DE2422642C3 - Process for the production of flame-retardant moldings - Google Patents

Description

R -CR, -C-

I. X

(I)

in which R is H or CH ₃ and X is CN, CONH ₂ or COOR ', where R' is an alkyl group and b) consists of 60 mol percent of other polymerized monomers,

(1) by external reaction of a crosslinking agent with the functional groups the polymer is crosslinked,

(2) the substituent X in general formula I is hydrolyzed to such a degree is that the polymer contains at least 40 mol percent free carboxyl groups,

(3) the free carboxyl groups with mono- to trivalent metal ions to such an extent be converted into COOM groups, in which M is a monovalent to trivalent metal ion, that the COOM group content 0.5 to 40 percent by weight, calculated as metal and based on the polymer, and optionally

(4) remaining carboxyl groups wholly or partially neutralized with ammonia will.

to make flame retardant; another method that uses a flame retardant monomer through copolymerization is introduced into the polymer in order to make the polymer itself flame-retardant, as well as an aftertreatment method a flame-retardant substance for the impregnation of moldings based on a polymer is used, the flame retardant fabric is then fixed. However, these ίο methods possess the most serious one Disadvantage that they affect the polymer in its physical properties, z. Legs Cause discoloration of the polymer or a change in the handle of the molded body, and above In addition, all of the above methods have common disadvantages that the flame-retardant Substances themselves are toxic and develop strong smoke and toxic gases when burned.

The invention is based on the discovery that this is the case with molded articles such as fibers or films Vinyl polymers can achieve excellent flame retardancy if the polymer is so modified that it has a networked structure and COOM groups (M is a mono- to trivalent Metal atom). For this purpose, a polymer is used that has 40 mol percent in its structural framework or contains more, based on the polymer, of a group which can be converted into a COOH group. This convertible group is converted into the COOH group, and thereafter those obtained Shaped body of a salt bond or crosslinking reaction with a mono- to trivalent metal subject.

The invention thus relates to a process for producing flame-retardant molded bodies, gis is characterized in that a prefabricated molded body made of a polymer consisting of a) at least 40 mol percent of repeating units of the general formula I.

CH ₂ -C

(I)

2. Application of the method according to claim 1 for the production of flame retardant

4en fibers, films or foils.

in which R is H or CH. and X means CN, CONH ₂ or COOR ^? has, where R 'represents an alkyl group, and b) consists of 60 mol percent of other copolymerized monomers,

The invention relates to a process for Hersteljng flame-retardant molded articles such as fibers or ilme ^r.

To obtain flame-retardant polymer compositions, many methods have been proposed so far, z. B. a method in which flame-retardant substances, such as metal compounds, phosphorus compounds or halogen compounds, are mixed into the polymer as additives to make this

(1) by external reaction of a crosslinking agent with the functional groups of the polymer is networked,

(2) the substituent X in general formula I is hydrolyzed to such an extent that that the polymer contains at least 40 mol percent free carboxyl groups,

(3) the free carboxyl groups with mono- to trivalent metal ions to such an extent in COOM groups, in which M is a mono- to trivalent

Metal ion means to be transferred that the aldehyde, in the presence of an acidic catalyst,

COOM group content 0.5 to 40 percent by weight

zem, calculated as the metal and based on the. The crosslinking reaction can take place during the shaping of the polymer, and, if necessary, the base polymer. j / - ι. ⁵ but preferred, the base polymer in the form of the (4) remaining carboxyl groups wholly or partially-molded body of the crosslinking reaction to be neutralized with ammonia at times. throw.

. , ". . . “As mentioned earlier, it is used to produce the

Examples of suitable alkyl groups R 'are flame-retardant moldings of the invention required

Methyl and ethyl _{groups loosely; the} ^ "^ ϋ ^ introduced COOH group

Examples of suitable polymers are homopes in the shaped polymer, the one through

polymers and copolymers of vinyl mono- covalent bonds due to the crosslinked structure

mers, which contain groups in the vinyl units, sits, completely or partially, during the salt formation

which are convertible to COOH groups, such as CN, or crosslinking using a one to

CONH ₂ or COOR. Suitable are e.g. B. Polymeri- 15 trivalent metal ions to participate, with COOM-

sate of acrylonitrile, methacrylonitrile, acrylamide, groups (M means a mono- to trivalent metal)

