DE1947807A1 - Process to increase the chemical and thermal stability and the flame resistance of bodies made of plastics - Google Patents

Description

Process for increasing chemical and thermal stability and the flame resistance of bodies made of plastics

Many plastics can be processed advantageously and brought into specific and complex shapes, and they can often also be spun into threads and fabricated at low cost. In many cases, however, the moldings obtained in this way have considerable disadvantages and are therefore unusable. For many applications, for example, of molded bodies made of polyamides, polycarbonate, polyvinyl chloride, polystyrene and polyester resins, the softening range, and thus the respective limit temperature for long-term stress, is too low. Dle0e border · temperatures for polycarbonate 12Q about ⁰ C, for lolyäthylenterephthalat about 130 ^σ 0, of polyamides about 105 ° G for polyvinyl chloride TMCT about 90 C.

In some cases, the shaped bodies, for example fabrics for filter material, are also exposed to solvents or chemicals. Since many plastics dissolve or decompose easily under the action of such substances, according to the state of the art on expensive, heavy and laboriously processable plastics, such as offered GpLeLawciae on polyimides or. ' l! ^l "luorcarbcm - Kun .. ^c ifc-

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Basically the Einsata del? Plastics in la; ii, öektöÄ.,. '. Interesting »Lots of plastics! but away from their / light weight«. . Flammability and combustibility are not used in this area *. ■ ■ '■ - ..' -. . -, ...... .. -. >

The subject of the present invention is a method! ZuK Er " ^: Emphasis on the chemical and thermal stability of bodies made of chemically and / or thermally unstable and / or flammable plastics, which is characterized by the fact that the plastic bodies are made from polyesters made from halogenated bivalent phenols or from mixtures of such halogenated phenols with non-halogenated phenols and acid dichlorides, preferably OJerephthalic acid dichloride alone or as a mixture with isophthalic acid dichloride, coated. ". : ·: · -.

The manufacture of the polyester used for the coating ' _t . which is not the subject of this invention ^ is carried out by reacting dichlorides of terephthalic acid or dichloride mixtures of tere- and isophthalic acid, which may contain 1 or 5 chlorine atoms on the aromatic nucleus, whereby these dichlorides can also contain allphötischej saturated dicarboxylic acid dichlorides and / or bisloroformic acid esters with dihydric phenols j in particular with halogenated dihydric phenols or with mixtures of halogenated, dihydric phenols and non-haloed, .dihydric phenols ^ if necessary in organic solvents, preferably in the presence of catalysts at a temperature of 50 to 250 ° G and splitting off from Hol.

As Kn hai Jf? η ta reu at illustrates the preparation d r erf fiidtingsgetaäßen lölykoiulori ';'il; o ir'nr.U '\\' floren Äiüinogruppe- tort in rp ArnIrte, component

or is not part of an aromatic ring system, and / or optionally N-mono- or N-disubstituted acid amides are used. Phosphines, arsines and similar compounds are also suitable as catalysts. They are used in amounts of 0.1 "to 20 moles , based on the acid halide. In principle, the quaternary ammonium compounds of these catalysts, in particular the hydrochlorides or the corresponding salts of the halogenated phenols and the tertiary amines, can also be used .

As hemogenated, dihydric phenols for the synthesis of the invent In accordance with the application of the polyester, both mononuclear and polynuclear phenols are imprinted. Chlorinated hydrochloride are therefore suitable, such as tetrachlorohydroquinone, 2-chlorohydroquinone, Trichlorohydroquinone and 2,4,6-trichlororesorcinol.

Suitable halogenated, polynuclear phenols are, for example, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-Hs- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis - (3 »5-dibromo-4-hydroxyphenyl -) - propane, 4.4 ^f -3) ihydroxy-5.5 ^l -difluorodiphenylmethane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) - 1-phenylethane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) hexane, 4,4 _{^{l-dihydroxy-3}}} 3 ^1, 5 »5'-tetrachlordiphenyl and the corresponding tetrachloro derivatives of 4,4 ^f -dihydroxydiphenyl ethers, 4,4'-dihydroxybenzophenones and 4,4'-Mhydroxydiphenylsulfons, 4,4 ¹ -dihydroxy-tetraphenylmethane, tetra- ^! chlorophenolphthalein.

