DE1793004A1 - Halogenated norbornene-methano-naphthalene derivatives, process for their preparation and their use in thermoplastics - Google Patents

Description

The invention relates to new compounds which are generally known as halogenated Horbornene derivatives (EOrbornenyl-Methano-naphthalene-Derivatives) can be designated. Such compounds have been found to have beneficial properties and they especially as flame retardants for normally flammable thermoplastics Materials are suitable. These flame retardants are, when mixed with the thermoplastic prior to compression molding, Extruding or the like are mixed, stable at normal processing temperatures, do not discolour the thermoplastic and have no unfavorable influence on its flow properties. Folglioh has the Use of the proposed compounds as flame retardants solved many problems with those up to now

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known flame retardants were connected. These were in many cases with certain polymers

un-materials tolerable and often have the work

availability of (thermoplastics worsened.

The connections can be made by the following mark general formula

in which X is halogen, preferably oil, Br or F, Y. and Y · Halogen, alkyl radicals with 1 to 4 C atoms, those with halogen can be substituted, or alkoxy radicals with 1 to 4 C atoms, which can be substituted by halogen, and E is hydrogen, an alkyl radical with 1 "to 4 O atoms or mean a halogen.

In a preferred embodiment, these products are obtained by a Diels-Alder reaction, wherein two moles of a halogenated cyclopentadiene with one Moles of a compound of the formula

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O = OH ₂

in which R can be hydrogen, alkyl radicals having 1 to 4 carbon atoms or halogen.

Examples of the last-mentioned compound are 4-vinylcyclohexane, a dimer of butadiene, 4- ( oC -chlorovinyjO-i-chlorocyclohexene, a dimer of chloroprene, and d, l-limonene (dipentene), a dimer of isoprene.

For the prior art of the compounds of this general character, reference is made to the work "The Chemistry of Perchlorocyclopentenes and Cyclopentadienes "by H. E. Ungnade and] 3. T. McBee, published in Chemical Reviews 58 (2) (1958), pages 249 "to 320, referenced. This work specifically covers a large number of Diels-Alder adducts made by reaction of halogenated cyclopentenes and cyclopentadienes with various dienophiles. In this work, however, is no indication of a class of Diels-Alder adducts made from two moles of halogenated cyclopentadiene with the dienophiles included. In addition, all are Dienophiles either linear or contain the double bond only in the ring} the meaning of this is derived from the

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become clear from the description,

In the Belgian patent 672 846 is a flame retardant for. Polymers described as having the following general formula » _s

Here, X denotes bromine, chlorine or fluorine, Y denotes bromine, fluorine, chlorine, alkyl or alkoxy radicals, and Z is a tetravalent ring hydrocarbon radical which is at least

Contains carbon atoms.

In the Belgian patent text every example of the reactant which forms the residue Z is marked by two double bonds restricted to the Ringsys. In contrast , according to the. present invention, the class of dienophiles can be regarded as those which are formed by a divalent oyolieohen and a divalent linear part } the most important example of this is 4-vinyl-1-0yoloaexen ·

In U.S. Patent 2,900,377 an example (V) iet described in-the equimolar amounts of 1-vinyl-Cyolo-

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ORIGINAL INSPECTED

1 Ί

793004

hexei: -5 (the lsi · T- *. ^r ~.: iyl-1-cyclohexene) can be reacted with hexachlorocyclopentadiene, but from this example it is assumed that only 1: 1 molar idiucts result from this reaction . In other examples given in this patent specification, d, i-limonene is reacted with hexachlorocyclopentadiene; but in this case the d, l-limonene was used in an over- moiaren length , and accordingly only a 1: 1 adduct was formed.

The novelty and progress of this invention lies in the fact that the proposed compounds can be prepared by reacting two moles of a halogenated cyclopentadiene with one mole of a diene (e.g. 4-vinyl-1-cyclohexane) which has a double bond in the straight chain (e.g. the vinyl group) and has a double bond in the ring (e.g. in cyclohexene). In this way, a norbornene-methanonaphthalene compound with a freely rotatable central C — C single bond is obtained. This new type of compound differs significantly from the reaction of halogenated cyclopentadiene with (1) cyclic dienes (which are described in the above-mentioned publication, published in Chemical Reviews and the Belgian patent) and with (2) linear dienes (e.g. Butadiene, which are also discussed in the publication in Chemical Reviews) can be obtained «

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It has been found that only about 1 to 30% by weight, preferably 5 to 25% by weight, of these new compounds need to be mixed into thermoplastics in order to improve their flame resistance. Up to 50 wt .- ^ S can be used. In addition, these compounds also improve certain other physical properties, that is, the brittleness is reduced, the elasticity is improved and the color retention is also increased.

Accordingly, it is an object of the present invention to provide new compounds of the general I-formula »

in which X is halogen, Y and Y ^{1 is} halogen, alkyl radicals having 1 to 4 carbon atoms, which can also be substituted by halogen, or alkoxy radicals having 1 to 4 carbon atoms, which can be substituted by halogen, and H is hydrogen , an alkyl radical with 1 to 4 carbon atoms or a halogen.

The invention will be better understood from the detailed description that follows.

