DE2658907A1 - HALOGEN-FREE, HARD-FLAMMABLE ACRYLONITRILE POLYMERISATES - Google Patents

Description

iayer Aktiengesellschaft 26 58907

Paterte, Mark jnd L.ze ^r iien

5090 Leverkusen, Bayerwa ^ s Dn / AB

23 Dec. 197 p

Hale free, flame-retardant acrylonitrile polymers

The invention relates to halogen-free, flame-retardant acrylonitrile polymers or molding compounds consisting of them.

It is known that polymers made from vinyl compounds by copolymerization of halogen-containing substances, in particular Vinyl chloride or vinylidene chloride, especially in combination with phosphorus compounds, is flame-resistant or difficult to burn can be made. A disadvantage here, however, is the high content of halogen compounds in the copolymers, which, although it is difficult to burn, also leads to the undesired elimination of hydrogen halides already, during spinning and burning.

It has now been found that acrylonitrile homopolymers or copolymers or moldings made from these polymers excellent flame retardancy can also be imparted if these polymers do not contain halogen Contain comonomers.

The flame retardancy is achieved by the fact that the Treated polymers or the moldings consisting of them with hydroxylamine and a metal salt solution.

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The invention therefore relates to halogen-free, hv / er -nnnnnable Acrylonitrile polymers or Molding compositions made therefrom, containing at least 0.1% by weight of metal ions, which are bound in a complex via groups that result from the reaction of the polymer with hydroxylamine came.

The polymers or the formed structures consisting of them are treated with a hydroxylamine solution in which the hydroxylamine should not be in the salt form, preferably within about 1 minute to about 1 hour, particularly preferably 5 to 30 minutes at preferably 30-TOO ⁰ C, and particularly preferably treated at 40 to 90.degree.

The concentration of the hydroxylamine solution can vary within wide limits, with concentrations of 5 to 20% by weight to be favoured. The solvent used for this treatment is preferably water or aqueous organic Solvents or also pure organic solvents such as dimethylformamide, methanol, dimethyl acetamide. Afterward there is a short wash, after which the molding compositions, if necessary to be dried.

It has proven particularly advantageous to carry out a treatment with a strong to moderately strong acid, for example preferably hydrochloric acid, sulfuric acid, phosphoric acid or an organic acid such as formic acid, oxalic acid, acetic acid, directly after the reaction with hydroxylamine. The treatment temperature is between room temperature and TOC ⁰ C, preferably 70-90 ° C, the treatment duration is expediently a few seconds to 15 minutes, preferably. 2 to 6 minutes.

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It has been shown that an aftertreatment of the complex-forming groups with acids not only leads to one Lightening of the material, but rather an instantaneous and intense complex formation in the ensuing process Treatment with metal salts already leads to room temperature. If you omit the acid treatment, what In principle, this is also possible, but is disadvantageous, so complexation only takes place after the structure has been loosened of the molding compounds which, however, are already associated with the destruction of the material. The concentration of the used Acids is preferably 0.01 to 0.2 N. Very particularly preferred is hydrochloric acid with a normality of 0.01 to 0.1 used.

As already indicated, the complex formation with metal salts that follows the acid treatment takes place almost instantly. However, the duration of this implementation depends on the desired extent of complex formation, so that it can advantageously be treated with a metal salt solution for up to 10 minutes. As a general rule the reaction of the pretreated substances with the metal salt solution should therefore take 30 seconds to 10 minutes.

Of even more importance for the extent of complex formation but is the concentration of the metal salt solution and the type of metal salt itself. It depends of course also depends on which property profile of the finished product is desired. In general, therefore, the Concentration 0.1 to 10% by weight, with 1 to 6% strength salt solutions being particularly preferred begins.

