DE2136277A1 - Polymers with reduced flammability - Google Patents

Description

Folder 22638 - Dr "K / hr
Gases FC ₀ 2296t

IMPERIAL CHSMICAI. INDUSTRIES LIMITED, London, UK

"Polymers with Reduced Flammability"

Priority; July 20, 1970, Great Britain

The invention relates to the production of polymers (this term also includes mixed polymers) which have reduced flammability. The invention relates in particular to the production of polyamides with reduced flammability. It relates calibration AUOH to said polymers and to articles such as, B ₀ threads, yarns, films and sheets, which have been prepared of the aforementioned polymers, for example, by extrusion or pressing "

Numerous attempts have been made to make normally flammable synthetic polymers flame resistant 2SU grant, especially if the named polymers in the manufacture of textile material! «! and the like are to be used. In many cases, halogenated « Compounds with success used in that Polymer.au

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at any suitable point in time ". However, in such a case, the polymers with which a success has been achieved are such" polymers that are relatively unreactive towards halogen groups * such as polyolefins ". In the case of relatively reactive polymers * such as »certain condensation polymers and especially polyamides _? e.g. Hylon-6,6, & ε has proven to be very difficult

halogenated
highlighted, suitable / compounds am found »which are already effective in small amounts and which do not react with the polymer, resulting in a discolored or degraded product. By the applicant, many were tried of the compounds used to date for this purpose, such as ₀ Chlorensäureanhydrid (chlorendic anhydride), hexachlorobenzene, "etc., but in all cases the resulting polymer was severely discolored j sometimes it was even almost black, or it has been so degraded that, due to its low viscosity, © 3 was unusable, for example, for the production of extile fibers by melt spinning »

It has now been found that the discoloration or degradation mentioned can largely be avoided if a special class of halogenated compounds are added to the polymers mentioned, and in particular polyamides, either during production or in the fully polymerized molten state «

The named class of compounds is defined as follows: (I) The molecule of the compound has one or more benzene cracks or one or more fused benzene cracks or a combination of the rings mentioned and the ring structures mentioned »Neighboring Benssol rings to be connected by one or two bonds »

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If there is only one bond, then it can be a direct bond or a bond with groups that are stable in the polyamide _{melt, such as Z 0} B. - (0R ₂ ) _n ~, -0-, -SO ₀ -, -0- (CR ₀ LO =, where R is, H or alkyl,

d. fc yes *

η is 1 or more and preferably 1 to 6 and m is 2 or more and preferably 2 to 6, or -M'-, where R 'is aryl, alkyl or (CH ₂ ) ί , where ρ is more than 1 and φ stands for a Benaol ring and in which each aromatic ring can carry halogen substituents »If there are two bonds, then at least one bond must be via one of the groups mentioned (XI) At least one benzene ring or at least one condensed ring structure is through substituted one or more halogen atoms.

(III) Certain points on the molecule can be substituted by polymer-reactive groups, such as, for example, amide-forming groups Groups or polymerizable © derivatives thereof, provided that these groups do not give the polymer any significant discoloration grant, these groups preferably being represented by an alkylene group separated by a benzene ring or a condensed ring structure o

(IV) No halogen atom shall be in the ortho position to another halogen atom or to any electron withdrawing group »

Each ring or each condensed ring structure can be further substituted by non-reactive, non-polar groups, such as methyl püppen, the substitution preferably being symmetrical, groups which carry substituents which are unstable in the polyamide melt, such as ZoB ₀ -KH-, all connecting groups as in requirement (I) are unsuitable because they cause excessive discoloration of the polyamide

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melt yield.

With the above definition "condensed singing structure" are for example a naphthalene or an anthracene structure Meant ο Bin © symmetrical substitution on the molecule is preferred, especially when the molecule is in the Polymer molecule is incorporated, since it has been found that such structures have the least disturbance compared to the | physical properties of the base polymer and one of them produced yarn

Examples of compounds of the present invention are: 3,6-dibromodurol
Bis (p ^ bromophenyl) ether
4 ^ bromodiphenyl

2,7-dibromo-9 »9-bis (ß-oarboxyethyl) flupren 2,5-dibromo-p-phenylene-diacetic acid 2,5-dibromo-3 »β-dimethyl-p-phenylene-diacetic acid.

Preferred compounds for use according to the invention) are:

Bis (p-bromophenoxy) ethane

Tris (p-bromophenyl) amine

2,4,6,2 ', 4', 6 · -hexabroaodipheny1

1 93 »5 * 2ribromobenaol

2 1 4,6-tribromomesitylene

2,7-dibromo * 9,9-bis (ß-oarboxyethyl) fluorene 2,4,6,2 ', 4', G "-hexabromodiphenyl-methane 2,4,6 _f 2 ³ , 4 ^J , 6'- Hexabromodiphenyl ether Iris (2 ₉ 4-dibromx> phenyl) amine.

It is preferred that these compounds be incorporated into the polymer

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_ 5 «■■

are incorporated in such amounts that a preferred halogen content of 0.5 to 5 »O Gewo-fi, based on the weight of the final polymer, is achieved. It has been found that the compounds defined above with the important. Requirement (IV) to be added to the condensation polymers, such as, for example, «the polyamides, which are too small for significant changes to be produced in the polymers mentioned, in addition to the good flame resistance.

The particular amount of the compound added to the polymer depends of course on many factors, such as, for example, on the Structure of a textile fabric ^ made from flame-resistant threads is made, on the degree of flame resistance desired

Of course, other additives can also be incorporated into the polymer, in particular suitable netalloxides, which are referred to here as non-discoloring oxides, such as ZoB. Titanium dioxide or antimony trioxide, which on the flame-resistant Compound exert a synergistic effect without sion an excessive discoloration or otherwise Change in properties result.

The preferred halogen is bromine as this element is a better one Resistance to chlorine results, which is why less of the compound must be added to the polymer.

If there are no polymer reactive groups present in the molecule of the compound, then the preferred is halogen Bromine.

