DE2148276A1 - Polyamide mold and extrusions with reduced flammability - Google Patents

Description

The invention relates to molding compositions and extrusion molding compositions based on linear polyamides, in particular molding compositions and Extrusion grades based on linear polyamides with reduced Flammability ο The term "polyamides" used here refers to synthetic linear polyamides, those from polymerizable monoamine carboxylic acids, their amide-forming derivatives or from suitable diamines and suitable dicarboxylic acids or amide-forming derivatives of these compounds can be produced »These polyamides contain repeating amide groups as an integral part of the polymer backbone, and the repeating intralinear ones Carbonamide groups in these polyamides are through Hydrocarbon radicals containing at least 2 carbon atoms, separated. The synthetic linear polyamides used in the Molding and extrusion compounds and can be used in the method according to the invention, all belong to Nylon type and have a relative viscosity between 15 and 4-00, preferably between 45 and 14-0, measured in a solution of 2 g of the polymer in 21.81 g of an above Ant liquid solution. The manufacture of such polymers will for example in UoSOAo patents 2,071,200,

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2 071 253, 2 130 948, 2 285 009 and 2 512 606 described » As examples of polyamides used in the molding and extrusion molding lines and in the process according to the invention are, in particular, polyhexamethylene adipamide, polyhexaraethylene sebacamide, polymerized 6-aminocaproic acid, polytetramethylene adipamide, polytetramethylene sebacamide and polyadipamide to mention those from di (4-aminocyclohexyl) ethane or 1,6-di- (4-aminocyclohexyl) hexane have been produced as a diamine component.

Compressible and injectable polyamides have attracted considerable attention in the plastics industry as .Preßharze due to a desired combination of technical properties such as tensile strength, flexibility and impact strength. For many applications where a pressable and injectable polyamide with improved properties, ZoB _e a polyamide with improved tensile strength, is required, this requirement is met by adding a reinforcing filler, ZoBo glass fibers, to the polyamide. “Both the polyamide as such and the reinforced polyamide thus have extensive use for the

ae

The most diverse purposes have been found, but have the disadvantage that they are flammable and combustible.

If an open flame to polyamides is maintained, the heat will melt the polyamide, and then ignites the surface of the molten polymer »The polyamides have a melting point of about 180 to 25O ⁰ C. The molten polymer is a low viscosity liquid. If this liquid is further heated to about 400 to 45O ⁰ G, pyrolysis takes place of the liquid with the formation of volatile, flammable products, which are ignited by the flame. Due to the large difference between the melting temperature and the ignition temperature in connection with the low viscosity of the melt, the molten polyamide can drip off and take the flame with it. These drops of liquid can burn on

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and in this way spread the fire,

The attempts made so far to improve the flame resistance of polyamides have generally been unsuccessful due to the chemical nature of the polymer.The carbonamide bonds in the polymer chain are much more reactive than many other polymer bonds, Z ₀ B ₀ those of the polyolefins, especially at processing temperatures of 180, for example up to 280 ^° C. Well-known fire-retardant or flame-retardant agents react with the polymer, causing severe degradation _o Generally known fire-retardant and flame-retardant agents, e.g. halophosphates and the combination of chlorinated paraffin, which contains about 50 to 80% chlorine, with antimony oxide decrease not only do not the flammability of the polymer, but react with polyamides at the processing temperatures in such a way that they have the opposite effect, ie "catalyze the pyrolysis of the polymer and lower its ignition temperature. Even non-flammable fillers, such as asbestos and silicon dioxide, have this effect on the polymer. In addition, the halides and phosphates usually used as flame retardants lower the melt viscosity of the polyamides and thereby increase their tendency to drip. The problem of the flammability of polyamides and the need to solve this problem thus remain.