Compounds come as non-halogenated, non-halogenated phenols? λ the general formula

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in! rage ", has in the Y already mentioned meaning. Typical of these phenols are the dihydroxydiphenyls, for example 2,2 ', 2,4', 3,3 ', 4,4'-dihydroxydiphenyl ^I, 4, 4'-DiIr / -droxy-2 ~ methyldiphenyl, 4 »4'-dihydroxy-2,2! -Dime thy Id iphenyl, 4,4 * - dihydroxy ~ 3,3 ^f -dimethyldiphenyl, 6.6 ^l ~ 3-dihydroxy- -3 »3 ^t ~ <iimethyldi ~ 'phenyl and others;

Dihydroxybenzophenones, such as: 2,2'-, 2,3'-, 2,4'-, 3,3'-, 3,4'- »4,4'-, 4,6'-, 6,6 ' ~ Dihydroxybenzophenone and others; Dihydroxydiphenyl sulfides such as: 2,2 ^r ~, 4,4'-dihydroxydiphenyl sulfide; Dihydroxydiphenylsulfones such as: 2,2 '~, 4,4'-dihydroXydiphenylsulfone; Dihydroxydiphenylalkanes, such as: 2,2'-, 4,4'-dihydroxydibensyl, 2,2'-, 2,3'-, 2,4'-, 2,5'-, 2,6 '-, 3, 3'- ,. 3.4'-, 3.5'-, 3.6'-, 4.4'-, 4.5'-, 4.6'-, 5.5'-, 5.6'- _v . S, ^ '- α3ihydroxydiphenyl-2, 2-propane, 2,2'- or 4,4'-dihydroxydiphenyl f methane, 4,4'-Dihydroxydiphenyimethylmethan ,. 4,4'-Dihydroxydiphenylphenylmethane, 4,4'-Dihydroxydiphenyldiphenylmethane, etc. As the acid dichloride for the production of the polyester used according to the invention for the coating, in particular the terephthalic acid dichloride comes in question whether, for example, the tetrachloroterephthalic acid dichloride is to be included. Suitable ■ mixtures of acid dichlorides can, in addition to isophthalic acid dichloride, also aliphatic, saturated dicarboxylic acid chlorides (branched and branched) such as oxalic, malonic, amber, glutaric, adipic, pimeline, cork, azelaic, sebacic and

Italeoiisäuredichlorid contain. Also icons

-. "Are used as additional acid dichlorides Bischlorameise.nsäureester Examples include the following substances are ι 2jfS-bis ¹ - (4-ehlQrameisensäurephenylester) -pro.pan 'and 2,2 ~ bis ~ 4-Gnlox ^v ~ formic acid (3) 5-dio; hlQrphenyl) ester —propan .. —The bis-chloroformic esters which can be used for the synthesis of the polyesters according to the invention can be prepared according to known "processes by reacting diphenols with phosgene in the presence of tertiary amines as catalysts. (See Makromol. Ghent, j)?,. 1 (1962)). Preferred diphenols for the preparation of bischloroformic acid are 2,2-bis- (4-hydrQxyph.enyl) -propane, 2,2-bls- (3-chloro-4-> hydroxyphenyl) -propane, 2,2-bis- ( 3,5-dl "bromo-4 ~ hydroxyphenyl) propane _y 2 j 2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane, and 4,4 Tetrachlordiphenylolsulfon ^I dihydroxydiphenyl.

In the production of polyesters to be used according to the invention, in which also bischloroformate is used one proceeds advantageously in such a way that one first the bisehlora formic acid ester with the excess. Halodiphenol or with the mixture of halodiphenol and the halogen-free one Brings diphenol to condensation. This reaction. stage does not require a catalyst and ends after about 2 to 5 hours when the excess of diphenol is sufficiently large. Then the terephthalic acid dichloride is added and with the remaining hydroxyl groups in the reaction mixture to react * A catalyst should preferably be used for this.

When using the aforementioned catalysts in the synthesis

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The polyesters used according to the invention are particularly high molecular weight polyesters with molecular weights from 15 to 160,000, preferably from 25,000 to 120,000 of a device (type 200) from _ „, .. ¥ aters Assoc, Inc., USA, was estimated .; The reduced viscosities were at 0, -5. wt .. ^ igen solutions of the polymer in chloroform at 25 ° C in the range measured by means of a falling ball viscometer. The viscosity values are in the range from 0 _r 3 to 2.1, preferably 0.5 to 1.5. '■ · ...