Methacrylamide, methyl acrylate, ethyl acrylate, methyl arise. When performing the salt formation

meihacrylat or ethyl methacrylate as well as copoly- or crosslinking with a mono- to trivalent ion

Merisate of the monomers mentioned with others are salts of monovalent metals, such as potassium or

Vinyl monomers such as styrene, α-methyl styrene, vinyl sodium salts, of weak acids such as carbonates

acetate, hydroxyalkyl acrylates, vinyl pyridine, vinyl or acetates, or oxides, halides, alcoholates,

pyrrolidone, vinylbenzenesulfonates or sodium meth- inorganic or organic acid salts, preferably

allyl sulfonate. These vinyl polymers become weaker due to inorganic or organic salts

known manner into fibers, films or the like. Deformed. Acids, such as carbonates or acetates, or two or

Polymers made from vinyl monomers that convert them to trivalent metals such as calcium, magnesium, iron,

COOH groups convertible groups, such as CN zinc, copper, nickel or aluminum, used

or CONH ₂ contain, such as acrylonitrile, methacrylic It wh d an about 1Weq aqueous solution of this Me-

nitrile, acrylamide or methacrylamide, are previously used to prevent salt formation or

modified so that a networked structure is created. Crosslinking at a temperature of 60 to 100 ° C

Subsequently, these groups are effected with an acid 30, the reaction conditions according to

or a base subjected to hydrolysis, so that depending on the type of metal compound, the Reak-

40 mol percent or more, preferably 60 mol percent, the reaction time, the type of

cent or more, based in each case on the polymer, solvent, the COOH group content and

COOH groups formed in the vinyl units differ in the degree of crosslinking. To the

will. 35 according to the invention intended flame retardancy

A cross-linked structure is necessary to achieve the deformed polymer of the invention contains

development of solvent resistance and prevents dung 0.5 to 40 percent by weight, in particular 1 to

excessive swelling or elution of the poly- 30 percent by weight (calculated on metal) based on

merisats during hydrolysis with an acid or on polymer, COOM groups (M is a one to

a base at which the COOH group is formed. 40 trivalent metal) consisting of COOH groups in the

The cross-linked structure does not in itself cause any deformed polymer by replacing water

flame-retardant effect, but rather leads to a substance due to mono- to trivalent metal on the

easier burning. Therefore, although ways of salt formation or cross-linking have been replaced

at least 0.1 mole percent of the polymer because of the. A metal content that is 40 percent by weight

crosslinked exceeds the desired solvent resistance 45 is undesirable because of the impairment

should be, preferably, the degree of crosslinking in relation to the physical properties of the deformable

keep ring as possible, provided the solvent- borne material. To improve the flame retardancy

resistance of the molded body is guaranteed. tion of the flame-retardant moldings of the invention

The methods of making a crosslinked manure is desirable to the remaining

Structure in the polymer use one of the fol- 50 COOH groups completely or partially in

lowing reactions: converting COONH ₄ groups. The transformation

can be done in a simple manner before or after the

(1) Conversion of CN groups in a poly conversion with a mono- to trivalent metal note, the Z. B. acrylonitrile or methacrylic bond made by deforming the nitrile contains, 55 polymer with an efva 10% aqueous solution from Z. B. ammonia, ammonium acetate or odei

(2) Conversion of CONH ₂ groups in an ammonium chloride, treated at 60 to 100 ° C.
Polymer z. B. acrylamide or meth- The flame-retardant molded article of the invention contains acrylamide. which have a networked structure and COOM groups (M

60 is a mono- to trivalent metal), are ge

When using the method according to reaction (1) is characterized by excellent flame retardancy if the base polymer is treated with a solution without the need to add a flame retardant, the hydrazine in the form of a hydrate or some substance and by complete charring Mineral acid salt, or with a solution on contact with a flame without any treatment, the hydroxylamine in the form of the hydro- 65 considerable amount of smoke or unpleasant smell Contains chloride or sulphate. Arises from the method. The main reason for the excellent « If the reaction (2) is required, the base polymer is flame retardant and the special combustion process with an aldehyde such as formaldehyde or benzene seems to be in endothermic reactions