Bromine compounds not only have more effective flame retardants

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Properties than chlorine compounds, but they are also less volatile under normal processing conditions Of course, the halogen loss is in massive molded articles not as large as in the case of melt-spun threads "

Sin advantage of the compounds that are made by being reactive with polymer Groups are substituted, consists in that they are linked to the Polymerkstt © «. This will reduce the loss Halogen during processing, for example during spinning or during wet processing of the yarns, etc. », considerably decreased

The compounds mentioned can be added at any suitable point in time during the polymer preparation or during the completely polymerized Material to be added, depending ..on .which Way the best results can be achieved · They can be added in the form of a solid or a solution or a melt ο You can be in the polymer either in the form of a rope's chemical polymer structure (via reactive groups linked) or, if no reactive groups are present, in 3? form a solution or dispersion in the polymer be incorporated «Before incorporation, they can be incorporated into a basic mixture consisting of the polymer, which contains a high percentage of this compound «being the master batch, then mixed with the rest of the polymer will. The flame retardant compound can also be given continuously in pelletized form to the molten polymer before this is extruded, for example in the spinning unit, the addition speed of the pellets so it is regulated that the desired concentration of the additive is created in the extruded polymer »

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To measure flame resistance, the following test is used. The device consists of a metal frame with 16 inches long and 8.9 inches wide and a slope of 45 ° C. A Bunsen burner is attached "so that it can be swiveled" around it with the bottom of the plane of the frame to bring in touch.

The sample used, which consists of a length of stocking, Measures 4o, 6 cm 10.2 cm when flat. A strip off a non-woven fiberglass fabric is attached to a Size of 16 inches χ 12.7 cn cut. The fiberglass fabric is then burned out in a flame to burn off any materials present. "To prepare the test samples, the length of the stocking is attached centrally to the fiberglass fabric." The line of stacks becomes vertical run to the center of the composite layer with the ends barely touching and with two parallel long edges stacked 10.2 cm apart will. The positioning of the stacks is important as they act as conductors of heat.

The sample is then attached to the metal frame, whereby the lower edge lies evenly against the underside of the frame. The sample is held with the help of pens, protruding from the top surface of the frame. The holder is then placed in a draft-free chamber, the The sliding door of the same is closed to within 10.2 cm from the underside of the chamber, the Bunsen burner is lit, and the flame is set to a height of 2.5 cm. Then the flame becomes 15 seconds long towards the center the lower edge of the sample held and then removed.

The burning time after removing the Bunsen burner and the The charred length from the lower edge is noted *

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Attempt is ait six samples _s carried out and the average burning times and the average Verkohlungslängen be calculated.

The invention will now be elucidated by means of the following examples explained

example 1

91? Eight sewn ropes of nylon-18ß-polymer, which contained 2 # antimony trioxide, and 8.2 volumes of bis (p-bromophenyl) ether were mixed well. The system was flushed with nitrogen and placed in an oil bath for 15 minutes under a stream of nitrogen 285 ⁰ C heated until the mixture melted. The mixture was then vigorously stirred for 15 minutes to produce a homogeneous viscous melt. It was then allowed to cool with the stirrer removed from the melt *

The virtually, waisse polymer besaes an inherent viscosity of 0.891, a Vicat Erweiohungspunkt of 266 ⁰ C, a relative viscosity of 49 »O ₇ a & lt Aminendgruppengeh (AEQ) of 26.45 eq / g i0, a Oarboxylendgruppengehalt (CBG) of 89 Equivalents / 10 g and a content of 3 * 42 f> bromine.

Ss was spun at 285 C into a 5-ply yarn, with a Take-up speed of 121.9 m / min was used. That Yarn was twisted cold under a ratio of 3.8, the following yarn properties were obtained:

Titer (den) 31 * 0

Elongation (#) 45.2

Tear strength (g / den) 4.06

Initial modulus (g / den) 22.3

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The yarn was knitted into stocking legs with an approximate width of 10.2 cm on a circular knitting machine, and the Stocking legs were made by the procedure described above Checked for flammability after being an aqueous. Had been subjected to cleaning to remove the spin finish. An analysis of the knitted fabric showed a bromine content τοη 0.5 #, 30 that is, a loss of bromine during processing and the cleaning took place.

At the same time, a cleaned comparison sample was made Hylon 6,6 yarn tested under the same conditions. the The results are summarized in Table I.

Sample mean mean

Distilling

Hylon-6,6 + bis (p-bromo-

phenyl ether + 2 i » Sb ₃ O ₅ 6.05 cm 3.6 seconds

Bylon 6.6 comparative sample 16.4 inches 35.6 seconds

So it could be shown that the bromine and antimony

The holding yarn had an increased flame resistance compared to the comparative yarn.

Example 2

45.9 parts by weight nylon-6,6 and 4.1 parts bis (p-bromophenyl) ether were mixed well, the system was purged with nitrogen and heated to 285 ° C. for 10 minutes under a stream of nitrogen heated. The mixture was then vigorously stirred for 15 minutes to produce a homogeneous viscous melt. It was then allowed to cool, the stirrer being removed from the molten salt was »

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The off-white polymer had an inherent viscosity of 0.92, a Vicat Erweichungspuakt of 267 ⁰ C, a relative viscosity of 48.9, an AEG of 33.2 equivalents / 10 g, a GBG- of 63.0 equivalents / 10 g and iron bromine content of 3.59 % o

It was at 273 ⁰ C with a winding speed of at 12f, 9 m / min in a 5-filamentous yarn schmelzgespoBnen. The yarn was cold drawn to a ratio of 4.0 with the following yarn properties:

Titer (den) 40.0

Elongation {%) 41.5

Tear strength (g / den) 3.93

Initial modulus (g / den) 23.5

The yarn was knitted into stocking legs with a width of approximately 10.2 cm on a circular knitting machine and tested for flammability by the method described above, after the stocking legs had been subjected to an aqueous cleaning in order to remove the spin finish. An analysis of the knitted fabric gave a bromine content of 0. 7 fi ° The results of the flammability tests are given in Table II below:

Table II

Sample mean mean

——— Charring long burning time

Nylon-6,6 + bis (p-broiao-

phenyl) ether 25.40 cm 51.0 seconds

The gam, which only contained bromine, was compared to the Verglsiohsprobe an improved flame resistance, however

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it was not as good as the yarn, which contains bromine and antimony trioxide (see example 1) contained,

Example 5

92.70 parts by weight nylon-6,6 containing 2 % antimony trioxide and 7.30 parts dibromodurol were mixed well, the system was vacuum purged with nitrogen and then heated ^{to 285 ° G for 20 minutes under a stream of nitrogen.} The mixture was then vigorously stirred for 10 minutes to produce a homogeneous viscous melt. It was then allowed to cool with the stirrer removed from the melt «,

The almost white polymer had an inherent viscosity of 0.94, a Vicat softening point of 267 ^° C., a relative viscosity of 87.9 »an AEG of 22.7 equivalents / 10 g» a CBG of 113.3 equivalents / 10 g and a bromine content of 2.91 jC.