U.S. Patent 3,418,267 states that that the flame retardancy of polyamides increased, their Flammability is reduced and the problem of dripping can be largely eliminated if the polyamides are used Combination of a) flame retardants in the form of organic halides, namely cycloaliphatic halides and aryl halides, the chlorides being preferred in each case with b) oxides of metals such as Sn, Pb, Cu, Fe, Zn and Sb is added. According to the U.S. Ar patent 3 410 267 are called ary! Halide mononuclear compounds,

-A-

ZoBa pentabromophenol, and polynuclear compounds, z <, B _o chlorinated biphenyl, used «

It has now been found that by admixing one of a brominated polynuclear compound and a metal of the Group Vb containing a combination of flame retardants or fire retardants moldable and injectable linear polyamides molding and S-ferrang molding compounds are obtained on the basis of polyamides, which have a significantly higher flame retardancy than the known Molding and extrusion molding compounds.

It has also been found that by adding the invention Combination of flame retardants or fire retardants to form mouldable and sprayable mixtures Based on polyamides, a considerable improvement is achieved in that certain physical properties of the Polyamide improves earth performance while not significantly degrading the other physical properties.

By adding the above-mentioned combination of flame retardants, consisting of a) a brominated polynuclear compound and b) a compound that is a metal of Group Vb of the Periodic Table (published in Advanced Inorganic Chemistry by Cotton and Wilkerson, Interscience Publishers, 1962) Polyamides which are suitable as molding resins are polyamide mixtures obtained, which have a significantly higher flame retardancy than the known mixtures, the chlorinated polynuclear compounds or brominated mononuclear compounds Connections included. In other words, with the same concentrations of bromine, that in the brominated raehrkernigen Compound is contained in comparison to equal concentrations of chlorine that in the chlorinated polynuclear Compounds are contained, result in the broraized polynuclear Compounds Polyamide mixtures with considerably better flame retardancy. In the case of the known form and strand

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molding compounds containing the brominated mononuclear compounds contained, there were great difficulties in their use, since the mononuclear compounds are thermally unstable and are degraded at the temperatures necessary for processing and using the polyamides » Furthermore, these brominated mononuclear compounds degrade quickly before the temperature of the polyamide rises its ignition temperature rises, so that it does not adequately protect the polyamide at its ignition temperature or in ensure their proximity »By using the brominated polynuclear compounds according to the invention, this Problem solved because they are in the range of temperatures required for processing the malleable linear polyamides as Melt are necessary, are very stable and also in connection with those containing the metal of group Vb Compound at the combustion temperatures of the polyamide are decomposable and a sufficient protection of the polyamide at or near its ignition temperature.

It has also been found that by admixture of the flame-retardant and fire-retardant agent according to the invention molding compounds and Strangpreßmassen based on linear polyamides, which is about 2 to 50 wt _o - (based on the total weight of polyamide plus reinforcing filler) $ of a reinforcing filler, molding compounds with exceptional flame resistance and low combustibility are obtained when the brominated polycyclic compound in amounts of about 20 to 30 wt _o - $, based on the weight of the polyamide is added and the Vb-containing compound in such amounts is present the metal of group that the weight ratio of the Group Vb metal-containing compound to the bromine contained in the brominated polynuclear compound is at least 0.1: 1.0. If the brominated polynuclear compound is added to the composition consisting of the polyamide and the reinforcing filler in an amount which is greater or less than this critically important amount,

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- D -

the flame retardancy of the polyamide mixture is worsened «.

The above-described pressable and injectable linear polyamides to which the invention is directed are flammable and combustible. 6 mm or 3.2 mm thick is held by a clamp so that the longest dimension is perpendicular. A piece of untreated cotton wool is placed 30.5 cm below the lower edge of the sample. A Bunsen burner with a tube of 9.5 mm in diameter is set so that a blue flame of 19 mm is formed. The burner is placed under the lower edge of the sample so that the lower end of the sample is 9.5 mm from the upper end of the Bunsen burner tube. The Bunsen burner is held in this position for 10 seconds and then removed. The duration of the afterburning or afterglowing of the sample is recorded. If the afterburning or afterglow of the sample stops within 30 seconds after the flame has been applied, the Bunsen burner is placed under the sample again for another 10 seconds immediately after the afterburning or afterglowing of the sample has ceased, after which the duration of the afterburning or afterglowing of the sample is noted again v / ird. The droplets of the polymer is also noted, being retained if the Verbandv / atte is ignited by the drop _o

When pressable and injectable linear polyamides of the above if subjected to the test described, the polyamide will burn, with burning droplets falling immediately, which ignite the bandages. When reinforced polyamide is subjected to this test, the polyamide will burn and after For a short time, burning particles constantly fall down and ignite the dressing until the entire sample is burned is.