which in the molded bodies of the invention when touched c) The measurement of the flue gas temperature (td &)

take place with a flame, as this takes place with the shape and smoke image coefficients (C ₄ )

body of the invention carried out differential according to JIS A1321.
thermal analysis pronounced endothermic peaks above

a wide temperature range from about 50 to about 5. The evaluation of the light stability of the moldings at 250 ° C. and barely detectable exothermic peaks are carried out by examining the change in the cracks. A heat-insulating effect of the charred doneness of the test specimen when exposed to UV layer, which is formed on contact with a flame eye rays for a predetermined time, also seems to contribute to the establishment of a light fastness tester of light charcoal high flame retardancy. It is still io bow type.
Zi suspect that the low smoke development that Example 1
one of the special features of the moldings of the

Invention represents, on the metal content of the invent- A cable made of 3 denier acrylic fibers (copolymer

is due to dgemäöen molded body. sat composed of 93 mole percent acrylonitrile and 7 mole percent

In the flame-retardant moldings of the invention 15 vinyl acetate) is immersed in an aqueous solution. B. to fibrous materials containing 200 g / liter of hydrazine hydrate, and 2 stun form of flakes, yarn or woven or allowed to react at 90 ° C. The fiber / liquor-knotted textiles are used, the ratio is 1:30. After the completion of the reaction for the manufacture of clothing of the most varied, the cable is washed with water, kind, e.g. B. of post-wash; Interior fittings, such as air-dried for 20 minutes and at 150 ^° C. for curtains or carpets; Mattress padding; heated to accelerate crosslinking. In this way, especially when equipping railways, one obtains an orange-yellow, networked wagons and aircraft, where a high degree of fiber, the weight of which is necessary due to the flame retardancy, and with protective treatment is 2%. Due to the IR absorption clothing for firefighters, welders, steel spectroscopy, fiber workers, racing drivers or pilots have been treated in this way. (hereinafter referred to as fiber A) 4 mole percent

In the case of the moldings of the invention, the one in the original, untreated fiber can be

also around films, non-woven textiles or other holding CN groups reacts with hydrazine,

trade shaped objects. They are suitable for Part of the fiber A is the hydrolysis treatment

Use in manufactured products, the flame 3 ° development by immersion in a 0.5 η aqueous solution

Must be retardant, like structural panels, subject to sodium hydroxide. With a two-

Pipes, rods, flat materials, wallpaper, filter hour treatment time at 90 ° C is the fiber /

cloths etc. liquor ratio 1:20. After treatment will

The examples illustrate the invention. In the two the fiber in a large excess of 1 η aqueous

play is carried out the evaluation of the flame retardancy 35 immersed hydrogen chloride solution, then

according to the specified test procedure. washed thoroughly with water and put in a hot

., ._, .. ",, fan oven dried. After drying shows the

(1) Qualitative test method _Fastr (referred _to as fiber B after f _o i _ge nd) a ge

Test sample weight increase of 17 percent. Due to the IR

a) fiber: soft, twisted spun thread, about 40 absorption spectroscopy have 63 mole percent of the 0.5 cm in diameter and about 7 cm in length. present in the original, untreated fiber

b) film strip, reacts 0.5 cm wide and about 7 cm lan ^de * "f CN groups to COOH groups.

^& Let part of the fiber B with 5% water

The test sample is held at the upper end, so riger potassium acetate solution for 1 hour at 80 ° C and arranged that it has an inclination of 45 °, react at 45 a fiber / liquor ratio of 1:20, The fiber is lit lower end with a matchstick or narh completing the reaction held in the flame and visually washed in terms of water, drained and dried. Flame retardancy and combustion behavior The measurement of the metal content gives a potassium observed, content of the fiber (hereinafter referred to as fiber C)

(2) Quantitative test method ⁵ ° ^ ?, ¹⁸ % by weight

Leave part of the fiber C with a 10% strength

a) Determination of the limited oxygen index of aqueous ammonia solution for 4 hours at 40 ° C and (LOI): The determination is carried out in accordance with JIS K 7201 with a fiber / liquor ratio of 1:50 react using an incinerator. The fiber is then washed with water, Type ON-I, Manufact. Suga Testing Machines Co.). 55 dehydrated and in a vacuum dryer for 2 hours. The following are used as test samples: for fibrous dried at 60 ° C. After drying, the materials show a nonwoven fabric, 0.17 g / cm ³ woven fiber (hereinafter referred to as fiber D) a counterweight, 0.3 cm thick, 6 cm wide and 15 cm long; weight increase of 3.2%>.