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' ⁷ "179300"

In the general class of compounds above has been described, those compounds in which both the X and Y radicals are halogen are one special class, and even more special are the compounds in which the X and Y radicals are chlorine. This compound is to be designated as follows according to the Geneva nomenclature: 6- (1 *, 4 ', 5', 6 *, 7 ', 7'-hexachloro-5'-norbornen-2'-yl) -1,2, 3,4,9 » 9-hexachloro-1,4,4a, ■ 5,6,7,8,6a-octahydro-1,4-methanonaphthalenine it will hereinafter abbreviated as CNB. CNB is made according to the Diels-Alder reaction, or more precisely it is reaction product of 2 moles of hexachlorocyclopentadiene with 1 IvIoI 4-vinyl-i-cyclohexene.

To better illustrate the making of these connections, some examples are given below, but these are only to be regarded as examples and not at all Set a limitation in terms of recipes and conditions.

Example I.

Said compound CNB, a white crystalline body of a melting point of 238-241 ⁰ C was prepared by reaction of 4-vinyl-1-cyclohexene with 2 moles of hexachlorocyclopentadiene, which was gradually added to the preheated 4 ~ vinyl-1-cyclohexene.

Slowly adding the CcOIg results in a strongly exothermic

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Avoided reaction, and high yields of CMB, 'about 82 / j, v / earth at temperatures up to 180 ⁰ C obtained.

Four hol (432.8 g) of 4 ~ vinyl-1-cyclohexene were preheated in a 2 l three-necked flask which was provided with a stick material inlet tube, a thermometer, a stirrer and a reflux condenser with an attached Drierite tube. To this, 2 g of 2,6-di-tert-butyl-4-methylphenol were added as an antioxidant. The ös ^ 12 ^was heated to reflux temperature (about 128 to 130 ⁰ C at 760 mm Hg) and 8 moles (2182.4 g) of CcGIg added dropwise or added in a thin stream over a period of 6 hours, the temperature gradually increasing about 148 ⁰ C, and later, after everything has been added

had been brought to about 160 ⁰ C. The temperature

was held at about 160 0 for a further 7 hours. [

The mixture was then brought to 100 to HO ⁰ O by adding an equal volume to room temperature

Isopropyl alcohol chilled. The GNB fell as white crystals \

in a yield of 68.4 $> and was by ^filtration!

collected and dried. Recrystallization from n-heptane j

is useful if analytically pure crystals with a \

relatively sharp melting point between 238 and 241 ⁰ C;

should be preserved. , f

Example II

Using the same device as in Example I.

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·% ■■ '■ 4. '"-

^{m <5 times} w «S >

viüräeu the following:! -. aalet an ten mixed at room temperature? 8! Io 1 (2182.4 ^) hexachlorocyclopentadiene (C-OIg, a pale yellow plasmid with a boiling point of 229 ⁰ C Dei 760 mis H &) and 4 Hol (432.8 g) 4-vinylt-cyclohexene (C ₀ H ^ ₀ , a colorless liquid v of a boiling point of 126-127 ⁰ C at 760 mm Hg), the following additives / ere the starting materials are added and mixed with them: 1 g of hydroquinone as Antioxydanz and 3 g of dibutyltin dimaleate CtEhermolite 13 "3 Irma Il? & £ Chemical Company) as Bntionisierungsmittel (scavenger) to remove traces of hydrogen chloride formed during the reaction. while slowly a stream of nitrogen was passed into the stirred mixture. reactants were heated by a mantle heater with which the flask was fitted. as the temperature increased, an orange colored clear solution was formed, and in about 6 hours a temperature of 160 ° was reached At this point a rapid exothermic heat was triggered, during which hot steam developed and the internal temp erature rose rapidly to 245 ⁰ O. The supply of heat from outside was interrupted during the exothermic reaction, and cooling was carried out from outside.

After the mixture had assumed a temperature of 245 ^° C., it became noticeably darker. After cooling the mixture to 90 ⁰ C, the Misohung became viscous, but was still stirrable, and at 25 ⁰ O (room temperature) solidified

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BAD ORlQIfWL

the whole mixture in the vessel.

The crude product was dissolved in acetone and purified by filtering through charcoal. After concentrating the filtrate, the product was obtained as white crystals in a yield of 60 % . Additional minor amounts were recovered from the filtrate and the final filtrate contained a dark brown viscous Ceer as a residue.

The crystals were further purified by recrystallization from acetone. The analysis showed a relatively pure product, which was identified as CNB and had a melting point of 241 to 243 ⁰ C? the results obtained were confirmed by the infrared absorption spectrum. The structural analysis gave the following result: C ₁₈ H ₁₂ Cl ₁₂ : Cl-65.07 #, C-33.08 #, H-1.85 fy molecular weight 653.8.

It should be noted that the essential difference between Examples I and II in the slow Addition of the CcCIg in Example I compared to Example II consists. The rapid exothermic reaction that takes place when the starting materials are mixed at room temperature and then heated increases the risk of a violent, uncontrolled reaction occurring. In addition, the yield is somewhat lower (45 to

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60 -, j in comparison with 70 to 82 ^l / i>) according to the process "obtained as in Example II". In spite of this, the technique described in Example II "can be quite suitable for experiments.