There was a windup speed of 115.8 a / ain at 290 ⁰ C in a 5-filamentous echmelzgesponneno yarn The yarn was hot verstreokt at a ratio of 3.6, with the following yarn property were obtained en;

Siter (den) 35.0

Extensibility (£) 39.2

Tensile strength (g / den) 4.49

Initial modulus (g / den) 32.2

The yarn was knitted on a circular knitting machine into a stocking leg with a width of approximately 10.2 cm and tested for flammability by the method described above ₉ after the spin finish had been removed by aqueous cleaning.

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At the same time a cleaned comparison sample made of MyIon »6 _s 6-yarn was tested under the same conditions. The results are summarized in the following table:

Table III

Sample mean mean

_{r i} , Yerko hl ungalong burning time ,

ffylQn-βίβ + dibromoduole

+ 2% SbgO »5, 92 cm 9 * 9 seconds

Nylon-ö ^ -comparison sample 4O _? 64 cm 35 »6 seconds

The sample that contained bromine and antimony trioxide _? beeasa has a better flame retardancy than the comparison sample * An analysis showed that it is 1 _? 71 Ji Brom contained ":

Example 4

An autoclave with a capacity of 4 1 was filled with 1550 parts of hexa-diethylene diammonium adipate, 226 (tew * parts of the hexamethylene ammonium salts of 2 _i 7-dibromo-9i9-bis (13'-carbO3cyäthyl) fluorene (DBi ¹ A), 2 öew .- ^. based on the finished polymer "Antimonf 1/3 mol ~ $ an aqueous solution of acetic acid, and Hexamethylendiaiain ICX) O wt 'parts by water charged _t and the polymerization was carried out in the usual manner ·

The polymer obtained had a relative viscosity of an ABa of 56.8 equivalents / 10 g, an OEO of 99.2 Equivalents / t 0 g and a bromine content of 3.70 Jt.

Bs was extruded into 20-ply yarn on a screw extruder, and the (Jam was drawn © with a 70 ⁰ O drawing pin at a ratio of 2.8, with the following

1098 & I / 172S

Properties obtained j

Titer (den) 92 _? 0

Elongation (^) 23.0

Tear strength (g / den) 3 »0

Initial modulus (g / den) 17.4

The yarn was knitted on a circular knit in stockings with a width of approximately 10.2 cm, "and the stocking legs were tested for flammability by the method described above, after extraction with methanol and cyclohexane to remove the spin finish had been carried out _o

At the same time, a cleaned sample of nylon-6,6 ~ garo tested under the same conditions The results are in given in the following table:

Table , IV

Sample mean mean

Charring length burning side

Nylon-6,6 + 2 # ₅

DBFA-SaIz * ° 3.57 cm 14.0 seconds

Nylon-6,6- ~ comparative sample 16 inches 64.5 seconds

The sample containing bromine and antimonyuroxide had better plasma inhibition than the comparison sample. It contained $ 3.42 bromine. (Eg there was no noticeable loss of bromine.)

example b

Dar rarde autoclave with 1620 parts by weight of hexamethylene-tunnel Ejamoniumadipat, 170 wt, parts by Heiamethylendiammoniumsalai of 2,7-Dlbromo ~ 9 »9-biö (beta-carboxyethyl) fluorene, 2 wt .- ^, based

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on the finished polymer _s antimony trioxide, O _5, charged $ 3 ftol- an aqueous acetic acid solution and IOOO parts of water "and a polymerization was carried out in the manner übliohen"

The resulting polymer had a Vieat-Erweiehungspunkt of 265 ⁰ Oj a relative viscosity of 39 "5, an AEG of 34 Iquivalenten / i0 g, a CEG of 111 ₃ 5 equivalent / g and a ί0 Bromgehalb from 2.78% ₀

It was extruded on a son corner extruder into a 20-filamentous yarn, and the yarn was verstreokt at a Streckstiftemperatur 70 ⁰ O and a ratio of 3 »2, to obtain the following properties> Rarden: Titer (s) 76.0

Extensibility (%) 16.0

Tensile strength (g / den) 4.10

Initial modulus (g / den) 23.2

The yarn was knitted on a circular knitting machine into 3 trumpet legs with an approximate width of 10 ₉ 2 cm, and the stocking legs were tested for flammability by the method described above, without having been cleaned beforehand ο

At the same time, a comparison sample made of nylon-6,6-gam tested- The results are given in Table V:

Table V

Sample mean mean

_—— VerkonluBfCBlänge burning time

ITylon-6.6 + 2 % Sb ₅ O, +

DBFA-SaIz ^d ° 4.19 cm 18.0 seconds

40.64 cm 62.1 seconds

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The yarn.? which contained bromine and antimony trioxide »was self-releasing and possessed a higher degree of flame retardancy than the comparative sample. It contained 2 ₉ 68 % bromine * (there was therefore no significant loss of bromine»)

Example 6

92 _? 94 wt. "Parts üylon-öyö-polymer * containing 2 fi antimony trioxide, and 7 _f 06 wt ₀ parts by bis (p ~ bromophenoxy) ethane were _T well mixed, the system was purged with nitrogen and under a nitrogen atmosphere in an oil bath 285 ⁰ O heated for 30 minutes? until the mixture had melted "The mixture then became. Vigorously stirred for 15 minutes in order to produce a homogeneous, viscous melt. _O Bs was then allowed to cool, the Bührer having been removed from the melt

The nearly white © polymer had a Vicat Brweichungspuakt of 274 ⁰ C, a relative viscosity von.61,3 * an ASG of 38 _p 2 equivalents / 10 g, a CEG of 146.0 equivalents / 10 g and a bromine content of 2 , 76 % _o