for film material a narrow strip, 0.3 cm Fibers A to D are cut to their fiber thickness, 1 cm wide and 15 cm long. 60 shafts, flame retardancy, light stability and combustion behavior examined. The results are

b) Measurement of the burning time, glow time and the ver in Table I compiled. Here in Carbonization zone: The measurement is carried out in accordance with Tables I to IV:

h ¹⁰ u ⁹¹ J x ^V ! 1 ^fa li ^rei J, ^A " ² ( ⁴⁵ ° - ^Meker - ^Brenner - X dry strength ... 1.0 to 1.5 g / denier

Method). Knotted joints are used as test specimens.

weave with a fabric weight of 788 g / m ", Naßfest.gke.t 0.5 to 1.0 g / den, er

1.41mm thickness and an air permeability XX dry strength .. more than 1.5 g / denier

of 8 ml / cmVsec used. Wet strength more than 1.0 p / Denip.r

Table I. Dry-
and wet
strength
of the chamois Flame retardancy
Flammlest LOI Light stability,
öOhrige
exposure Combustion behavior fiber XX burns at the first
inflammation 19.0 no brittleness burns with the appearance of flames
and charred A. X something burns and
goes out 23.5 the same burns with the appearance of flames
and charred, with traces of the
original shape remain B. X hardly burns 31.0 the same instantly charred without flames
education C. X hardly burns 32.5 the same instantly charred without flames
education D. XX burns at the first
inflammation 19.5 the same burns with the appearance of flames
under melting and shrinking,
being a black, hard mass
remains behind unconcerned
acts

Example 2

A cable made of acrylic fibers (copolymer of 93 mol percent acrylonitrile and 7 mol percent vinyl acetate) is immersed in an aqueous solution containing 200 g / liter of hydrazine hydrate. One leaves a fiber / liquor ratio of 1:20 for 4 hours react at 90 to 100 ° C. After completion

After the reaction, the cable is washed with water, drained of water, air-dried and heated to 150 ° C. for 30 minutes. This gives an orange-yellow fiber with a weight increase of 5.3%. It is found that in the fiber treated in this way (hereinafter referred to as fiber E) 2 mol percent of the CN groups present in the original fiber have reacted with hydrazine with crosslinking.

Table II

Metail connection

Metal content

(Weight percent)

Fiber suitability for dry, light and stability,

Wet exposure for 60 hours

Flame retardancy
Flame test LOI

Combustion behavior

E. - XX none burns at 19.0 burns in flames 609 653/338 Brittle the first appearance and charred speed inflammation F. X the same something burns 24.0 burns in flames and extinguishes appearance and charred. being traces of the ur original form too lag behind G Ca (OCOCH ₃ ) ₂ 7.6 X the same hardly burns 34.5 charred immediately without " 22.9 *) 35.0 Flame appearance, where a mass in dei original shape too remains H Mg (OCOCH ₃ ), 5.8 X the same the same 31.5 the same 13.0 *) 33.5 I. Mn (OCOCH ₃ ), 5.9 X the same the same 32.0 the same J Zn (OCOCHg) ₂ 6.1 X the same the same 36.5 the same K Cu (OCOCH ₃ )., 14.6 X the same the same 34.0 desgL L. Fe (OCOCHa) ₂ 2.6 X the same the same 31.5 the same M. Al (OCOCH ₃ ), 6.7 X the same the same 34.5 the same unconcerned XX the same burns at 19.5 burns in flames acts the first Appearance under Schmel inflammation zen and shrink being a hard massi remains behind *) 2-hour reaction at 100 ⁰ C