In'organischen are used for the process according to the invention Solvent-soluble polyesters are preferred, which contain terephthalic acid residues as the main part.

In Table 1 are examples of the composition, those polyesters which are suitable for the invention, listed. There are the starting substances and the of synthesis; Specify the quantities used. The details of the Mol percentages relate in each case to the total amount of Säuredichiοride or to the total amount of dihydric phenols, - ~ '.-' "■

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Table 2 shows the properties of the polyesters compiled according to Table 1. The term "reduced viscosity" is defined under Example 1.

A "preferred embodiment of the invention Procedure represents the impregnation of the combustible / plastic body by the polyester solution, i.e. the wetting of the body with these solutions and subsequent drying.

In most cases, those for the coating are grounded the plastic body to be modified according to the invention is made in solution from the outset. Otherwise, the respective polyester after the synthesis solved. The following solvents are preferred: aliphatic or aromatic hydrocarbons, simple or cyclic Ethers and halogenated hydrocarbons. The concentration of the solutions should advantageously be between 0.5 and 10% by weight on the solution, lie.

The polyester solution is applied by painting the plastic body, by spraying the solution onto the plastic

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fabric body pder by dipping the same in the polyester lo-. sings. In the case of the coating of fabrics, ITonwovens and. the like is used advantageously coating machines with appropriate doctor blades.

The bodies so moistened are preferably dried in drying cabinets or drying tunnels and at elevated temperatures.

The thickness of the coating can be varied as required. she depends on the concentration of the solution. However, it can easily be increased by multiple coatings.

One can in the process according to the invention, in particular at crosslinkable plastics, also in the. Proceed wisely that you first make a roughly preformed body from the partially reticulated Plastic with a film made of the respective polyester made of preferably halogenated dihydric phenols or mixtures covered or enveloped by dihydric phenols and acid dichlorides and then this blank thus covered, for example under a heating press, is finally shaped and cured. A such a method can be used, for example, in the case of modification of bodies made of unsaturated polyester resins, epoxy resins and diene-rubber mixtures. The polyester film used here must first pass through. Applying a solution "of the polyester to a base and then Evaporation of the solvent produced v / earth.

In a similar way, pre-hardened foils made of "■: ...,. -109814 /? 06 4-

Polyester also, for the coating of bodies made from chemically and / otter thermally unstable and / or flammable thermo- • use plastic plastics. Here the one with the Polia-covered bodies, however, are heated so high under the press v / ground that the plastic core softens and connects with the slide comes about.

"If a polyester film is used for the coating, the use of adhesives or primers may sometimes be necessary or appropriate for bodies made of thermoplastic plastics as well as for bodies made of crosslinkable plastics. Epoxy resins and polyurethane adhesives in particular are to be mentioned here For example, triphenylmethane-4, 4 ', 4 ¹ ' -triisocyanate in question. Adhesive or primer solution are applied to the surfaces of the film and plastic body to be joined and then the solvent is evaporated. In many cases, the treatment of a ..- Surface, for example that of the plastic body.

By the method according to the invention, the bodies are turned on unstable and flammable plastics. Their properties are fundamentally improved * In particular, bodies with large Surface, such as threads, fabrics and nonwovens, are according to the invention Treatment can also be used where the use of the untreated body is completely impossible. For example Filter cloths made of polystyrene, which .an-der. surface modified according to the invention. * are readily available can be used for the filtration of mixtures of substances which Solvent solvents that dissolve polystyrene, such as aroma * tirjohc coal fuel. The filter cloths

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after coating with polyesters made of preferably "chlorinated -dihydric phenols" and acid dichlorides constantly against these solvents.

Fabrics made of polyethylene terephthalate or polyamides, plural marriage according to the invention have been coated with the polyesters "can easily" be used for decoration in theaters or cinemas because of their flame resistance.