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JUe invention sets itself the task of solving the problem of Flammability and combustibility of malleable and injectable linear polyamides and pressable and injectable to solve reinforced linear polyamides. The invention is particularly directed to solving the problem of a more effective anti-flammable system for polyamides directed

For the purposes of the invention, the following have been found special brominated polynuclear compounds as suitable:

Compounds of the Pormel

(D

in which R. stands for Wasöorstoffatome or bromine, with at least 2, preferably with at least 4 Bromatoraen in the molecule. Examples are 2,2 ', 4,4'»6,6'-Hexabromobiphenyl and 2,2 ', 4,4' ~ Ietrabromobiphenyl _o

Compounds of the Pormel

-OR

^: B.

(II)

in which R.sup.1 represents carbon atoms, acetate groups or methyl radicals and R.sup.1 represents hydrogen atoms or bromine atoms, with at least ?., preferably with at least 4 bromine atoms in the molecule. Examples of this are 5, 5,3 ', 5'-Tetraborn-2, 2-

,: -J9815 / 1PS8

- 8th -

bis (4,4'-dihydroxyphenyl) propane, 3,5,3 ', 5'-ietrabromo-2, · 2-bis (4,4'-diacetoxyphenyl) propane and 3,5,3 ', 5' ~ Tetrabröni-2,2 · bis (4,4'-dimethoxyphenyl) propane.

Compounds of the formula

¹ Vs

(III)

in R ₇ , for oxygen atoms, sulfur atoms, sulfur dioxide, jj · - ■ * - -

Methylene or phosphonate radicals and Rp for hydrogen atoms or bromine atoms, with at least 2, preferably at least 4 bromine atoms in the molecule Examples of such compounds are 3,5,3 ', 5'-tetrabromobiphenyl ether, 3,5i3', 5'-tetrabromobiphenyl sulfide, 3,5,3 ', 5'-tetrabromobiphenylsulfoxide, 2,4,3 ', 4', 5'-pentabromobiphenyl methane, 2,2 ', 4,4', 6,6'-hexabromobiphenyl ether and decabromobiphenyl ether "

Particularly preferred for the purposes of the invention are brominated polynuclear compounds of the formula (III) in the ryj is an oxygen atom »

As compounds which contain a metal from group Vb, compounds are suitable for the purposes of the invention which Contains phosphorus, arsenic, antimony or bismuth. Particularly suitable here are compounds, the oxides of these Contain metals of group Vb, of which antimony trioxide is particularly preferred »

With the inventive combination of flame-retardant or fire-retardant agents can be pressed and sprayable linear polyamides may be made flame retardant, from about 2 to 50 wt _o - $>, preferably about 10 to 40 wt _o -% of a reinforcing filler (based on the total weight of

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Polyamide and reinforcing material). A wide variety of reinforcing fillers can be used in the context of the invention, for example Astest fibers, cellulose fibers, cotton fabrics, paper, synthetic fibers, metal powder, glass beads or glass fibers in the form of staple glass silk or endless glass silk strands _o Particularly preferred of these reinforcing fillers are glass fibers in the form of endless glass silk strands or Stacked glass silk, the length of which can be approximately 1.6 mm or less to 6.4 mm or more _e

Pressable and injectable unreinforced polyamides is the brominated polynuclear compound in amounts of about 2 to 35 Gewo-5 &, preferably about 3 to 15 wt .- ^, based on the weight of the polyamide, while the Group Vb metal-containing compound is added in such Amounts added that the weight ratio of these Compound to bromine contained in the brominated polynuclear compound, at least 0.1: 1.0, preferably about 0.5ϊ1 to 2.0: 1, in particular about 0.8: 1 to 1.3: 1 is ο