The fiber E is subjected to hydrolysis by immersion in a 0.5 η aqueous solution of sodium hydroxide (Fiber / liquor ratio 1:30) subjected to 2 hours at 90 to 100 ° C. After completing the reaction the fiber is immersed in a large excess of 1η hydrochloric acid and then placed in a hot air dryer dried. After drying, the fiber (hereinafter referred to as fiber F) exhibits a Weight gain of 20 percent. The fiber is found to be 74 mole percent of that in the original CN groups present in the fiber have been converted into COOH groups. The fiber F is with a 100% aqueous solution of one of the seven metal compounds listed in Table II for the reaction brought. The reaction time is 1 hour at 70 to 80 ° C and a fiber / liquor ratio from 1:20. After completion of the reaction, the fiber is washed with water, drained and dried. 7 fiber types are obtained here (hereinafter referred to as fibers G, H, I, J, K, L and M). Every fiber is examined for its metal content and its suitability. The results obtained are compiled in Table II. As can be seen from Table II, polyvalent metals exhibit one particularly pronounced effect. ;

Example 3

The same acrylic fiber cable as used in Example 2 is immersed in an aqueous solution, the 200 g / liter hydroxylamine sulfate and 20 g / liter; Contains sodium dihydrogen phosphate. At a fiber / liquor ratio of 1:50, the mixture is left for 1.5 hours react at 100 "C. After completion of the

Reaction, the fiber is washed with water, de-) ^V c ^a 'o ^e £ · ^a · u ^{air eIrock} g net and heated for 30 minutes L. nu. A yellow, crosslinked fiber is obtained (hereinafter referred to as fiber N), the increase in density being 7 percent. It is found that 13 mol percent of the CN groups contained in the original fiber have reacted with hydroxylamine (from the IR Absorption spectroscopy).

The fiber N is the hydrolysis by immersion "ο in a 0.5 η aqueous solution of sodium hydroxide at a fiber / Fleet ratio of 1: 30 and subjected to a 2,5stundigen reaction time at 90 to 100 ⁰ C. After completion of the reaction, the fiber is immersed in a large excess of 1 η aqueous • 5 hydrogen chloride solution, washed with water

Dehydrated 2 '""ι' * ⁰ * g ^{1 Zentrifu 'older} and dried in emein hot air dryer at 110 ° C. To

«N iod ^e " ^{If the fiber shows an increase in} weight

* _N ^ c ^rcent · ^Darüb he addition, it is found that 7nof ^r n ^{he (nachf0} 'quietly referred to as fiber O) ni / o of CN groups contained in the original fiber m COOH-groups are converted, "ie J ^ aser υ is JE in a 5 ° / oi _ge aqueous solution

"Zl TfT ^{1" of the FIVE in the} following table Pin ⁸ J ^rten ^ '^ immersed connections. With a fiber / fleet ratio of 1 * 20 is allowed for 1 hour at 70 to 80 ° C to react. After Vervoll-S ⁸ T ^{8 he reaction} becomes the fiber with water

ο!, Τ? ' ^drained and dried. Here receives

o the fibers P, Q, R, _S or T

The aforementioned fibers N to T are examined for their E equation. The results are in Table III compiled.

Table III

fiber

Metal compound metal content

(Weight percent)

Fiber suitability for dry, light and stability,

Wet exposure for 60 hours. Flame retardant
Flame test LOI

N- _

O - _

PK ₂ CO ₃ 13

Q Ca (OCOCH ₃ ) ,, 4.8

R Mg (OCOCE,) ,, 3.4
S Zn (OCOCH ₃ )., 4.5
T Al (OCOCEy ₃ 3.5

XX X

X X

X X X

none burns at 19.5

Brittle - the first
inflammation

also burns something 23.5 and goes out

the same hardly burns 32.0 the same the same 33 _{> 0}

like. like. like. like.

the same.

31.5
34.0
31.0

Combustion behavior

burns with the appearance of flames and charred

burns with the appearance of flames and charred, leaving traces of the original Lingering shape

immediately charred without the appearance of flames

charred immediately without the flames, leaving a mass that of the original fiber form corresponds exactly

the same
the same
the same

Example 4

An acrylic fiber made from a copolymer of 20 mol percent acrylamide and 80 mol percent acrylonitrile is immersed in a 10% strength aqueous formaldehyde solution, the 2% triethanolamine as a catalyst contains. The mixture is left to react at 70 ° C. for 3 hours at a fiber / liquor ratio of 1:60. The obtained methylolated fiber in the reaction medium, which is then acidified with sulfuric acid is heated to obtain a pale yellow crosslinked fiber (hereinafter referred to as fiber U which is insoluble in dimethylformamide.