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As a metal salt, apart from alkali salts, in principle any metal salt can be used can be used, e.g. copper, iron, cobalt, nickel, zinc, magnesium, bismuth salts. However, salts are preferred of metals from the IV. to VIII. group of the PSE are used. Antimony or titanium salts are preferably used. Here if you take solutions of these salts in water, organic or aqueous organic solvents such as methanol, ethanol, dimethylformamide, dimethyl sulfoxide. Particularly beneficial the complex formation is controlled so that the amount of metal ions absorbed is 0.1-10% by weight.

The temperature of the metal salt solution is preferably 10 to 70 ° C.

The polymers used or the moldings made from them can be acrylonitrile homo- or copolymers. In the case of the copolymers, the inventive flame retardants Articles are produced particularly well if at least one of the comonomers contained is particularly good Reacts easily with hydroxylamine. This is e.g. with the comonomers, diketene, (meth) acrylamides and (Meth) acrylic acid esters and unsaturated carboxylic acid anhydrides, such as maleic anhydride is the case.

It is therefore preferred to use acrylonitrile copolymers which contain about 0.1-30% by weight of (meth) acrylic acid esters and / or 0.1 to 10% by weight of (meth) acrylamide and / or 0.1 to 6% by weight of diketene and / or 0.1-10% by weight of unsaturated anhydrides are copolymerized contain.

Of course, these comonomers, which are only mentioned by way of example and preferred, can also be used together or in combination with other ethylenically unsaturated comonomers known in the art in the polymer to be available.

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In principle it is also possible to use acrylonitrile copolymers to start with 3 to 10 wt .-% acrylic acid or methacrylic acid and this with a suitable reagent such as Thionyl chloride, phosphorus trichloride, phosphorus pentachloride, Phosphorus oxychloride or phosgene, preferably without any further inert solvent, on the carboxyl group to the acid chloride to implement. This reaction should be as complete as possible, since there is a larger excess of carboxyl groups interferes with the further reaction. The acid chloride is then in an aprotic dipolar solvent such as Dimethylformamide, dimethylacetamide, N-methyl! Pyrrolidone or Dissolved dimethyl sulfoxide and reacted with hydroxylamine.

Since crosslinking via the metal ions also occurs during the complex formation reaction, this can result in insolubility of the appropriately treated products result. It is therefore preferred to use the acrylonitrile polymers to form moldings, in particular formed into threads, fibers and foils according to known processes and only afterwards the flame retardant treatment connected.

In this way, moldings with excellent flame-retardant properties can be produced. The special advantage One of the reasons for these materials is that, without containing halogen or phosphorus compounds, they are flame-retardant i.e. that they do not emit any toxic gases in the flame. At the same time e.g. keep threads after the Invention in the flames contributes to their structure.

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Example A.

In a nitrogen atmosphere at 55 C, the pH value is 3.6 in 7000 parts by volume Water 69 5 parts by volume of acrylonitrile with stirring with 4.4 parts by weight of potassium peroxodisulfate and 22 g of sodium bisulfite started. The reaction has ended after two hours. The polymer is filtered off with suction and washed with methanol and water and dried in vacuo at 60 ° C.

Yield: 436 parts by weight, K value: 81.5 Example B

In a nitrogen atmosphere at 55 ° C and pH 3.9 in 7000 parts by volume of water 657 parts by volume of acrylonitrile and 28.8 parts by volume of methyl acrylate with 2 parts by weight Potassium peroxodisulfate and 8 parts by weight of sodium bisulfite started. After 4 1/2 hours the reaction is complete completed. It is worked up analogously to Example A.

Yield: 410 parts by weight, K value: 79 Example C

In a nitrogen atmosphere at 55 ° C. and pH 3.0, 618 parts by volume of acrylonitrile, 56 parts by weight of acrylamide and 6 parts by weight of methallylsulfonate with 4 parts by weight of potassium peroxodisulfate and 16 parts by weight of water are added to 7000 parts by volume of water Parts by weight of sodium bisulfite started. The reaction has ended after 5 1/2 hours. The usual work-up takes place.
Yield: 481 parts by weight, K value: 82.5

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Example D

Under nitrogen, 81 parts by volume are added to 900 parts by volume of water Submitted acrylonitrile and adjusted the pH to 3.8. You start at 50 ° C. with the aid of 0.7 parts by weight Potassium persulfate and 28 parts by weight sodium bisulfite. After the reaction has taken place, the mixture is left under nitrogen within 20 Minutes 4.9 parts by weight of diketene are added dropwise. After 4 1/2 hours Stirring is complete. It is then filtered off with suction, washed neutral and the product is dried in vacuo. The yield is 58 parts by weight (85%), the K value: 84.

