ^ (1400 psi) was applied to the joint in the 177 ° C (350 ° F) form for 5 minutes. The resulting pressed part was removed from the FoX ¹ Ii) and cooled to room temperature *

Average properties of the molded plastic part were obtained by standard ASTM methods including thermosetting plastics. The results were as follows: Test Unit Value

Specific weight mm ^ m (pei) I ₃ L4 200) Hardness, Barcol ... (pei) 72 400,000) Flexural strength 998 ₄ Bending module, 23ι kg / cm ² , 944 :, 23.9 ° C
(75 ⁰ F) .26 (: .9 ⁰ C (75 ⁰ F) 98 420 (1

Dielectric ,

constant, 100 KC "*> ^ö

Loss factor, 100 KC - 0.004

Various modifications can be made to this invention without deviating from the scope and content of the following claims.

009836/2069 ^'22 "

Claims (1)

Claim IJ method star production of blown, hardenable resin articles, thereby marked, daft nan (A) (1) a polydiene, velohe0 (i) polyfunctional groups, selected from the group consisting of hydroxy, carboxy and Has amino groups and (ii) a predominant amount of vinyl groups attached to the polydiene backbone, (2) a polyfunctional chain extender capable of n to react with the functional groups of the polydiene and (3) Mixes a peroxide free radical initiator, creating a elastomeric material, which essentially contains the peroxide contains unreacted pore dispersed, is produced, (B) the aforementioned elastomeric material is formed into an elastomeric plate by further processing, (C) the aforementioned elastomeric sheet is placed in a heated mold and (D) the aforementioned plate by the use of hitee and pressure see below a »hard, thermoset molded resin article cures. 2. The method according to claim I _1, characterized in that the polydiene is selected from the group consisting of 1,2-polybutadiene and 3,4-polyisoprene. 3 «Method according to claim I ₉ daduroh characterized in that the - 23 009836/2069 letteorerlgerer, which 1mbtand · let, »It the functional parts Hydroxyl group * 4 ·· Polydienes su react, consisting of the group from (a) Diisoeyaaat-substituted aliphatic compounds (b) Diieocyanate-substituted aromatic compounds fertilize, (o) diaoid halide-substituted aliphatic compounds (d) Diaeid halide-substituted aromatic compounds »(e) Diocarbonalure-substituted aliphatic compounds, (f) Dioarbonature-substituted aromatic compounds, (g) diester-substituted aliphatic compounds, O>) Di "et * i * -Biibetitul * rten" rozaatleehen connections, .lipb.ti.ch. _n teMrt ^ _{un (t} is. .llphati .. _h . " (W »!« Iridla -. ^. Ti ^ .rt. ,, ««! .Rt ,, _connexions "• selects i« t. 009836/2069 BATH ORIGINAL 5. The method according to claim 1, characterized in that the Chain extender that is able to old the functional ones Amino groups of the polydiene cu react, without the group consisting from (a) diisocyanate-substituted aliphatic compounds, (b) diisocyanate-substituted aromatic compounds, (c) anhydride-substituted aliphatic compounds, (d) anhydride-substituted aromatic compounds, (e) dianhydride-substituted aliphatic compounds, (f) dianhydride-substituted aromatic compounds, (g) dicarboxylic acid-substituted aliphatic compounds, (h) dicarboxylic acid-substituted aromatic compounds, (i) diacid halide substituted aliphatic compounds, (j) diacid halide substituted aromatic compounds, (k) diester-substituted aliphatic compounds, (1) Dieeter-substituted aromatic compounds, (m) Diepoxy-substituted aliphatic compounds and (n) Diepoayd-substituted aromatic compounds selected is. 6. The method according to claim 1, characterized in that a filler material is added to (A), said filler material being selected from the group consisting of metals, metal oxides, metal bides, metal nitrides, metal borides, metal silioates, inorganic minerals, inorganic salts and polymers. - 25 009836/2069 BATH ORIGINAL 7. The method BMb claim 1, characterized in that in Ku (A) a polyoxyalkylene polyol is added. 8 «The method according to claim I ₉ is characterized by the fact that A ■ β» sit (A) a polyfunctional butadiene hydrocarbon chain Hars adds · 9 «method» according to claim 1, characterized in that daA aan su (A) adds a polyfunctional polyester, said polyester from the group consisting of (1) adipates, sebaeates, terephthalates ^ isophthalates, oxalates, Qlutaraten, Supoina ^ ten, Aselaaten and Malonaten selected is and functional groups selected from the group consisting of hydroxyl and carboxy groups that are able to «1t the functional groups of the chain extenders8 react, having. Io. Method according to claim 1, characterized in that smn add a Sohausalttel homogeneous see (A) and this but the production of a foam brings about a reaction, whereby the mentioned fluids from the group consisting of water; Proyan; Butane; Penta »; Trihlorofluoromethane; Dichlorodifluorine «Ethaaj 1,2-Dlohlortetrafluorfithan; 1,1-difluoro-1-chloroethane; Dinitrosopentaeethylenetetrajalnj Oxybis- (bensolsulfonhydrasid); 2,2-asoblsisobutyronitrile; Ammonium carbonate; Asodicarbonasdd; 1,4'-n, n'-DlJaethyl-n, n »-nitro8ottrephthalaMid is selected. 009836/2069