The fiber U is immersed in a 1 η aqueous sodium hydroxide solution and with a fiber / Liquor ratio of 1: 30 1.5 hours at 100 ° C heated. After the completion of the reaction, the fiber is dipped in a large excess 1 η hydrochloric acid completely neutralized with

Table IV

Washed with water, dehydrated by centrifugation and dried. The dried fiber (hereinafter referred to as fiber V) shows a weight increase of 22%. It is found that 66 mole percent of the CN groups originally present in the fiber have been converted to COOH groups, such as results from the IR absorption spectroscopy.

The fiber V is further immersed in a 10% aqueous solution which is one of the four in the following Table contains metal compounds listed. With a fiber / liquor ratio of The mixture is allowed to react 1:20 for 45 minutes at 70 to 80.degree. After the reaction, the fiber is mixed with water washed, drained and dried. In this way the fibers W, X, Y and Z are obtained.

The results of the proficiency testing for fibers U through Z are summarized in Table IV.

Fiber metal compound metal content

Fiber suitability for dry, light and stability,

Wet-o-hour

(Fixed weight exposure

Percent) speed

Flame retardancy
Flame test LOI

Combustion behavior

U -

V -

W Ca (OCOCH ₃ ) ₂ 7.2

Mg (OCOCH ₃ ).,
Zn (OCQCHj) ₂
Al (OCOCH ₃ ) J.

5.3
5.8
6.1

XX

X X X

none

Brittle

speed

the same

the same

like. like. like.

burns at 18.5
the first
inflammation

burns something 24.0
and extinguishes

hardly burns 32.0

like. like. like.

30.5
33.5
33.0

burns with the appearance of flames and charred

burns with the appearance of flames and charred, leaving traces of the original Lingering shape

charred immediately without the appearance of a flame, leaving a mass that dei corresponds exactly to the original fiber shape

the same
the same
the same

Example 5

A cable made of acrylic fiber (copolymer of 93 mol percent acrylonitrile and 7 mol percent vinyl acetate) is immersed in an aqueous solution containing 200 g / liter of hydrazine hydrate. At a fiber / liquor ratio of 1:30, the mixture is left to react ^{at 100 ° C. for 4.5 hours.} After the reaction, the fiber is washed with water, dehydrated, air-dried and heated to 150 ° C. for 1 hour. This gives an orange-yellow fiber which shows a weight increase of 5.1 percent by weight. This fiber is subjected to hydrolysis by immersing it in a 0.5 η aqueous solution of sodium hydroxide. With a fiber / liquor ratio of 1:30 and a temperature of 100 ° C, different immersion times are used. After neutralization with a large excess of 1N salt & acid, two different types of fibers with different COOH group contents of 35 mol percent and 55 mol percent are obtained. When these fibers are treated with an aqueous solution of calcium acetate, fibers with different calcium contents are obtained. The LOI values of these fibers are given in Table V. From Table V it can be seen that embossed flame retardancy is obtained when the COOH group content of the fiber is 40 mole percent or higher and the metal content is 0.5 weight percent or higher

Table V

metal LOI 55 salary 22.5 (Weight COOH group content of the fiber 24.5 percent) (Mole percent) 26.5 0 35 29.0 0.7 21.0 31.0 2.0 21.0 4.2 22.0 7.5 22.5 23.5

Comparative example

a) Treatment of moldings so that they contain only metal

Contains 7 mole percent vinyl acetate is placed in an Obermeyer reactor equipped with a reflux condenser and an aqueous solution implemented, which contains 400 g / liter of hydrazine hydrate. Leaves at a fiber / liquor ratio of 1:10 react at 100 ° C. for 1.5 hours. After the completion of the reaction, the yarn becomes thorough washed with water. The weight increase of the yarn is 5.8% from the measurement of the

4 g of zinc acetate are dissolved in 100 ml of dimethylformamide. Then 10 g of a copolymer are added from 93 mole percent acrylonitrile and