Compressible and moldable reinforced polyamides which the reinforcing filler in an amount of about 2 to 50 wt _e - preferably%, about 10 to 40 $ of the total weight of polyamide and a reinforcing filler, ikann reduced flammability, be imparted by the reinforced polyamide about 15 to 35 wt .- ^ of the brominated polynuclear compound, based on the weight of the polyamide, and a Group Vb metal-containing compound is added in such amounts that the weight ratio of the Group Vb metal-containing compound to bromine in the brominated polynuclear compound at least 0.1: 1.0, preferably about 0.5: 1.0 to 2.0: 1.0, with a weight ratio of about 0.8: 1.0 to 1.3: 1.0. is particularly preferred for the production of pressable and injectable reinforced polyamides with exceptionally high

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Flainmwidrigkeit however, the brominated polycyclic compound preferably in amounts of about 20 to 30 wt _o - $, based on the weight of the polyamide, and added to the metal of group Vb-containing compound in such amounts that the weight ratio of the metal of group Vb containing compound to bromine in the brominated polynuclear compound has the aforementioned values.

The brominated polynuclear compound and the Group Vb metal-containing compound cannot enhance this or reinforced polyamide by any known method in which homogeneous mixtures are obtained, can be added. For example, the flame retardants or fire retardants in the barrel with the Polyamide are mixed, whereupon the mixture is extruded to form a homogeneous mixture, or the Flame retardants can be added to the polyamide during extrusion to form a homogeneous mixture added to ground.

The invention is further illustrated by the following examples. In the experiments described there, the Flame retardancy of all samples according to that described above Method determined, whereby all samples had a thickness of 3.2 mm »

example 1

A polyhexamethylene adipamide having a relative viscosity of 50 was made using a 28.3 g injection molding machine "Mini-jeetor" at a cylinder temperature of around 288 ° C and a mold temperature of about 79 ° C into a sample 127 now in length, 12.7 mm in width and 3.2 mm in thickness The sample was tested for flame retardancy using the method described above Each of the first inflammations tested burned the sample for 6 seconds, whereupon burning particles covered the cotton wool inflamed, dripped down.

This example illustrates that untreated, un-

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reinforced polyamides are very easily flammable and combustible.

Example 2

The polyhexamethylene adipamide described in Example 1 was mixed with 3.2 mm glass fibers evenly to a composition containing 33 wt _o ~ $ glass fibers, based on the total weight of polyhexamethylene adipamide and glass fibers contained by the polymer and the glass fibers were dry blended and Mixture was then extruded with a 19.05 mm Brabender extruder with a length / diameter ratio of 20i1 at about 277 ° C through a 3.2 mm extrusion die. "The strand was granulated and the granulate for subsequent shaping used.

The mixture described above was made into a sample 127 mm in length, 12.7 mm in width and 3.2 mm in thickness Pressed in the manner described in Example 1. The sample was subjected to the flame retardancy test described above. After the initial ignition, the sample burned longer than 55 seconds, with burning particles forming the cotton wool ignited after 20 seconds, continuously dripping down until the entire sample was burned.

This example illustrates that untreated reinforced Polyamides are very easily flammable and combustible.

Examples 3 to 11

Two blends were prepared by adding 200 g of the polyamide described in Example 1 to that in Example 1 dry blended in the manner described with the following additives and then extruded:

a) 60 g of chlorinated diphenyl with 68 wt. ₀ - ^ chlorine ("Arochlor 1268") and 40.8 g of antimony trioxide and

b) 50 g of decabromodiphenyl ether (with 81.9% by weight of bromine) and 40.80 g of antimony trioxide.