Another significant advantage of the coated according to the invention Body, especially the fabric, llonwovens and the like, is that they are 'stain resistant'. This is also important for wet and! dry filters, because cleaning is made easier. Curtains stay dust-free longer. .1

Another subject of the invention are polyesters made of halogenated dihydric phenols or mixtures thereof halogenated dihydric phenols with non-halogenated dihydric ones Phenols and acid dichlorides, preferably terephthalic acid dichloride alone or as a mixture with isophthalic -. ^ acid dichloride, coated bodies, preferably fqlien, ^ tapes, Threads, fabrics, Ilonwovens and the like, made of chemical and / or thermally unstable and flammable plastics ». ,,. . ? _

BATH

Example 1.:

a) Manufacturing__of_pol ^ ester

In a three-necked flask equipped with a stirrer, condenser and inlet pipe, were 73.6 g of 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 20.3 g of lerephthalic acid dichloride and 20.3 g of isophthalic acid dichloride dissolved in 500 ml of o-diehlorbensol, and the resulting solution was mixed with 0.5 ml of ghinolin. The reaction mixture was stirred to the boiling point of the o-dichlorobenzene heated. After 36 hours of simmering "it was split off theoretical amount of HCl. The resulting polyester (yield 95 g, reduced viscosity 1 * 4, measured on 0.5 ■ wt. ^ igen solution in chloroform) was precipitated with methanol, filtered and dissolved in approx. 1003 ml of chloroform. (The following applies: reduced Viscosity £ red =

spec. = - ~ - 1 ; IJ '= viscosity of the solution,

= Viscosity of the solvent)

b) Coating of a polycarbonate plate

A plate made of polycarbonate having a reduced viscosity 0 "5 (screened eat at 0.5 wt .- $ strength by weight solution in chloroform at '25 ⁰ C) and having the dimensions 20 10 χ χ 1 mm was coated with the polyester solution. After 1 hour of drying at 100 ⁰ C., a uniform Piim of 15 μ thickness was formed, which firmly adhered to the plate. It was thermally stable, non-flammable and did not dissolve even when the coated plate was boiled in water for 8 hours. '

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Example 2:

A plate (1 mm) .. made of polyamide based on terephthalic acid 2,2,4-trimethylhexamethylenediamine with a relative viscosity of 2.5 (measured in phenol tetrachloroethane, 60:40) with a 10% solution of the polyester used in Example 1 coated. After drying at 100 ° C., a film resulted 15M thick. This thermally stable, incombustible film remained stick even after 8 hours of boiling in water.

Example 3i

The procedure was as in Example 1, except that a 5 mm thick Hart — PYC disk was used. The polyvinyl chloride had a K value from 60 to 65. (The K value is a measure of that Molecular weight of a high polymer. It is a constant in Fikentscher's law, which, for example, in the magazine Oellulosechemie JT3, (1932) 60 -has been described). The resulting film remained even after 48 hours of questioning stick firmly in water.

a) Manufacture ^ es_Po!. ^ esters

In the apparatus used according to Example 1 a, 13> 7 g 2,2-bis (4-hydroxyphenyl) propane, 40.6 g of terephthalic acid dichloride dissolved in 500 ml of o-dichlorobenzene, and the resulting Solution mixed with 0.5 ml of quinoline. The reaction mixture was heated to the boiling point of o-dichlorobenzene while stirring. After boiling for 3 hours, the theoretical amount was 30 Mo1 $

BAD ORJGINAL “10 98U / 2064

Hydrogen chloride was split off, and 51.2 g of 2,2-bis (3,5-diehlor-4-hydro: x: yphenyl) propane were added, after which the reaction was over for 30 hours. The polyester was missefal.lt with methanol, filtered off and dried. The amount was 87 g. It was dissolved in 580 ml of chloroform so that a 10 gevi. follow solution present »

A 260 μ thick film made of a copolymer of "vinyl chloride and" vinyl acetate (molar ratio 87: .13) with a K value of 50 to 56 was treated with the polyester solution on both sides: ■ by dipping the film in the solution and. subsequent drying (1 hour at 70 ° C) coated. The firmly adhering protective layer was each 50 ρ thick. It was difficult to detach from the base plate, even under severe mechanical stress (for example due to kinking).

A similar film made from a copolymer of vinyl chloride and maleic anhydride (80; 20 molar ratio) was coated with the polyester in the same manner. It resulted an equally stable overall structure.