7 mole percent vinyl acetate too. The mixture is set at io, and 14 mole percent of that originally in the Room temperature sufficiently stirred so that one fiber has CN groups present with hydrazine a solution is obtained which reacts transparently and pale yellow as colored from the IR absorption spectrum is. After defoaming, the solution is a copy

poured onto a stainless steel sheet, the yarn remaining in the reactor is mixed with

a film about 3 mm thick is obtained. 15 of a 2 η aqueous solution of sodium hydroxide

(Fiber / liquor ratio 1:10) added. The hydrolysis time is 1.5 hours at 100 ° C. After completion After hydrolysis, the yarn is washed thoroughly with water for 1 hour at room temperature Treated with 1 η-sulfuric acid, washed again with water, drained and put in a hot-convection oven dried. The weight gain after drying is 21.4% and 78 mole percent of the CN group originally contained in the fiber

v while the LOI value of a film that is similar in 25 pen have been converted into COOH groups, Has been produced in a manner which, however, does not produce zinc, as is evident from the IR absorption spectroscopy.

A test sample (knotted fabric, double yarn layer) is produced using the yarn treated as above and a flat knotting machine (8 gauge). The fabric obtained is treated with a 10% strength aqueous solution of calcium acetate for 30 minutes at 90 ° C. and a fiber / liquor ratio of 1:20, then washed with water, dehydrated and dried. The calcium content of the fibers in the fabric contained in the above-mentioned metal salts is tende film in the air for 1 hour at 120 ° C according to the analysis 8.2 percent by weight. That heats up. By this treatment, the film LOI of the fabric dyed is 32.5 and remains unbraun, but is sufficiently tough and can not be changed after the tissue at 40 ⁰ C and are easily torn. The film is insoluble in a dimethyl 40 fabric / liquor ratio of 1:20 5 times with a formamide. When igniting with a 0.1% aqueous solution of Emal40 (product: Matchstick burns a cut from the film by Kao Soap Co .; sodium salt of sulphated narrow strips only for a short time and then extinguishes. Coconut alcohol) has been washed. This shows that the LOI of the film is 23.5, which indicates an excellent resistance to flame retardancy, improvement in flame retardancy. 45 mung. With the knotted fabric, a

Flame test carried out, the results of which are in the

Example 6 Tables VI and VII are compiled. How out

as can be seen from the tables, the linked structure

A skein of spun yarn (2/48) made of weave provides excellent flame retardancy for both Acrylic fiber, the 93 mole percent acrylonitrile and 50 reduced smoke.

This film is first dried in air and then for 3 hours at 35 ° C. in a vacuum dryer. The film treated in this way is transparent, pale yellow in color, very brittle and in dimethylformamide soluble at room temperature. The analysis shows a zinc content of the film of 9.3 percent by weight. A narrow strip cut from this film burns through after ignition Match. The LOI value of the film is 21.0,

holds, is 19.5. Thus, the flame retardancy is achieved by simply introducing a metal salt alone not improved.

b) Treatment of moldings so that they are caused solely by a metal

Contain networks

Table VI Flame test *) (45 ^O -Meker burner method) Duration of the flame Narfiglimmen charring zone Combustion behavior

fsec) (see) (cm ¹ )

9.9

no flame formation;
only charring

*) 1- Flame length of the Meker burner: 65 mm.

2. After contact with the pilot light: 2 minutes.

Table VII

Tesiart test sample *)

knotted knotted comparative fabric * *)

tissue

from

Example 7 ABC

Weight in front of
Combustion (g) 38.4 36.4 24.7 27.4 35.6 Weight according to the
Combustion (g) 10.4 6.0 2.7 8.6 11.8 burned
Weight amount (g) 28.1 30.4 22.0 18.6 23.8 Flue gas temperature (f dö) 15th 164 38 169 199 Smoke development
coefficient (C _Λ ) 6th 3 29 111 90 ·) Size of the test sample: 22 X 22 cm. **) A: phenolic synthetic Fiber, described in SA-PS 6 91 356.

B: flame-retardant viscous fiber containing a flame-retardant fabric * which is described in the published JA-PA 31 720/72.
C: Modacrylic fiber containing copolymerized vinyl chloride. D: Fiber made from a polyvinyl chloride-polyvinyl alcohol emulsion.

Claims (1)

Patent claims: 1. Method of making flame retardant Shaped body, characterized in that a prefabricated shaped body made of a polymer which consists of a) at least 40 mol percent of recurring units of the general Formula I.