Example III

The reaction was carried out as in Example II, but additional amounts of an antioxidant ¹ in the form of 2 g of 2,6-di-tert-butyl-4-methylphenol were added. A mixture of methanol and petroleum ether was also used in place of acetone to dilute the solidified product prior to purification. A yield of 1160.8 g, that is 55.3 ° of theory, was obtained. An additional yield of 26.6 $ was by combining the wash water filtrations AU3 based on the starting material obtained what the G-esamtausbeute fi increased to 81.9.

Further experiments according to Example II were carried out using other solvents such as chlorobenzene, tetrachlorethylene, xylene, ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol and / or excess CcCl ₆ . The use of the different solvents resulted in different reaction times and temperatures before the start of the exothermic reaction. It has also been found that small amounts of Lewis acid such as

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Iron (III) chloride, aluminum (III) chloride or boron trifluoride / the Response speed increased, which shortened the heating season! Those made from acetone, ethanol, Diethyl ether, n-heptane and / or petroleum ether recrystallized Products were dried. The purified products were all determined by means of the Mixed melting points that showed no lowering of the melting point in the various processes were identified as OHB. When the crystals were pure, they consistently melted at 241 to 245 ° 0.

Example IV

Ten moles or 1362.5 g of dipentene or d, l-limonene (Cjo ^h iö) » ^a colorless liquid with a boiling point of 178 to 180 ⁰ G at 760 mm, molecular weight 136.25, was 16 moles (4365 g) at room temperature Mixed hexachlorocyclopentadiene. 5 g of 2,6-di-tert-butyl-4-methylphenol (antioxidant) and 7 g of dibutyltin dimaleate (deionizing agent) were added to this mixture.

When heated to 60 ⁰ O calibration solved the additives, so that a clear pale orange-colored mixture was; at 145 ⁰ C SiOH developed a dark red color. Heating was continued for about 15 hours under a nitrogen atmosphere with continuous stirring. The 2s1 adduct, later identified as ^ (Αβ ⁰¹ ^ ^, was made by diluting the misohung with petroleum ether and leo

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propyl alcohol precipitated. The solidification of the product by conventional techniques led to the formation of white crystals having a melting point above 210 ⁰ C. \ 7egen the presence of stereoisomers in the G-Glg bridge could not be obtained, a sharp melting point. The product was ala 6- (1 ^f , 4 ', 5', 6 ', 7', 7 ^l -hexachloro-2'-methyl-5'-norbornen-2'-yl) -1, 4, 4a, 5 , 6, 7, 8, 8a-octahydro-1, 2, 3, 4, 9 »9-hexachior ~ 8a ~ inethyl-1,4-metharfhaphthalene identified, a compound with the following structure:

Example V

The following equation gives the synthesis of another Diels-Alder adduct, namely 6- (1 ', 4 ¹ , 5 ¹ , 6'-a) etrachlor-7', 7 ^f -dimethoxy-5'- norbornene-2 » ~ yl) -1, 2, 3, 4-tetraohlor-9, 9-dimethoxy-

1, 4, 4a, 5, 6, 7, 8, 8a-octahydro-1, 4-methanonaphthalene,

^σ 22 ^Η 24 ⁰¹ 8 ° 4 ^or * e " ^br a- ' ^me '^{t; n} . ^{o: x} y ~ ^onlorier ' ^tes norbornene derivative, hereinafter referred to as I0NB

-H-

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bad original

Cl

Oil

οι

In this example, 0.5 mol or 132 g of 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene or O ₅ Ol ₄ (OCH ₃ ) ₂ , a light yellow clear liquid (b.p.

108 to 110 ⁰ C at 11 mm, 102 to 105 ⁰ C at 5 mm,

Refractive index n- ^ = 1.5288, calculated molecular weight 263.94) dropwise with mechanical stirring and under nitrogen to 0.25 mol or 27.05 g of 4-vinyl-1-cyclohexene or OgH ₁₂ (a colorless liquid, b.p. 130 ⁰ O at 760 mm), which was ^{preheated to 110 0} C, was added dropwise. ! The addition was completed after 46 minutes, and during this time was gently heated by an electric heating mantle to maintain the Eeaktionstemperatur in the range 103-144 ⁰ O. After the addition was complete, the golden yellow reaction mixture was heated to 110 to 142 ° for 2 hours and then ^{kept at 142 to 152 0} O for 9 hours.

Duroh thinning of the viscous raw product at tree temperature with approximately equal volumes of isopropyl alcohol and acetone a white solid was obtained which

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BATH ORIGINAL

was isolated by nitration. ITach recrystallization from -. ,. ceton melted, the white crystals "at 209-210 ⁰ C without decomposition Compound 2CNB (see above) or ^G 22 ^{'t' i} 24 ⁱ '^ 8 ⁰ 4 ^w u ^r de of this purity level for found suitable to be used as flame retardants in various resins. to analytical purity obtained to which Huster, however, was recrystallized from anhydrous Biäthyläther, after snow-white crystals having a melting point of 224 ⁰ C (the crystals melted to a colorless fluid without decomposition), which was identified by liikr ο analysis as the product ^ 22 ^ 24 · ^ Β ^ Α ^ic3 , also by determination of the molecular weight and the infrared spectrum. The yield of this product was 79.3 % or 126.1 g a crystallization,

Around-
and after / crystallize, 92.8 f «were obtained back.