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Mixtures were formed which contained the various halogens in equal parts by weight, and in which the weight ratio of antimony trioxide to halogen was 1: 1. About the far superior flame retardant effect of the brominated polynuclear compounds used according to the invention in comparison with the known chlorinated polynuclear compounds To illustrate compounds, each mixture was sampled in the manner described in Example 1 127 mm long, 12.7 mm wide and 3.2 mm thick. These samples were tested for flame retardancy and Subjected to flammability by the method described above.

After the first ignition, the sample (a), which contained the chlorinated biphenyl, burned an average of 7 seconds, whereupon burning particles dripped down and ignited the cotton wool.

The sample (b) which brominated the brominated used in the present invention polynuclear compounds with the same amount of halogen as in sample (a) and the same amount of antimony trioxide as contained in sample (a), burned on average 0.25 seconds after the first ignition and then went out without that particles dripped down. After a second ignition, the sample (b) burned an average of 2 seconds and then went out without any burning particles dripping down.

The results obtained are shown in Table I. This table illustrates that those used in the present invention brominated polynuclear compounds as flame retardants for non-reinforced polyamides chlorinated polynuclear compounds used in the known processes at an equivalent halogen concentration are far superior.

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Table I * example

Multinuclear compound, g

Kalogen

salary,

Antimony trioxide

salary,

First inflammation after drops? Inflammation of the duration, Seko wadding through

Drops?

Second inflammation

To Drops? inflammation burning the cotton wool duration, by Sec. drops

NJ O CD OO —Jk CfI -v,

5 5 7 8 9

10 11

60 ** 60 ** 60 ** 60 ** 60 ** 50 ***

50 *** 50 *** 50 ***

40.8 40.8 40.8 40.8 40.8 40.8 40.8 40.8 40.8

40.8 40.8 40.8 40.8 40.8 40.8 40.8 40.8 40.8

5 5

15 5 7 0 0 0-

Yes

nem no no

no

no no no no no no no no

* All samples contained 200 g polyamide

♦♦ Chlorinated biphenyl with 68% by weight of chlorine ("Arochlor 1286") *** Decabromobiphenyl ether with 81.9 wt .- ^ bromine

Examples 12-19

Two blends were made by adding 400 grams of the glass fiber reinforced polyamide described in Example 2 dry mixed with the following additives to the V / ice described in Example 1 and then extruded became:

c) 77.12 g of chlorinated biphenyl with 68% by weight of chlorine ("Arochlor 1268") and 52.40 g of antimony trioxide and

d) 64.00 g of decabromobiphenyl ether (with 81.9% by weight of bromine) and 52.40 g of antimony trioxide o

Reinforced polyamide blends were formed that contain the different halogens in the same proportions by weight and contained antimony trioxide and halogen in a weight ratio of 1: 1 «,

To the significantly superior flame retardant effect of the brominated polynuclear compounds used according to the invention in comparison with those in the known processes To illustrate chlorinated polynuclear compounds used, each mixture was based on that in Example 1 in the manner described, formed into specimens 127 mm long, 12.7 mm wide and 3.2 ram thick. Every sample was on Flame resistance tested according to the method described above "

After the initial ignition, sample (c), which contained the chlorinated biphenyl, burned an average of 41 seconds. Burning particles dripped off the sample, igniting the cotton wool.

The sample (d), the brominated polynuclear compound used according to the invention at the same halogen concentration as the sample (c) contained and antimony trioxide in the same amount as the sample (c), burned after the first Inflammation did not continue and did not drip. Each of a second ignition burned on average in sample (d)

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0.75 seconds and then went out without separating Particles dripped off <>

The results obtained are shown in Table II. This table illustrates that the invention used brominated polynuclear compounds as flame retardants for reinforced polyamides at an equivalent halogen concentration, the chlorinated polynuclear compounds used in the known processes are far superior.