It was spun at a windup speed of 121.9 m / min at 310 ⁰ C in a 5-filamentous yarn "The yarn was verstreekt at 120 ⁰ C under a ratio of 4.0 hot, and the following yarn properties were obtained:

Titer (den) 40.4

Elongation (#) 39.0

Tear strength (g / den) 3.07

The yarn was made into hosiery on a circular knitting machine. " knitted with öinar approximate width of 10.2 cm, and the St3? UmpfbeiJäe were made by the method described above

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«Ρ 16 -

Checked flammability _? after they had been subjected to an aqueous cleaning process to produce the spin finish. The analysis of the knitted fabric showed a bromine content of 1.13 #c

At the same time a cleaned comparison sample from Kylon " 6,6-gara tested under the same conditions »The results are shown in the following table;

Table VI

Sample mean mean

.. charring length firing time

Nylon-6,6 + bis (p-bromo-

phenoxyjethane + 2 $> Sb ₃ O ₃ 5 _S 92 cm 28.9 seconds nylon-6,6 comparative _{sample 40 * 64 cm 76 f} 0 seconds

The Gara _? which contained bromine and antimony trioxide, had better flame resistance than the comparison yarn,

Example 7

94f16 parts by weight nylon-6 _? 6-polymer, which contained 2% antimony trioxide »and 5» 84 parts by weight of tris (p-bromophenyl) amine were mixed well, the system was flushed with nitrogen and ^{heated in an oil bath at 285 0} O for 30 minutes under a nitrogen atmosphere » until the mixture was melted. The mixture was then stirred vigorously for 10 minutes to produce a homogeneous viscous melt. It was then allowed to cool with the stirrer removed from the melt.

wöisse polymer had a Vioat-Erweichuagepunkt of 266 ⁰ C, a relative viscosity of 71.3, an ABG 26.6 & Ätttival nt "n / 10 ⁶ g, a OEG of 89.5 Äcjuival tflaa ^ / & lö and a Örejugehalt of 5, Oi jC.

Ss was on with a winding speed of 121.9 m / min "at 300 ⁰ in G © in 5-filamentous spun yarn" The yarn was cold-drawn at a ratio of 3 _S 5, wherein the following yarn properties obtained wurdenι titer (s) '22.2

Tear strength (g / den) 4 »15

Extensibility {%) 64 ₉ 1

The yarn was knitted into stocking legs approximately 10.2 cm wide on a circular knitting machine, and the stocking legs were tested for flammability by the method described above after being subjected to aqueous cleaning to remove the spin finish. The analysis of the knitted fabric showed a bromine content of $ 2.43,

At the same time, a cleaned control sample made of Hylon 6,6 yarn was tested under the same conditions. The results are given in the following table:

Tahelle

Sample mean mean

Brennaeit

Nylon-6,6 + tris (p-bromophenyl) -

amine + 2 # Sb ₃ O ₃ 4.77 cm 10.7 seconds

] iIylon-6 _? 6-Comparative Proba 16 ”141» 2 seconds

The yarn; which contained bxom and antimony triocide, beease better flame retardancy than the comparative ganxc

Example 8

94.65 parts by weight of Hylon ~ 6,6-polymer, welohes 2

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contained, and 5 , 35 wt., - ropes 2.4? 6 * 2 _? 4 ^; , 6 ⁵ -hexabromodiphenyl were mixed well * the system was flushed with nitrogen and ^{heated to 285 0} O for 20 minutes under a nitrogen atmosphere in an oil bath? "Until the mixture was melted. The mixture was then stirred vigorously for 20 minutes to produce an iriscous homogeneous melt. It was then allowed to cool with the stirrer removed from the melt.

The white polymer besaes a relative viscosity of 38 _P 2 ₅ a Vicat softening point of 264 ⁰ C, an AEG of _5? 8 equivalents / 10 g _P a CSG of 157.0 equivalents / 10 g and a bromine content of 4.19 fi *

It was melt-spun at 280 ⁰ C in a 10 ~ filamentous yarn under a winding speed of 121.9 m / min. The yarn was stretched hot at 100 C under a ratio of 4.0, the following game properties being obtained *

Titer (den) 36.1

Tensile strength (g / den) 3.55

Elongation (#) 25.30

Initial modulus (g / den) 20.70

Hot water shrinkage (#) 12.6

The yarn was knitted into stocking legs with an approximate width of 10.2 cm on a circular knitting machine, and the Stocking legs were tested for flammability by the method described above after they had been removed from the spin finish had been subjected to aqueous cleaning * Analysis of the knitted fabric showed a bromine content of 2.70 #.

At the same time, a cleaned comparative yarn was aue

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Hylon-6 _? 6 tested under the same conditions The results are given in the following table?

table VIII

Sample mean mean

Verkohlu ng s length focal tent

+ Hexabromodiphenyl
O,

Nylon ojo comparison sample 4O _? 64 cm 141.2 seconds

yj py

+ 2 % SbgO, 5.18 cm 4.2 seconds

The yarn? which contained bromine and antimony trioxide a better flame retardancy than the comparison yarn «

Example 9

96.06 parts by weight of STylon-öjö-polymer, which contained 2 %> antimony trioacid, and 3 »94 parts by weight of 1,3,5-tribromobenzene were mixed well, the system was purged with nitrogen and 30 minutes under one nitrogen atmosphere, heated in an oil bath at 285 ⁰ C until melted, the mixture was- the mixture was? stirred at 0 minutes vigorously to produce a homogeneous, viscous melt, "It was then allowed to cool, the stirrer was removed from the melt.