Example YI

Sin brominated norbornene derivative, 6- (1 ', 4', 5 ', β ¹ , 7 ¹ , 7 ^l -hexabromo-5 ^t -norbornen-2'-yl) -1, 2, 3, 4, 9, 9- Hexabromo-1, 4, 4a, 5, 6, 7, 8, 8a-octahydro-1, 4-methanonaphthalene, hereinafter referred to as BEB, can be produced by the following reaction

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'■■■ .3

C-I

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0.1 2.1ο 1 or 53.95 £ Hoxabromocyclopentadiene or C _r 3iv (a yellow crystalline body, pp. 83 to 85 ⁰ O) were at tree temperature with 0.05 mol or 5.4 g of 4-vinyl-1 ~ cyclohexene (a colorless liquid, iCp. 130 ⁰ C at 760 mm) mixed. After heating to 50 ° C., a yellow, homogeneous solution resulted. Bie was kept at a temperature of 100 to 130 ^° C. for hours and at a temperature of 130 to 135 ^° C. for 4.5 hours. The brown product was treated with boiling acetone and then with boiling tetrachlorethylene. The dark brown solid body, which was insoluble in these solvents, was dried over phosphorus pentoxide under reduced pressure over laughing. The product was a crystalline powder, black-brown after drying, and had a pp. Above 420 ^° C. The composition C ₁₈ H ₁₂ Br ₁₂ or BNB (see the structural formula given above) was confirmed by analysis.

Example VII

1 mol or 269.5 g of tris (2-chloroethyl) phosphite (ClCH ₉ CH ₉ O-) ,? a colorless liquid, bp. 132-135 ⁰ C at 10 was added dropwise dissolved a preheated to 55 ⁰ C solution of 1 mole or 272.8 g of hexachlorocyclopentadiene (CcCIg, a light yellow liquid) in 1 1 (860 g) xylene mm. NaOH addition has ended, the golden yellow Reaktionemieohung at 70 ⁰ C was hitzt it, whereupon an exothermic reaction set in, and

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BATH ORIGINAL

the temperature rose ^{to 105 °} C. despite external cooling. The mixture was cooled to 58 ⁰ C and then heated to 70 ⁰ O (total of 6.5 hours), the! Was temperature-regulated by a heating bath. After two fractional distillation under reduced pressure, the main reaction product obtained was a pale yellow liquid with a boiling point of 96 to 102 ^° G at 0.58 mm. This product was analyzed as 1- (β- chloroethyl) 1,2,3 t 4,5-pentaehlorcyclopentadiene or G ^ ILGlg, the analysis was confirmed by the IR spectrum.

This compound, C “H.Clg, was used for synthesis of a product according to the invention according to the following Equation used:

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BATH ORIGINAL

CM

CM

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This compound 6- (1 ·, 4 ¹ , 5 ^!, 6 ', 7 ^! -Pentachlor-7'- β- chloroethyl-5-norbornen-2'-yl) -1, 2, 3, 4, 9-pentachlor -9-p chlorothyl-1, 4, 4a, 5, 6, 7, 8, 8a-octahydro-1, 4-methanonaphthalene, hereinafter referred to as BON, was prepared as follows:

Half a mole or 158.4 g of O ₇ H ₄ Cl ₆ or 1 ~ (/ 3 chloroethyl -) - 1,2,3,4, S-pentachlorocyclopentadiene (a yellow liquid, see Kp. And analysis above) were at Room temperature mixed with 0.25 Hol or 27.05 g of 4-vinyl-1-cyclohexene. The mixture was heated with stirring in a nitrogen atmosphere, first for 3 hours at 125-138 ⁰ C and then for 20 hours at 162 ^ reitere ⁰ O kept. The liquid products were stripped off by fractional distillation under reduced pressure and the undistillable brown residue was recrystallized first from acetone and then from diethyl ether and then precipitated in aqueous isopropyl alcohol, an almost white crystalline powder being obtained, which under reduced pressure over CaSO until constant weight was dried at room temperature. This product, pp. 76 to 78 ⁰ G, was described in the same way as the products in the preceding examples, by IR spectrum and elemental analysis

identified. The Summenfbrmel ^C 22 ^H 20 ^{C! L} 12 ^{WUR <ie} ^ ¹⁶ "confirmed.

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BATH

Example VIII

Dimeric chloroprene, 4- (οό-chlorovinyl-) 1-chloro-1-cycloh ex en (hereinafter referred to as GD), was prepared according to the method described by Zlebanskii et al .; published in Vysokomolekul Soedin 4 ^ 1145-50 (1962 ), see also Ghem. Abstracts ££, 1819 a (1963). Γ / 7 g of CD produced in this way was placed in a reaction vessel and ^{heated to 70 °} C. under nitrogen; 545 g of hexachlorocyclopentadiene were added to the reaction vessel with stirring over a period of 4 hours, the temperature being gradually increased to 160 ^° C. Haoh completion of the addition of the reactants was dan stirring continued for a further 18 hours and the temperature to 160 to 190 ⁰ C. The reaction mixture was distilled in vacuo to remove unreacted CVCIg and the 1: 1 adduct. The 2s1 adduct, 6- (l ', 2 », 4 ^!, 5', 6 ·, 7 ¹ , 7'-heptachlor-5 ^l -norbonen-2'-yl) -1,2,3,4, 8a, 9,9-heptachlor-1,4,4a, 5,6,7,8,8a-octahydro-1,4-methanonaphthalene, C ^ gH ^ Cl ^. (CDMB) was obtained with a yield of 25 de i * from the distillation residue by recrystallization. The reaction can be described by the equation below :

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ίλ.