χ 0 9 8 1 5/1 β 5 8

Seisniel More halogen Antimony- Table II * •Inflammation Inflammation
dung the
Cotton wool
by
Drops? To-
burning
duration,
Sec ₀ Second inflammation Inflammation
dung the
Cotton wool
by
Tronfen? l \ ^T rO robust
Connect
dung, g salary,
a trioxide
salary,
& First Drops? Yes _ Drops? _ 12th 77.12 ** 52.40 52.40 To
burning
duration,
Sec. There Yes - _ - 13th 77.12 ** 52.40 52.40 41 Yes Yes - - - 14th 77.12 ** 52.40 52.40 40 3a Yes - - - 15th 77.12 ** 52.40 52.40 43 Yes no 1 - no O 16 64.00 *** 52.40 52.40 40 no no 1 no no co
co 17th 64.00 *** 52.40 52.40 0 no no 1 no no in 18th 64.00 *** 52.40 52.40 0 no no 0 no no 19th 64.00 *** 52.40 52.40 0 no no ■?>
'Ti
QO 0

* All samples contained 400 grams of polyamide with 33 percent _o - based $ glass fibers (the
Total weight of polyamide and glass fibers) reinforced v / ar "

** Chlorinated biphenyl with 68 wt _o - $ chlorine ( "Arochlor 1268").
*** Decabromobiphenyl ether with 81.9% by weight of bromine

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Examples 20 to 24

Several glass reinforced polyamide blends were added to the for Examples 12 "to 14 described manner with different Amounts of the brominated polynuclear compounds used according to the invention are produced to the crucial important area of the sets of these ^ bonds, the required for the production of reinforced polyamide yarns with exceptional flame retardancy, too illustrate. All blends contained 300 g of the glass reinforced polyamide described in Example 2 and the following additions:

example Decabromobiphenyl ether Ant imontrioxyd 20th 36 g 29.48 g 21st 48 g 39.30 g 22nd 54 g 44.22 g 23 66 g 54.06 g 24 Comparative sample without f] .ammwidrifünachen

middle

In all of the above mixtures, the weight ratio of antimony trioxide to that in decabromobiphenyl ether contained bromine e-twa 1: 1.

Samples were formed from all mixtures and tested for flame retardancy by the method described above. The results obtained are shown in Table III below. This table illustrates that by admixing the brominated polynuclear compounds used according to the invention to reinforced polyamides in amounts which are within a wide range, the combustibility and flammability of the reinforced polyamide is reduced, but that there is a critically important amount range of the brominated polynuclear compounds in the reinforced polyamides with exceptional flame retardancy obtained ₀

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example Multi-core connection 36 Weight -? £ *** Table III * 48 H, , 7 First inflammation Drops? Inflammation
manure
the
Cotton wool
by
Drops? Yes Second inflammation Trop
fen? Inflammation
dung the
Cotton wool
by
Drops? I. G** 48
54 18th Antimony trioxide 30th
22nd 19th
22nd , 6
"1 To-
burning
duration,
Seko Yes no
no To
burning
duration,
Sec. - - 20th 66
0 24
27 06
0 27 ,1 40 no
no no - no
no no
no 21
22nd 33 29 0
0 no
There 0
α no no NJ
O
CO 23
24 39
44, 14th
> 55 γ 815/1 54, 65 8

■ ^ All samples contained 300 g of glass fiber reinforced polyamide, which was 33% by weight?
Contained glass fibers, based on the total weight of polyamide and glass,

** I) ecabroEibiphenyläther with 81.9 wt. <> - $ bromine
*** Based on the weight of the polyamide alone.

Examples 2-5 to 29

Several glass-reinforced polyamide blends were in the manner described for Examples 12 "to 19" with different Quantities of antimony trioxide and a constant quantity of the brominated polynuclear compound produced, the influence of a change in the weight ratio of the Group Vb metal-containing compound to Bromine in the brominated polynuclear compound to illustrate the flame resistance of the reinforced polyamide. All mixtures contained 150 g of the glass-reinforced polyamide described in Example 2, 24 g of decabromobiphenyl ether and the following amounts of antimony trioxide:

Example 25: 39.3 g of antimony trioxide

Example 26: 19.7 g of antimony trioxide

Example 27: 12.8 g of antimony trioxide

Example 28: 9.8 g of antimony trioxide

Example 29: 0.0 g of antimony trioxide

Samples were prepared from all mixtures in the manner described in Example 1 and tested for flame retardancy checked. The results are shown in Table IV below. This table illustrates that the Weight ratio of the compound containing the metal of Group Vb to the bromine in the brominated polynuclear Compound is an important factor in the production of flame-retardant compounds based on polyamides.