The white polymer had a Vicat-Erwslchmngspuakt of 270.5 ⁰ O. a relative viscosity of 52 * 8, an AEG of 19 * 4 equivalents / 10 g, a GEG of 137.3 equivalents / 10 g and a bromine content of 1, $ 89 > *

There was an up winding speed of 121.9 m / min at 305 ° 0 in a filamentous 5-spun yarn "The yarn was b" i ^Q 120 0 ttnter a ratio of 4.0 verstreekifc hot, w <^ ei t oligöHänen 'Gameig ^ naoniiifte was obtained © *

Pus (den) 26 , 5

Bite resistance (g / den). 4? 30 Extensibility (#) 29 _s 4

The yarn was made into stocking legs on a circular knitting machine knitted with an approximate width τοη 10 * 2 cm * and the Stocking legs were made by following the procedure outlined above Flammability investigated, after being used for the purpose of removal of the Spin finish has been subjected to aqueous cleaning was.,

At the same time a cleaned comparison sample was made from HyIon-6,6-yarn tested under the same conditions The results are given in the following table:

Table IX

Sample mean mean

_ '. Charring length burning time

Nylon-6 _S 6 + 1 s.3,5-tribromo

benzene + 2 % Sb ₃ O ₅ 14 _S 61 cm 14 _? 0 seconds

Hylon ~ 6, 6 <-comparative sample 38.10 cm 69? 6 seconds

The yarn which bromine and antimony trioxide contained _f beeass a better flame retardancy than the comparative yarn,

Example 10

94 «06 Gewo-! Ropes Hylon-6,6-pol.ymer. which contained 2 $ antiinone trioxide, and 5? 94 parts by weight 2 _? 4 _S 6'-Tribromomesitylen were well mixed _t gsapült with nitrogen and 20 minutes under a nitrogen atmosphere in an oil bath at 285 ⁰ G heated "to that mixture geechmolsen was," The Gemiecli was stirred vigorously for 10 minutes to a homogeneous, viscous melt. u

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BAD ORfGINAL

It was then allowed to cool * with the stirrer turned off Melt had been withdrawn "

The white © polymer possessed a Vicat ~ E: nreichungspunkt of 266.5 ⁰ C, a relative viscosity of 71 "9, an AEG of 32.0

C f.

Equivalents / 10 g, a UEL of 87.0 equivalents / 10 g and a bromine content of 3 »42 $> _o

Bs was melt-spun into a 5-ply yarn at a winding speed of 121.9 m / min at 296 ^{0 O The yarn was drawn at 8O 0} O with a ratio of 4 * 0 heat, the following yarn properties being obtained * titer ( den) 35 * 2

Tear strength (g / den) 3 »21

Extensibility (#) 54.4

The yarn was knitted on a circular knitting machine in stocking legs with approximately 10.2 cm width, and the stocking legs i tested by the method described above on combustibility after »weeks removal of the spin finish an aqueous cleaning been subjected

At the same time a cleaned comparison sample was made from aylon 6,6 yarn checked under the same conditions. The results are given in the following table;

Table I.

Sample Mean Mean V erkohlu ngslänge Burning time

Nylon 6,6 + 2 _s 4.6 ~ Tribromo-

+ 2 # ^3to o ⁰ 3 4 ^ 44 cm 19? 12 seconds

Nylon ~ 6j6 'comparative sample 40 ₉ 64 cm 42.6 seconds

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It showed that the yarn, which bromine and antimony trioxide contained better flame resistance than the comparison sample exhibited.

Example 11

95.88 parts by weight of nylon-6,6 polymer containing 2 % antimony trioxide and 4.12 parts by weight of 2,4,6-tribromoaniline were mixed well, purged with nitrogen and 25 minutes under a nitrogen atmosphere heated in an oil bath to 285 ⁰ O until the mixture was melted. The mixture was then vigorously stirred for 15 minutes to produce a homogeneous viscous melt. Ss was then allowed to cool with the stirrer removed from the melt.

The white polymer had a relative viscosity of 55.7, a Vicat softening point of 274 ⁰ O, an AEG of 50.7 equivalents / 10 g, an OEG of 87.0 equivalents / 10 g and a bromine content of 2.21 # .

Bs was melted into a 5-ply yarn at a winding speed of 121.9 m / min at 295 ^{0 O.} The yarn was cold drawn at a ratio of 4.0, with the following yarn properties being obtained:

Titer (den) 36.5

Elongation (#) 25.7

Tensile strength (g / den) 3.92

The yarn was knitted into stocking legs approximately 10.2 cm wide on a circular knitting machine, and the. Stocking legs were aof. By the method described above Flammability examined after removing the swecks Spin finish had been subjected to aqueous cleaning =

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At the same time, a purified comparative sample from HyIoa-6,6-gam The results tested under the same conditions are given in the following table *

Table XI

Sample mean mean

_mmm Charring length of burning time

Hylon-6,6 + 2,4 _S 6-tribromo

aniline + 2 f> Sb ₂ O ₃ 6.55 cm 25.8 seconds

Nylon öjö comparative sample 40.64 cn 141 »2 seconds

It turned out that the yarn, which bromine and antimony trioxide contained a better flame retardancy than the comparison sample exhibited.

Example 12

95.22 parts by weight of nylon-6,6 ~ polymer containing 2 i "Antlmontrioxyd, and 4.78 parts 2,4,6,2 ·, 4 *» ß '-Hexabromodiphenylather were well mixed, purged with nitrogen ^{and heated to 285 0} O in an oil bath under a nitrogen atmosphere for 25 minutes until the mixture was melted. The mixture was vigorously stirred for 20 minutes to produce a homogeneous viscous melt. It was then allowed to cool with the stirrer removed from the melt,

The almost white polymer besaes a relative viscosity of 40.0, a Vicat softening point of 268 ⁰ C, a CEG of 175.0 equivalents / 10 g, an AEG of 5.1 equivalents / 10 g and a bromine content of 3.64 % ·>

Eb was at 292 ⁰ C under a Aufwiokelgeschwindigkeit of 121 s9 in / rain in a 10-filamentous spun yarn The yarn was

109885/1726
BAD ORIQiNAt.

verstreokt at a ratio of 4 ₉ O "bsi 10O ⁰ C heisB, wherein the following yarn properties were obtained: titer (s) 7O _5?

Tear Strength (g / den) '3.55 Extensibility (#) 33.6

Initial modulus (g / den) 22.6

Hot water shrinkage (%) 13? 2

The yarn was knitted into stocking legs approximately four inches wide on a circular knitting machine, and the stocking legs were tested for flammability by the method described above after aqueous cleaning to remove the spin finish. Analysis of the knitted fabric indicated a bromine content of 2 _? 9 $ » (^ / 17 # loss of Br).