Example 5; ·

A 1 mm thick sheet made of polycarbonate according to Example 1 was treated analogously to this example with a mixture of two polyester solutions (10 wt. in each case in chloroform). The one Polyester corresponded to that prepared according to Example 1a. Of the

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Polyester differed from the former in that that in the synthesis instead of 2,2-bis- (3,5 ~ diehlor ~ 4-hydro?: yphenyl) -prDpan the bis (4-hydroxyphenyl) propane used was v / orden.

After the treatment, the polycarbonate plate was protected by a 40 μ thick polyester layer. This withstood boiling in water for 0 hours and "adhered firmly to the plate.

Example 6:

A 2 mm thick plate made of Weieh PVG (containing 70 ^{parts by weight of suspension polyvinyl chloride with an XV, r} ert of 70 and 30 parts by weight of dioctyl phthalate) was with a. Coated 10% polyester solution according to Example 1 (reduced viscosity = 1.4). After drying for 2 hours in warm air, a sheet protected by a 25 / x thick polyester layer was obtained.

Example t :

. A 2 »5 mm thick. Epoxy resin panel on the basis of. 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin (containing maminodiphenyl methane as hardener), v / which had been pre-hardened by heating to 170 ° G (10 minutes), vmrde on both sides with a 100 jx thick film Polyester (basis: 80 Mo1 $ 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 20 KoVfo tetrachlorohydro-. Quinone, terephthalic acid and isophthalic acid dichloride, ratio ■ 1: 1) coated. The composition layered in this way was pressed under a press at 170 ° 0 and 80 kp / cm ^{2 for} 120 minutes, and the epoxy resin was cured as a result. A strength of the molded plate was an inlaid iron Forrarahmen of 1,8mra _m m? ^^ ^m 1098147.206-4 ■■ 'bad

achieved. The plate is excellent due to the polyester exterior Properties on. It was dirt-repellent and chemically resistant. Due to its good electrical properties, the Plate can also be used in the electrical sector.

Tab e 1 1 e.

Poly O .Terephthal ■ '■ ι 75 ■ isophthalic acid - ■ halogenated bivalent M015S not halogenated 2-valued ester <o 3) acid di- dichloride Phenols 100 Phenols .No. ~ 4) chloride
Mole% M0I5S ', - Type Type Mq1? S 1) C -5) 100 ■ "■ '■■. ■■; ■ - 2.2 bis (3.5 di ο ⁶⁾ - ■ ■ '' chlorine-4-hydroxy- * 80 co 7) ■ '■ ■■■ -. ■■ ' phenyl) propane 2) r- 8) 100 - II Il 70 2,2-bis (4-hydroxy- 20th . ? ■) -. ■ ■ 60 phenyl) propane 100 _ Il H 50 ti 'ti 30th .10) 100 Il Il 8Ö ti It 40 100 - '■■■ Il H - 70 Il It 50 11) 100 Il Π 60 ρ, ρ'-diphenol 20th 100 20th Il II 100 Il It 30th 100 Il Il Phenolphthalein 40 12) 100 Tetrachlorodiphe 50 _ mm 20th nylene sulfone 13) 100 It It 100 2,2-bis (4-hydroxy- 50 25th phenyl) propane 80 2.2 bis (3.5 di chloro-4-hydroxy-. 80 phenyl) propane 80 Il Il 100.
i. 2,2-bis (4-hydroxy- 20th phenyl) propane Il Il - ■ ν · '-. ■

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16)

- '17)
ο
co
co

18)

19)

20th

21

75 100

100

100

100

■ 100

100

100

η η 80 2,2-bis (4-hydroxy- 20th • _Λ
i '<Γ \ pheny1) -prop Cl-J
4> ti H 70 Il ti 15th ψ Tetrachlorohydro- 15th O chinone 2.2 bis (3.5 di 70 20th chlorine-4-hydroxy phenyl) propane 2 j 2-bis-t 3-chlorine- - 10 4-hydroxyphenyl) - propane 2.2-31s- (3.5-di- 60, »» 20th chlorine-4-hydroxy TDhenvl) —Orotian 2,2-bis- "(3-chloro- 20th 4-hyäroxyph.enyl) - ■ propane 2.2 bis (3.5 di 70 4 »4 ^T -dihydroxy- 20th chlorine-4-hydroxy diphenyl sulfone phenyl) propane 2,2-bis- (3-chloro- 20th 4-hydroxyphenyl) - propane 2.2 bis (3.5 di 70 U tJ 20th chlorine-4-hydroxy
phenyl) propane 2,2-BIs-. (4-hydr oxy- '
phenyl) propane 10 , 2,2-bis- (3, Wi 60- 2,2-bis (4-hydroxy- 35 ch! or-4-hydr oxy- phenyl) —sulf op. phenyl) -pr opane 4,4'-diphenol 5 2.2 bis (3.5 di 65 2,2-bis (4-hydroxy- 30th chlorine-4-hydr oxy-
phenyl) propane phenyl) propane
2 "2-3is- (3,5-dibroa- 5