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Table IV *

With- more- bromine-antimony- ratio afterburning core content, trioxide- antimony duration, sec, No. ₀ connection content, g trioxide / dung, g ** bromine

25th 24 · 19.64 39.3 2.0 0 26th 24 19.64 19.7 1.0 1.7 27 24 19.64 12.8 0.65 6.0 28 24 19.64 9.8 0.50 7.0 29 24 19.64 0.0 0.0 > 30.0

* All samples contained 150 g of glass fiber reinforced polyamide with 33% by weight of glass fibers, based on the Total weight of polyamide and fiberglass.

** Decabromobiphenyl ether with 81.9

«- $ bromine.

Examples 30 and 31

Two mixtures of the following composition were made

Example 30; Glass fiber reinforced polyhexamethylene adipamide containing 25% by weight (based on the total weight of the polymer plus glass fibers) glass fibers 3.2 mm long (as in Example 2) and no flame retardant.

Example 31: Flame-retardant reinforced polyhexamethylene adipic acid amide, containing 25 wt .- ^ glass fibers a length of 3.2 mm, based on the weight of the total mass, 25 GeWo- ^ decabromobiphenyl ether, based on the weight of the polyamide alone, and antimony trioxide in such an amount that the weight ratio of antimony trioxide to the bromine contained in the decabromobiphenyl ether is 1 $ 1 (according to Example 12 to 14).

To illustrate that by adding the invention Combination of flame retardants to polyamides the physical properties of the polyamide blends graze not significantly deteriorated,

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were the physical properties of these mixtures Determined by ASTM Methods The results are below compiled in Table V. This table illustrates that by adding the invention Combination of flame retardants too compressible and injectable polyamides some physical properties, e.g. hardness, tensile strength and flexural strength, are improved and the other physical properties are not significantly deteriorated.

Table V

Example Mr. 3O ^ 31 **

Tensile strength at break, kg / cm 1600 1630 Elongation at break, ^ 3 3

Flexural Strength, kg / cm ² 2270 2306

Notched Izod impact strength, mkg /

25.4 mm width 0.18 0.166

Rockwell M hardness 94 99

■ ^ Glass fiber reinforced polyamide with 25 wt. - $> glass fibers, based on the weight of the total mass; no flame retardants.

^ Glass fiber reinforced polyamide, contain 25 wt .- ^ Glass fibers, based on the weight of the total mass, 25 wt .- $ deeabromobiphenyl ether, based on the weight of the polyamide alone, and antimony trioxide in such an amount that the weight ratio of antimony trioxide to bromine in the deeabrombiphenyl ether is 1: 1.

Of course, the flame-retardant pressing the invention, injection and molding compositions based on polyamides may optionally contain, in addition Wärniestabilisatoren, eg _o combinations of copper acetate with alkali metal iodide, pigments, dyes, color stabilizers, crystal nucleating agents, fluorescent whitening agents, lubricants and matting agents.

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Claims (13)