At the same time, a cleaned comparison sample made of Hylon 6,6 yarn was tested under the same conditions. the Results are given in the following table:

Table XII

Sample Mean Mean Charging Length Burning Time HylosMS, 6 + Hexabromodiphenyl

+ 2 % Sb ₂ O ₃ 5s> 79 cm 24.09 seconds

Nylon-6,6 comparative sample 16 inches, 117.5 seconds

The yarn, which contained bromine and antimony trioxide, had one better flame retardancy than the comparison sample »

Example tft

94 »68 parts by weight of Jfylon * 6,6-polymer _P which contains 2 # antimony trioxide

and 5-32 parts by weight of brominated 15 3 ₅ 5-triphenylbenzene (Br-content 65-8) were mixed well. ^ flushed with nitrogen and 25 minutes under a stream of nitrogen in an oil bath with 285 ⁰ C heated * until the mixture was melted. The mixture was stirred vigorously for 15 minutes to produce a homogeneous viscous melt. It was then allowed to cool with the stirrer removed from the melt

The white polymer had a relative viscosity of 47 »9», a Vicat softening point of 270 ° C., an ABG of 17 * 1 equivalents / 10 g, an OEG of 138.0 equivalents / 10 g and a bromine content of 3 * 62 $> ₀

.Bs was schmeiagesponnen at a speed of 121.9 m / min at 294 C in a 1 0-filamentous yarn "The yarn was stretched at projecting TOO ⁰ O at a ratio of 4.0 hot, and the following yarn properties were obtained:

Titer (den) 42.6

Tear strength (g / den) 3 »95

.Extensibility (#) 29? 0

Beginning: ^ üJ.ol (g / den) 22.1

Hot water shrinkage (#) 12.5

The yarn was knitted into stocking legs approximately 10.2 cm wide on a circular knitting machine, and the stocking legs were tested for flammability by the method described above after they had been subjected to aqueous cleaning to remove the spin finish Analysis of the knitted fabric showed a bromine content of 3 »5 % (low loss of Br).

At the same time a © cleaned comparative sample © from Hylon

109885/172 6

26 -

6 _? 6-yarn water tested under the same conditions «The results are given in the following table:

Table XIII

Sample mean mean _rm _ _m char length / ge burning time Hylon-6.6 + brominated 1.3 * 5-

Triphenylbenzene + 2 % Sb ₂ 0 "7.62 cm 36.3 seconds UTylön-6 _s 6 ~ comparative sample 40 * 64 cm 117 _S 5 seconds

The yarn, which contained bromine and antimony trioxide, possessed a better flame retardancy than the comparative sample.

Example 14

95.23 parts by weight of Iylon ~ 6,6-polymer _? the 2 i> antimony trioxide contained ₉ and 4 "77 G-EWO parts by brominated terphenyl m ~ (Br content * 73.4? °) were mixed well, purged with nitrogen and heated for 20 minutes _south was melted until the mixture. The mixture was stirred vigorously for 20 minutes in order to produce a homogeneous viscous melt. It was then allowed to cool with the stirrer removed from the melt.

The almost white polymer has a relative viscosity of 39.4, a Vicat softening point of 260 ⁰ O, an AEG of 7.5 equivalents / 10 ⁶ g, an OEG of 183.0 equivalents / 10 g and a bromine content of 3.46 fi »

It was schraelssgeaponnen at a winding speed of 121.9 m / min at a temperature of 285 0 to a 1-O filamentous * yarn The yarn was verstreokt at 100 ⁰ O at a ratio of 4 »0 hot, and the following yarn properties were obtained :

109885/1726

Tiber (den) 42.8

Tensile strength (g / den) 3.92

Extensibility {<$>) 21.9

Initial modulus (g / den) 25? 3

Hot water shrinkage ($) 11 »9

The yarn - was knitted into stocking legs approximately four inches wide on a circular knitting machine, and the stocking legs were tested for flammability by the method described above after they had been subjected to aqueous cleaning to remove the spin finish knitted fabric gave a bromine content of 3.05 i ° (~ 11 Jt loss of Br),

At the same time, a cleaned comparative sample was made from # Nyloa-6,6-yarn The results tested under the same conditions are summarized in the following table:

Table XIV

Sample mean mean

BrenngejLt

Hylon ~ 6 _r .6 + brominated m-

Terphenyl + $ 2> SbgO, 6.05 cm 22.08 seconds

Kylon ~ 6 _? 6-comparative test 16.4 inches 76.0 seconds

The yarn, which contained bromine and antimony trioxide, had one better flame retardancy than the comparison sample.

Example 15

The autoclave was charged with 1600 parts by weight of hexamethylene diammonium adipate, 246 wt, parts by Hexamethylendlammoniumsalz of 2,7-dibromo-gig-bisCß-carboxyäthylJfluoren (DBI ¹ AJ 3 wt _o -? 6, based on the final polymer, antimony trioxide, 0 * 5 moles? S one

10988571726

aqueous acetic acid solution and 1000 parts of water "charged _" and the polymerization was carried out in the usual manner

The resulting polymer bssass re'lative a viscosity of 27 "6, an AEG of 31 $ 7 equivalents / 10 g ₉ · a CEG of O equivalents / 10 g and a bromine content of 3? 89 $><>

Bs was sehmelzgesponnen with a windup speed of 121.9 m / min at 279 ⁰ C in a 1-O-filamentous yarn. The yarn was ^{hot drawn Tasi 80 0} G at a ratio of 4 »0, the following yarn properties being obtained: titer (den) 86.5

Tear strength (g / den) 3 »44

Extensibility (? S) 23.3

Initial modulus (g / den) 25 »7

Hot water shrinkage (#) 15.9

The yarn was knitted on a circular knitting machine in stocking legs with a width of approximately 10.2 cm, and the stocking legs were examined by the method described above for w flammability, after they had been subjected in order to remove the spin finish an aqueous cleaning. The analysis of the knitted fabric showed a bromine content of $ 3.63> °

At the same time, a cleaned comparative sample made of nylon 6,6 yarn was made checked under the same conditions. The results are summarized in the following table »

Table XI

Sample mean mean

- ~ - .. Ver kohlungslange burning time

Nylon-6 _f 6 + 3 $ SbpO ,,

+ DEFA-Baig ' 5.56 am · 45.8 seconds

Hylon-6,6-vepgleiohBprob-e 40.64 era T 17.5 seconds

109885/1726

BAD ORfGJNAl.