CVJ

CNJ

HO

HO

CM

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Halogenated urbornene derivatives as flame retardants

'Die Flaminr.; Ohutzügeenschp.ften halogenated eggs
Lorbornene derivatives are determined on a large number of the most varied of polymeric resins. In the examples,
In the following, the flammability of a "certain luster was determined by three methods":

. By testing according to the ASTLi-IvI method 1) 635-63

(all quantitative burn rate measurements were carried out according to this method).

2. By the match test, "in which a sample, as described in the AS TLi-Vors Ehr if t D635-63 ", is held in the vertical direction and a match flame is held at its free end will. The degrees of flammability can be defined as follows:

a) Weight flammable (HP), after removing the flame no flame remains.

b) Self-extinguishing (SE) - after removing the flame (match test and / or G-asflaraiiienteat) the flame goes out spontaneously, i.e. in less than 1 second or within

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BATH ORIGINAL

half a set number of seconds under 30.

c) Flame Resistant (FR) '- the sample burned at less than twice the burning rate of the standard material (measured in cm / min according to the formula of the ASTM method D635-63).

3. Burning Tests for Plastics - Underwriters' Laboratories Subject 94 (U.L. Test). All patterns were qualified as "self-extinguishing, group 1", insofar as they did not drip flammable materials or drips during the burn test resigned.

Example IX

A self-extinguishing ABS molding compound was prepared according to Table I below:

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Components

ABS resin *

CNB (C ₁₈ H ₁₂₁₂ ) antimone (III) oxide

Thermolite

Pluronic F38 Hekon "White

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TABSLLE I

function

Flame retardants according to the invention

Additive for synergistic effect with the Flame retardants

Deionizers for acid traces; a stabilizer

Mold release agents
Brighteners for synthetic resins

Parts by weight

74.8 15.3

7.2

O , 9 O , 45 1 _T 35

100.00

* ABS resin is an acrylonitrile-butadiene-styrene graft copolymer

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The constituents in table I were "mixed with one another in powder form at room temperature, ^{treated on the roller at 32 0} O for about 7 minutes to produce a homogeneous, almost creamy-white (slightly creamy white - the usual color for ABS polymers) synthetic resin film to obtain that this rolled product was hard when cooled to room temperature was as deformed at about 216-243 ⁰ C after the Sx ^ ritzgußverfahren in known ', -. so as ^ plates and rods of the deformed, selbstlönchenden resin was obtained containing the had the same white color and were completely thermally stable at these temperatures, showing no streaks and no discoloration.

This illustration was after rolling and injection molding white, smooth, and no odor or sublimate had developed during the rolling and shaping, ilin another cough was compression deformed in the same way with the same results. ■. .

The product retained the high tear strength, hardness and heat recovery temperature of the ABS resins. - .. '. Ss also showed high flexural strength and was not brittle. The flow of the resin was noticeably improved by the presence of CiHj in contrast to other known anti-inflammatory agents, which the flow ^; the ; · Inhibit hot synthetic resins so that full bars and panels

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BAD ORIGINAL J ^ ^ O CA ⁵ ?

ii: the ο o en for the ', slurping and compression deformation, just en i'caperaturbereich cannot be produced, would result in a higher temperature range in view of its high value:.; c ~ stability, durability C.C3 showed surprisingly good results against decomposition and improved insolubility, as well as being an effective protective agent, and was far superior to other known additives in its behavior in synthetic resins.

The influence of the CIiB on the impact strength of injection molded ropes of the composition given in Table 1 is particularly noteworthy. In repeated tests on various "lascivious" compositions of this type, the breaking strength according to Isod was in the range from 36.99 to 40.25 cm kg / cm, YvO compared to injection molding parts made from a synthetic mixture, known in the CIiB by the same Ilen Additive (see i3. By O ^ H ^ OvGlg, that is the equimolar Diels-Alder-iiddukt of I.ialeinic anhydride, 1,3-butadiene and hexachlorocyclopentadiene) an Izod impact strength in the range of 11.88 to 14.14 cm kg / cai, ie the notched impact strength was about three times lower.

Dien p.pjgt immediately the great practical importance of this invention, e.g. 3, from OI \ 3 as plamm

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BATH ORIGINAL

Protective agents in AßS resins with such properties, that they are very suitable for the production of new synthetic resin smells with excellent properties «, pur many ./.applications is high impact resistance absolutely necessary. ν

The high degree of flame resistance of plastic parts of the composition, as indicated in Table I, was determined by the light flammability test of the Underwriters' w Laboratories ¹ (hereinafter abbreviated to UL test)

shown at an otab of this composition of 60 mil (i.e. 1.5S7 mm) thickness as described in the Underwriters' Laboratories for this test is carried out.

The plastic parts of the composition according to Table I with only 15.3 parts by weight of CHB or ^ 8 ¹¹ 12 ^ "M 2 passed the UL test, which is one of the most severe tests for IT non-flammability of plastic. The new .'ixS resin- Composition containing CEB was classified under Group 1, self-extinguishing, falling; Group 1 is the best group for plastics, i.e. a plastic falling into the group is self-extinguishing, and the luster did not drip when it came into contact with the ilamne The time for the flame to extinguish itself (on average for six ignitions of the 60 mil thin tablet) was only 2.8 seconds, and the minimum maximum

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BAD ORJQINAL

muni ratios of the attempts in seconds 1/5.