, (3,5d 4 -hy dr oxyphenyl.) .-

Polyester Mr.

Reduced viscosity (0.5 wt.% In chloroform at 25 ⁰ C)

Jeh 11 e 2

Melting area (ZapiJlar method)

solubility in chlorinated hydrocarbons

D. - '' ■. : 330 - 355 "insoluble,, 2) 1.57 '.; ■ ■ ^{; 1} 320 - 350 ■ insoluble 3) 1.55. ·. : ■ '■ 315 - 335 ; soluble ■ ■ ■, ■ '■ ... 4);. ■■■ ' 0.95 310 - ■ 340 soluble. . '' ■■■: ... ■. ■ ' 5) ■■■ ν, ι 0 * 92, 320 - 350 soluble "· 6) . -1.15 315 - 340 soluble "" 7) ' 1.12 '■> ■■■ - soluble 8th) -, 300.- 350 · soluble 9) 0.75 ·: - insoluble ** » 10) - ■ 305 - 335 soluble (up to 5 #) 1 * 1;) 0.96. . . ■ insoluble ' 12) 310 - 540 V soluble. : 15) 33.0 - 3.S5-.? : .'poorly soluble 14) 1.1. ' 325 - 360 soluble. . ' , 15) 1 »25. 325 - 355 ..; soluble 16). "0.9 315 - 350 soluble ':.' ",: 17) ^{: 'V14:;} ■■ ■■. ■■. '.; ■ '310 - 340 / \ soluble '. '.' . ; ,, 18), o, 9 '.; ; ^..: 025 "- §60 ^; ■ '' ■ ■■ soluble ■: ".: '..; ■■ 19) : '.' ¹ V ² 7 .'-; . ι ■ ■ ^; :. '.. Op?.;
. ■■ ^. > .; ; 365; .. :: · ". soluble · ^ι . ~, 20) soluble: '. 21) ^; soluble ■

Claims (5)

Patent claims: il Process for increasing chemical and thermal stability and the flame resistance of bodies chemically and / or thermally unstable and / or combustible plastics, characterized in that the plastic body with polyesters made from halogenated divalent ones. Phenols or mixtures of such halogenated bivalent ones Phenols with non-halogenated dihydric phenols and acid dichlorides, preferably terepthalic acid dichloride alone or as a mixture with isophthalic acid dichloride, coated. 2. The method according to claim 1, characterized in that the Coating takes place in such a way that on the surface of the body from chemically and / or thermally unstable and / or flammable plastics solutions of the polyester applied and the solvents are then evaporated. 3. The method according to claim 1, characterized in that the coating is carried out in such a way that one roughly preformed Body made of chemically and / or thermally stable and / or combustible plastics with a film made of the respective Polyester covered or wrapped and the so covered or the encased body is finally shaped under a heating press and, if necessary, cured. 4. The method according to claim 3 »characterized in that one for the purpose of good bonding between the roughly preformed bodies and the polyester film primer used for coating 1098U / 2064 '■■■ ■■■' "'' '■■■: ■. ■ ■ - 20 - ■■.; ■■;. ■ .- ■■■' /..: ■". ■■■■ ': or adhesives, preferably epoxy resins or polyurethane adhesives, layered. 5. With polyesters made from halogenated dihydric phenols or from mixtures of such halogenated dihydric phenols with non-halogenated dihydric phenols and acid dichlorides, preferably terephthalic acid dichloride alone or as a mixture with isophthalic acid dichloride coated Body, preferably foils, tapes, threads, fabrics, ITonwovens and the like, made of chemically and / or thermally unstable and flammable plastics. Troisdorf, September 15, 1969 Patent department Dr P / Ro T098.U / 20.64