The GaTi ¹ H ₅ which contained bromine and antimony trioxide? possessed better flame retardancy than comparative sample ₀

Example ,,, 16

The polymer of Example 15 was processed into test bars as set forth in A8 ™-D635-68 and their flammability was compared to similar test bars made of pure nylon-6,6. According to ASTM-D635-68, both samples were to be classified ^{as "non-burning * 1} _s d _a ho _? That after two ignitions the fire did not reach the 2.5 αΐα mark. The combined burning times for the two ignitions are as follows: Test sample 3.0 seconds

Uylon 6.6 comparison test 18.5 seconds »

Example 17

95? 27 parts by weight of mixed polyamide-öj.e / ö-polymer, which contained 2.40 # antimony trioxide and 10.0 # ffylon-ö, and 4.73 ropes 2,4,6,2 ', 4 ³ »6 ⁵ -Hexabromodiphenylmethane were mixed, purged with nitrogen and heated in a 285 ° O oil bath for 20 minutes under a nitrogen atmosphere until the mixture had melted. The mixture was vigorously stirred for 10 minutes to produce a homogeneous viscous melt. Ss was then allowed to cool with the stirrer removed from the melt.

The polymer had a relative viscosity of 39.3 _9, a Vicat softening point of 255 ⁰ and a bromine content of 3.62

There was an up winding speed of 121.9 m / min at 258 ⁰ C in a 1-O-filamentous yarn melt spun. The yarn was cold verstreokt at a ratio of 4 ^ 0, where the following yarn properties were obtained t

109885/1726, BADORfGIMAL .;

liter (den) 100 _s 5

Tear strength (g / den) 3 »88

Elongation (%) 49.3

Initial modulus (g / den). 16.4

Hot water shrinkage (#) 17.7

The yarn was knitted into stocking _{legs approximately 10 9} 2 cm wide on a circular knitting machine, and the bootlegs were tested for flammability by the method described above after being subjected to aqueous cleaning to remove the spin finish. Analysis of the knitted fabric gave a bromine content of 2.9

At the same time a cleaned sample of a Hylon 6j6 yarn was made checked under the same conditions. The results are summarized in the following table;

Tabel

Sample mean mean

Burn time

Mixed polyamide-6,6 / 6 + 2,41 #

SbpO »+ hexabromodiphenyl 4.78 cm 15.6 seconds Iylloss-» 6 _f 6-vsr comparative sample 40.64 cm 117.5 seconds

The yarn, which contained bromine and antimony trioxide, had one better plaami inhibition than the comparison yarn.

Example 18

94.7 parts by weight of mixed polyamide oil / e-polymer containing 10,96 nylon-6 and 2.8 % antimony triocide and 5.27 parts by weight of tris (2,4-dibromophenyl) amine mixed p flushed with nitrogen and generally in an oil bath for 20 minutes under a nitrogen

1098 85/1726

BATH ORIGINAL

«31 -

The atmosphere was ^{heated to 285 °} C. until the mixture had melted * The mixture was stirred vigorously for 10 minutes in order to produce a homogeneous, viscous melt. Ba was then allowed to cool with the stirrer removed from the melt.

The white polymer had a relative viscosity of 42.3, a Vicat softening point of 254 ⁰ O, an AEG of. 55 »5 equivalents / 10 g, a CEG of 112.5 equivalents / 10 g and a bromine content of 3? 63 $ ">

There was an up winding speed of 121.9 m / min at 281 ⁰ C in a 10-filamentous yarn melt spun. The yarn was cold drawn at a ratio of 4.0 with the following yarn properties:

Titer (den) 81.3

Heat (g / den) 3? 95

Elongation (#) 56.2

Initial modulus (g / den) 10.2

Hot water shrinkage (#) 18.7

The yarn was triturated into stocking legs about 10.2 µm wide on a circular knitting machine and tested for flammability by the method described above after being subjected to aqueous cleaning to remove the spin finish. An analysis of the knitted fabric showed a bromine content of 3.05 % (15 # loss of Br).

At the same time, a cleaned comparative sample made of nylon 6,6 yarn was made tested under the same conditions * The results are summarized in the following table:

109885/1 7 2 6

Table XVIII

Sample 'mean mean

. carbon length burning time

Sb gO, + Tris (2,4-dibromophenyl) 4.70 cm 19.6 seconds

Nylon δ ^ comparative sample 16.4 inches, 117.5 seconds

The yarn, which contained bromine and antimony trioxide, possessed a better flame retardancy than the comparison oven »

Example 19

The hexamethylenediamine salt of 2,7 "-dibromo-9 * 9-bis (earboxyethyl) fluorene was processed into a" half-made "polymer (degree of polymerization c: 4) by stirring 1500 isils of the salt with 1100 ropes of distilled water in an autoclave ^{, the temperature was raised from 20 to 200 °} C. over a period of 2 3/4 hours, and then maintained for 1 hour a temperature of 200 ° C. The autoclave was allowed to cool and the "half-milled" polymer was removed from the Separated water and dried. The "half-made" polymer was pulverized (mesh size 0.7 mm) and the particles were coated with poly (ethylene oxide) glycols with a molecular weight of 1540 or 4000 (1 Gewo-Ji, based on the " half-made "polymer), A methanolic solution was used for application, which acted as a binder. After the methanol had been evaporated off, the large granules were broken up again, and the product became pellets with an average weight of 0 .087 g using a pelletizing measure *.

Nylon ~ 6 "6-polymer _s which contained 2 _Ρ 3 $ antimony trioxide was extracted at a rate of 5 _? 5 kg / st on a usual

1 09885/1726

Sehmelt spinning machine, which has a melt pool capacity of 1020 g as spun. 152 g of the above "half-made" polymer pellets, which had a bromine content of 27 % , were added in one batch via a feed line to the melt pool in order to bring the bromine content of the melt pool to a calculated value of 3-5 % . Then the pellets were regularly introduced through a pellet dispersing machine at a rate of 11.9 g / min (137 pellets / min).