Numerous "known additives have been tried out in ABS-Iiarzen, and with none could such an excellent combination of _{properties be achieved as with GWß t} namely thermal stability, improved plus, very high impact resistance, other excellent physical properties and self-extinguishing according to the UL- Test with only 15.2 parts by weight of the flame retardant.

Example X

A relatively pure sample GlTB ₇ produced according to Example I was assessed for its flame resistance properties in a large class of polymers. Unless otherwise noted, the CIiB was rolled into the polymer in order to obtain a homogeneous mixture. Each sample contained CIIB in an amount of 16.5 Grew .-> i and, with the exception of the chandeliers, which could not be rolled, still contained 7.7 Grew .- ^ e L ^ O *, a common stabilizer and synergistic flame retardant.

Table II below gives the grades of flame resistance the polymer pattern containing Oiffl again:

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9SAI / 98860L

Base material

Polyisoprene

(Naturkaut s chulr)

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TABLE II

Identification of the basic material (if applicable.)

Smoked Sheet, Burton Rubber Company

ABS graft polymer Cycolac T, Marbon Chemical

division

Polybutadiene., linear

Polybutadiene, cross-linked

h butyl rubber (polyisobutylene)

Q polyamide (nylon)

Polyamide (nylon, type 8)

Firestone ED-55-A, 35 ¹ Pis-Marbon Chemical Division

2 i> isoprene units Enjay Chemical Co.

Dupont, Zytel Dupont, Zytel Parbe and appearance after rolling ^

schv / ach beige-v < ^T eii3, looked, sticky, very elastic

roughly white, smooth surface, firm, not very flexible, shiny, not brittle

not rollable ^, coating of xylene solution

contains soot, etc .; black, smooth film, rubbery, very flexible

white, rubbery, porous, very flexible, very tough

not rollable ', coating of m-cresol solution

roughly white, smooth, not very flexible, very hard

SntflpiLibarkeitserad *

S.E.

1 see.

IT.I ¹ .

P.R. - 7.62 πα / min.

S.E. - 12 sec.

P.R. - 6.51 mm / min.

S.E. - 13 see. S.E. - immediately

If the pattern doesn't; became rollable, a coating was produced by dissolving the polymer
and the flame retardant in a suitable solvent, the solution is applied to the cough
and the solvent evaporates completely.

All of the polymers listed in this table were, if they did not contain a flame retardant, ςο flammable and not self-extinguishing. Thus, the non-flammability or fire resistance is directly due to the effect of the ClTE. O

- 31 -

TABLE II Green fluids

Styrene / acrylonitrile polyurethane

Polystyrene

Ethylene / propylene chew school:

Ethylene / propylene terpolymer

Polyethylene

Identification of the base material (if applicable)

liarbon Chemical Division Shell

Enjay

Nordel 1070 marlex 1531

Poly (cyclopentadiene) Yelsicol AD-57

Marbon Chemical Division

Methyl-raethacrylat / c £> Chloracrylnitril- (30:20) copolymer

Styrene / oC -chloroacrylonitrile

(75:25) copolymer

Marbon Chemical Division g and Aus are said to be after rolls ¹ ^

soft, somewhat shiny,
yellowish-v / oi.0, v.'cnig
flexible, be tough

hard, somewhat brittle, tough, smooth, roughly white, weak glittering"

tendon εν / ε iß, porous, gunrai-like, flexible, very tough, strong film

slightly gray, porous, flexible, very tough, somewhat rubbery

slightly gray, porous, flexible, very tough, somewhat rubbery

brownish gold, brittle, firm

brownish, hard, brittle, rigid, rigid body

.S.

.S.

IT.?.

IT.?. IT. F.

S. Xi.

- 5 see.

- 1 see.

brownish, hard, brittle, weakly shiny, inflexible S.E,

2 see.

immediately

CD U) O O

TABLE II (PORTSETZTOIG-) Basic nat erial

Styrene / oC ' -chloroacrylonitrile /
Methyl methacrylate (60:10:30) copolymer

Yinyl toluene /

Butadienoo (91: 9) copolymer

Identification of the base material (if applicable)

Carbon Chemical Division

Marbon Chemical Division

- * Acrylonitrile rubber B. F. Goodrich

Polycarbonate
Polypropylene

Styrene / butadiene
(85:15) copolymer

Lexan 105, General Electric

Avisun, type 1014

Marbon Chemical Division - color and appearance after the rollers 1)

Inaccessibility to deflate

roughly white, hard, inflexible, smooth and shiny polie S.E. - 2 see.