Pat e nt ans'pr ehe 1) Shape and Strangpreßmassen ^al * f based on linear polyamides with reduced flammability comprising a) a pressable and injectable linear polyamide with a relative viscosity between about 15 and 400, b) a brominated polynuclear compound that occurs in the Processing temperatures of the polyamide are essentially stable and at the combustion temperatures of the polyamide is decomposable and in an amount of about 2 to 35 percent by weight based on weight of the polyamide, is present, and c) a metal of Group Vb of the compound containing the periodic system, ^ i ₆ j_ _n such an amount is present, that the weight ratio of the metal of group Vb-containing compound to the bromine in the brooiierten polynuclear compound is at least 0.1: 1, Is 0. 2) Molding and Strangpreßmassen according to claim 1, characterized in that the brominated polycyclic compound in amounts of from about 3 to 15 wt. -I _'t based on the polyamide, and the metal of group Vb * containing compound in an amount that the weight ratio of the Group Vb metal-containing compound to the bromine contained in the brominated polynuclear compound is about 0.5: 1.0 to 2.0: 1.0, and the moldable and moldable linear polyamide is relative Has viscosity between about 45 and 140. 3) Reinforced molding and extrusion molding compounds based on linear polyamides with reduced flammability and increased flame resistance, containing a) a pressable and injectable3 linear polyamide with a relative viscosity between about 15 and 400, 209815/1658 2U8276 b) a TDromized multinuclear compound, which is used in the Processing temperatures of the polyamide essentially stable and at the combustion temperatures of the polyamide is decomposable, in amounts of about 15 to 35 wt <, - $ based on the weight of the Polyamides, c) a compound containing a metal from group Vb of the Periodic Table in such amounts, that the weight ratio of the compound containing the metal of Group Vb to that in the brominated polynuclear compound containing bromine is at least 0.1 * 1.0, and d) a reinforcing filler in amounts of about 2 to 50 GeWo $ based on the total weight of the polyamide plus reinforcing filler. 4) molding and extrusion compounds according to claim 3, characterized in that they use glass as a reinforcing filler contain. 5) molding and extrusion molding compositions according to claim 3 and 4, characterized in that it is used as a reinforcing filler Glass fibers in amounts of about 10 to 40 wt .- ^, based on the total weight of polyamide plus glass fibers, the brominated multi-core compound in Quantities of about 20 to 30 wt .- ^, based on the The weight of the polyamide and the compound containing the Group Vb metal in such amounts that the weight ratio of the compound containing the metal of Group Vb to that in the brominated polynuclear compound contained bromine is about 0.5: 1.0 to 2.0: 1.0, and the polyamide is a relative Has viscosity between 45 and 140. 6) Form and Strangpreßinas sen according to claim 1 "to 5, characterized in that the metal of the group Vb containing compound ice metal phosphorus, antimony, 2U9815 / 1658 2U8276 Contains arsenic or bismuth " 7) molding and extrusion molding compounds according to claim 1 "to 6, characterized characterized in that, as a brominated polynuclear compound, it is a compound of the formula in the row each for a hydrogen atom or bromine atom, with at least 2 bromine atoms in the molecule, or a compound of the formula —-OR a in which R _B each represents a hydrogen atom, acetate or methyl radical and R _ß each represents a hydrogen atom or an eromatic atom, with at least 2 bromine atoms in the molecule, or a compound of the formula (R ₁₅ ) ₅ in which R _{11 is} an oxygen atom, sulfur atom, sulfur dioxide, a Mothylen- or Phonphonatrect and TIp is a water to ff ο torn odor bromine atom, with 209815/15 [beta] 2U8276 at least 2 bromine atoms in the molecule, contains » 8) molding and extrusion molding compounds according to claim 1 to 7> characterized in that it is a brominated polynuclear compound with at least 4 bromine atoms in the molecule contain. 9) molding and extruding compounds according to claim 1 to 8, characterized in that the weight ratio the compound containing the Group Vb metal to that in the brominated polynuclear compound contained bromine is about 0.8: 1 to 1.3: 1. 10) molding "and extruded compounds according to claim 1 to 9, characterized characterized in that they contain a brominated polynuclear compound of the formula (III) in which Ry. an oxygen atom is » 11) molding and extrusion molding compounds according to claim 1 to 10, characterized in that they are as linear polyamide Contain polyhexamethylene adipamide. 12) molding and extruding compounds according to claim 1 to 11, characterized in that they are used as a compound, the contains a metal from group Vb, contain antimony trioxide. 13) molding and extrusion molding compounds according to claim 1 to 12, characterized in that they are as a brominated polynuclear Compound Decabrorabiphenylather contain. 209815/165