The white 20-thread yarn obtained, which had a bromine content of 3.2 $> , was drawn at a ratio of 4.0 at 120 ^D 0, a yarn having the following properties being obtained:

2iter (den) 66

Tear strength (g / dexi) 3 »6

Extensibility (#) 19

Start module (g / den) 20

On this thread stocking legs were knitted, these were cleaned and according to the previous examples for flammability examined. The following results were obtained:

table XIX

sample

Hylon-6.6 + £ 2 SbgO * + 3.2 (from dibromo- ^M F "acid)

Nylon 6,6 comparative sample

Medium charcoal monkey

4.06 om

full length (16 inches)

Medium Brannatite

9.3 seconds 149 seconds

Example 20

The following compounds that are not covered by the scope of the

109885/1726

Invention fall were added to molten nylon-6,6, so that a halogen content of 2 # resulted. Ea iat evident that all of these compounds gave heavily discolored products:

Urine of compound observations in the nylon. , _t aohmelze

Irie (2,3-dibromopropyl) phosphate

2,3,5,6 * tetra <ailoro-p-xylylenediamine

1,2,4,5- * Tetraohlorobenzene

Poly-2,2-bie (chloromethyl) oxypropylene

(Detrabromophthalic anhydride

Tetrabromobisphenol-A pentabromophenol
Pentachlorophenol
Hexachlorobenzene

4, 5-Dibromohexahydrophthalsäureanhydrid

2,5-dibromoterephthalic acid

2-bromoterephthalic acid 4 "-Bromoisophthalic acid 2,5 * dichloroterephthalic acid

Dimethyl-2,3 »4,6-tetrachloro« terephthalate

2,3,5,6-tetrafluoroterephthalic acid

Chloric anhydride (ohlorendic anhydride)

P entaerythrityl dibromide black $> sublimate off (suruok remains a cream-colored polymer)

Brown

greenliqh-brown (low Ä.V _O )

black and black black orange

orange (low RV ₀ )

yellow (large part not ami »dated and during processing lost)

khaki

dark gray

Brown

dark gray

khaki

dark brown (low R ₀ Vo)

dark gray

1 09885/1726

21 3627?

Name of the connection

Pentaerythrityl tribromide pentaerythrityl mcmochloral Fentaerythrityldichloral decabromod iphenyl Dibromoisophthalic acid

5 , 6,7,8,9 »9-Hexaohloro-i, 2, 3 , 4-4a, 5 j 8 _? ea-octahydronaphthalene-2,3-dicarbonic anhydride

2,5-dibromohydroquinone-0,0-acetic acid

Tetrabromo-bis-phenol-A-0,0-diacetic acid

Bis (2-bromo ~ 4'-oarbomethoxyphenoxy) ethane

Bie ( 2j 4-dibromopüeny 1) amine Bis (4-bromophenyl) amine observations in the Kylon-t achmelae

glaring gray

dark brown

dark brown

Brown

khaki

dark brown

swarm dark brown

Brown

purple-violet roga * purple

Claims j

109885/1726

Claims (1)

Claims ι Polymer with reduced flammability, characterized in that it has been prepared with the addition of one or more compounds having a structure of the following definition to the original polymer: (I) The molecule of the compound has one or more benzene rings or one or more condensed benzene ring structures or a Combination of the above-mentioned rings and the above-mentioned hanging structures. Adjacent benzene rings can be linked by one or two bonds. If there is only one bond, then it can be a direct bond or a bond through groups * that are stable in the polyamide melt, such as «0-, -SO ₂ -, -0- (0R ₂ ) _a ⁰ ^ ^{V0Tin H} ^ ^{Γ H or} alkyl, ₉ η is 1 or more and Torzugweiae is 1 to 6 and m is 2 or more and preferably 2 to 6, or -HR ⁸ -, where R ^(is aryl, alkyl or (CH ₂ ) 6 , where ρ is more than 1 and i is a benzene ring and where each aromatic ring can carry halogen substituents, If two bonds are present, then at least a bond takes place via one of the groups mentioned c (II) At least one benzene ring or at least one condensed ring structure is substituted by one or more halogen atoms «, (Hl) Certain points on the molecule can be substituted by groups reactive with polymer, such as, for example, amidblldende groups or polymerizable derivatives thereof, provided that these groups to the polymer _$ give any beträchtliohe discoloration, these groups being an alkylene group are separated by a benzene ring or a condensed ring structure preferably duroh., 1 09885/1726 (IV) No halogen atom shall be in the ortho position to one other halogen atom or to any electron withdrawing atom Group, stand " 2o polymer according to claim 1, characterized in that the original polymer is a polyamide, 3o polymer according to claim 1 or 2, characterized in that that the original polymer eats polyhexamethylene adipamide. 4 »Polymer according to claim 1 or 2, characterized in that the original polymer is a Hisohpolyamid * 5. Polymer according to one of claims 1 to 3, characterized in that η in the compound or in the compounds is 1 to 6 _o 6. Polymer according to one of claims 1 to 4, characterized in that that in the compound or in the compounds m is 2 to 6. 7. Polymer according to one of Aneprüohe 1 to 5, characterized in that that the halogen in the compound consists of bromine. 8 ο polymer according to one of claims 1 to 5 »characterized in that the compound or compounds are selected from the following group; Bis (p-bromophenoxy) ethane
Tris (p-bromophenyl) amine
2,4,6,2 \ 4 \ 6 ³ -Hexabromodiphvny 1
1 _f 3 »5-tribromobene 8ol 109885/1726 2,4 »6-fribromo- * aeeitylen
2,7-dibromo-9,9-bis (β-carboxyethyl) fluorene 2,4,6,2 ', 4% 6' -hexabromodiphenylmethane iris (2,4-dibromophenyl) amine. 9 ο polymer according to one of claims 1 to 7, characterized in that that it is non-coloring synergistic metal oxides contains, 1Oo polymer according to one of claims 1 to 8, characterized in that indicates that the compound is in pelletized form for the molten polymer has been added prior to molding or extrusion. 11 * Use of the polymer according to one of the preceding Claims for the production of threads, yarns, films, foils or shaped objects 109885/1726