roughly white, brittle, solid body, hard, smooth, slightly shiny

smooth, non-porous, roughly white film, shiny, rubbery, tough

Coating of xylene solution, white solid body

Coating of xylene solution, white solid

gray, hard, brittle solid body, inflexible

S. E. - immediately \
VU f. S. E. - 5 sec. S. E. - immediately S. E. - immediately S. E, - immediately 79300

uic YoX ¹ I) Inuim; j, αϊ3 '.20IiI ₁ icicntifiiiiert, and' oaiuJ
L-ei-Vicl Y iiüi'ijöctollt, \ / urcle as iPlaüurjcim ίι-, ΐ ^ Ι Ϊ. ü jptuoiQ'b · ϋίβ wuvilö rai'b bogiij-i-mwbu «Aoryl'ui.-iit'i.l - '. ji.i'St7rül-; i £ irr.t: n boi icaumtt-Liperatur in Julv. ; r: \ - ru vo unJi some other ^ ücii-bive v / urcien nor hixuui ^ ejeΰ. The Les'uatultoile el or ± 'ouerfe £ iten Harsraischuii ": .sin aCiiüteiiei-Kt aiU ^J rjei'leads;

109886/1756
WHEEL ORIGINAL

Weight parts C, ^ I ₀₁ Wl .0 Mw &quot; 2CIB ¹¹ ,

. c- * r O 'τ

V / G i Ιό β ^ iX ¹ J. :: j "t IiL-L O βο« ο «οο ··« οοοοοοοοοο οοο 21, 62

31sndöx 101 (an ABJ resin from

I. 'Carbon Chemical Division) .. ο »50.45

: i-3ö (a -uJb-Karz der LIarbon

ChemieLiI jJivision) ........., ..., .., ...... 18.03

uard S (or SbpO-,
White dust) . ο <, ο <> _βο <> ». <>. ».» Ο <> ο _ββ . _{β β} <. » * ο 7.21

Thermo Lite 25 (Hitaestabi-

™ * A - - · - N f \ C \ "\

-L X fcj cL Ü O L / OOOeÖOOOoO'OOOOOOOOOOOOOOOOOOOUO V- * J ./ '

Pluronic 1 ^ι -38 (iOrmtrenn-

111 J- U ut X y * ΟΟΟΟΟΟΟ ΟΟΟΟ ΟΟΟΟΟΟΟΟΟΟΟ0ΟΟΟΟΟ W ρ ^ Lekon l / iiite (additive with ^ uf-

hellun ^ sv / effect) ο * β9βοο ₀ <· οο «ο.οοοοβββ · ₀ ο . Ί, 35

100.00 weight bag

This mixture was rolled for 5 minutes at 166 ° C., and a white (almost white with slightly cream-colored I ¹ UULUIf;), bare, smooth, flexible plastic film was obtained, after the A3TM method D-635 tested and found to be self-extinguishing in 3.3 seconds. This fact was confirmed by a match test. This; iarz could be molded into self-extinguishing, pale creamy-white plates in apritz-cast molds. The remarkable and surprising advantage of the use of SCrIB in the ABS composition described consists in the combination of easy molding and deformability, significantly improved flowability of the resin at elevated temperature and a high degree

- 35

ϊ ν u ■ :: · <.: ■

109886/1756

BATH ORIGINAL

rf eoti ^ 'keit with juter iVrbo and G 1.Mn: ;; ? the Pli £ _tik-: j.Oüü tc ;.. ^; . :) he surface of the plastic object v / sr ./latt, and ι;, as product was ^ .oruchion. Another advantage of the 'I'CiiL (above like dec C13 and other products of this invention) was the fact that never showed no turning under the conditions of the'.'ill κ en? are Druokverfornens, that is, in the case of increased toilet proportions, r: u sublir / .ieren, whereas numerous other plaiiimschntsinmittel eckanntor kind (which in "oezuj on structure and Ji ^ en30hi.i" t ^ n are not related to the products of this invention) the ability to process from the hot resin showed what was found to be unfavorable and dangerous to the worker. This difference is essential to the practical use of the products of this invention, including CHB and

In the same quietly was I ¹ CiB or 0,., .- ₀ Ji .Cl-.0. in

^ ac dl \ OH

a length of 15 to 22 wt .- ', ο (with 4 to 7 Gc ubpO-r) incorporated into other resins (dio above in detail at. the use of CJTB), including polystyrene, poly ~ (ntyrol-acryl « nitrile) or Poly-S ^ Ui, polypropylene, Eisphenol-A polycarbonate. In this way, self-extinguishing, flame-retardant Iaraci mixtures were obtained, which improved Eliei3barki:; koit and other favorable physical Properties exhibited.

109886/1756 BAD ORlGlNAU J ^ '

The product designated as 3? Ι · Π3, da3 according to Example VI Was produced as a flame retardant checked. A mixture, a light brown powder, was made from the following ingredients at room temperature manufactured:

Weight parts

₁₈₁₉₁₂ , dark brown

w * v ^^% ^ X «* \ -f J * 9 9 9 o 9 OOOOO ν ^ v © © O ^ r O w ^ * ^ t ^) OOO ^} ^ / V V3 O ^^ ^ v £ ^ * ft ^^ 'm> *

Blendex 101 (A3S resin from

Ilarbon Chemical Division) oe ... oo 57.64

X-80 (an ABS resin of the

Ilarbon Chemical Division) .. · -., · 18.03

(Dhermolite 25 (heat stabilizer) .ooooooooeoooeoooooooe ··· * · »« «» 0.91

Pluronic P-38 (mold release agent) _ββ ..ο <, 0,4-5 llekon Vhite (additive with
Lightening effect). _O ..oo _ο . ·· ο 1.35

100.00

The mixture was ^{rolled at 166 °} C. for 7 minutes. A shiny, dark-brown, very hard and somewhat elastic film of flame-retardant plastic was obtained. This plastic product was self-extinguishing against the match flame and within a second on the ASEM test D-635. Particular attention should be drawn to the fact that self-extinguishing properties are also imparted to the synthetic resin when SbpO ^ is absent, which is a

- 37 -109886/1756

BATH

is a relatively expensive additive that is widely used in order to increase the flame resistance properties of various halogen-containing additives in plastics. In this ITaIl, a surprisingly high degree of flame resistance was found in the absence of Sb ₂ O ₇

represents. The use of Gi8 ^ i212 colored and black plastics are indicated (e.g. where kiss is generally added). ] for light colored or white resins, however, the chlorine-containing compounds of this invention are recommended.

^ g ₁₂₁₂ showed the same Plammschufczeffekt in Poly-SAiT, polystyrene, polypropylene and in other synthetic resins, if it was used in the same concentration.

Example XIII

The product identified as BCIi, prepared according to Example VIE, was also found to be an effective flame retardant in various synthetic resins. About 15 "to 22 ^c / o of the flame retardant were used in the resins together with 4 to 7 /» SbpO, in order to avoid burning or quickly To produce suitable plastic samples according to class 1 of the U. I. test. The same resins as those described in Example I became fireproof with this new compound.

- 38 -

109886/1756
BADORIQiNAt '

- 28 -

..orui cierse Jrfindun ^ has also been written in connection with certain specific embodiments, so cina these only al. ^r ; VeriUiKchaulichunij serving aui'-, aio do not represent any limitation.

. κ η car

109886/1756

BAD ORIOINAt

Claims (1)

pete ntanwnltn Dr. Ing.H. Negrndank Dipt. Ing.H. Hauck Dipl. Phys. W. Schmilz 2 Hamburg 36 [\ leusr Wall 4 1 bouth IMichigan Avenue
CIiIOAGO, Illinois 60604 ( July 22, 1968 Claims "connection, - e know ε ei without χ through the general in which X is halogen, Y and Y ¹ halogen, alkyl radicals with ϊ οis 4 carbon atoms, which can also be substituted with halogen, or alkoxy radicals with 1 to 4 carbon atoms, which can also be substituted with halogen kümi'-Ti, and H is hydrogen, an alleyl radical with 1 to A C atoms or a halogen. 109886/1756 BATH ORIGINAL ' 2. Compound according to claim 1, characterized in that X is chlorine, bromine or fluorine. 3. A compound according to claim 1, characterized in that X is chlorine, Y is chlorine, Y ^{1 is} chlorine land's hydrogen
is. 4. A compound according to claim 2, characterized in that R is hydrogen. 5. A compound according to claim 2, characterized in that R is chlorine. 6. A compound according to claim 2, characterized in that that R is methyl. 7. A compound according to claim 2, characterized in that Y is chlorine and Y 'is chloroethyl. 8-compound according to claim 1, characterized in that X is chlorine, Y is methoxy, Y ^{1 is} methoxy and H is hydrogen. 9. Compound according to Claim 1, characterized in that that X, Y and Y 'are bromine. - 3 109886/1756 10. A compound according to claim 1, characterized by the formula 6- (T ¹ , 4 ¹ , 5 ', 6', 7 ', 7'-hexachloro-5'-norbornen-3'-yl) -1,2,3 , 4>9> 9-hexachloro-1,4,4a, 5, 6, 7,8,8a-0c tahydro-1,4-methanonaphthalene. 1. Process for the preparation of compounds according to claims 1 Ms 10, characterized in that 1 fetch a first connection of the general formula G = OH, in which E is hydrogen, an alkyl with 1 to 4 carbon atoms or halogen, heated to about 100 to 150 0, gradually 2 moles of a second Connection of the general formula YY ¹ in which X is chlorine, bromine or fluorine and Y and 109886/1756 - 4 * r , Alkylreates with 1 to 4 carbon atoms, which can also be substituted with halogen, or alkoxy radicals with 1 to 4 carbon atoms, which can also be substituted with halogen, are added and the mixture obtained is added at a temperature of about 120 to 190 ⁰ C is held for about 6 to 24 hours. 12. ' Method according to claim 11, characterized in that that the first compound used is one in which hydrogen is hydrogen. 13. The method according to claim 12, characterized in that such a second connection is used in which X, Y and Y 'are chlorine. 14. Use of the compounds according to claims 1 to 10 as flame retardants for polymers Materials by mixing them into the polymer, if necessary together with antimony trioxide. 15. jTlammeproof polymeric materials, labeled duroh a content of 5 to 50 wt .- ^ one Compound according to claims 1 to 10. - 5 ■ - ■ - 109886/1756 16. j? Lamiflfeste polymer materials nacii claim 15 » characterized by a content of antimony trioxide. 17. JTlaam-resistant polymeric materials according to claim 15 and 16, characterized in that the polymeric material is a polymer made of the the following group is selected: polyisoprene, ^ .crylonitrile-butadiene-etyrene graft polymer, linear polybutadiene, cross-linked polybutadiene, polyisobutylene, polyamide, styrene-acrylonitrile polyamide, Polystyrene, ethylene propylene rubber, Xthylene-propylene polymer, polyethylene, Polycyclopentadiene, acrylic rubber, polycarbonate, polypropylene and high impact polystyrene. 109886/1756 BAD ORIGINAU