The oxygen analysis shows a diketene content of approx. 5%.

Example E.

81 parts by volume of acrylonitrile and 2.2 parts by volume of methyl acrylate are dissolved in 900 parts by volume of water under nitrogen submitted. At 55 ° C. and a pH of 3.8 one starts with 0.5 parts by weight of potassium persulfate and 2 parts by weight of sodium bisulfite. Then 2.8 parts by weight of diketene are added dropwise over 30 minutes. After 4 1/2 The usual work-up takes place in hours.

Yield: 55 parts by weight (80%), K value: 84

Example F

There are 625 parts by volume of acrylonitrile and nitrogen

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28 parts by weight of acrylamide in 7000 parts by volume of water Submitted 55 C and adjusted the pH to 3.8. Man starts with the help of 3.5 parts by weight of potassium persulfate and 14 parts by weight of sodium bisulfite. Then be 28 parts by weight of diketene were added dropwise within 35 minutes. After stirring for 5 hours, the usual work-up is carried out.

Yield: 464 parts by weight (83%), K value: 85 Example G.

under nitrogen, 1,800 parts by weight of dimethylformamide 1090 parts by weight of acrylonitrile, 72 parts by volume of methyl acrylate and 50 parts by weight of diketene were initially charged and started according to the following scheme:

Time / minJ Acetylacetone Ammonium peroxodisulfate /Vol.- Part §7 /£5ew.-parts7 0 3.5 5.5 90 1, ^ 3 180 1.5 3 240 0.5 1.5

The reaction has ended after 20 hours. By distilling off unreacted monomers (21%) and the like Dilution with dimethylformamide gives an immediately spinnable solution (450 p / 20 ° C).

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Example H

Dilute sulfuric acid is added to a solution of 604 parts by volume of acrylonitrile, 28 parts by weight of acrylamide, 28 parts by weight of acrylamide N-methylol methyl ether and 17.5 parts by volume of methyl acrylate in 7000 parts by volume of water the pH is 3.5. Under nitrogen and at 55 ° C., 3.5 parts by weight of potassium bisulfite and 14 parts by weight of sodium persulfate are added to the solution. The polymerization time is 4 1/2 hours. It is suctioned off and washed neutral. After drying at 60 ⁰ C, the yield is 400 parts by weight, K-value: 83rd

Example I.

In 7000 parts by volume of water there are 525 parts by weight of acrylonitrile, 39.2 parts by weight of methyl acrylate and 5.6 Parts by weight of methallyl sulfonate submitted. The pH is adjusted to 3.5. It will be at 50 ° C and below Nitrogen worked. The polymerization is carried out with the aid of 55 parts by weight of potassium persulfate and 22 parts by weight of sodium bisulf it started. It is stirred for 5 hours. After vacuuming, washing and drying the product the yield is 486 parts by weight, K value: 82.

Example K

498.4 parts by weight of acrylonitrile, 56 parts by weight of methyl acrylate, 5.6 parts by weight of methallyl sulfonate in 7000 parts by volume of water are initially introduced. At a

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pH 3.5 is maintained under nitrogen with the help of 5.5 parts by weight of potassium persulfate and 22 parts by weight of sodium bisulfite started. The reaction temperature is 50 ° C. After stirring for 5 hours, it is suctioned off, washed neutral and dried.

Yield: 457 parts by weight, K value: 90 Example L

20.9 parts by weight of hydroxylamine hydrochloride are mixed with 12.3 parts by weight of sodium hydroxide in 150 parts by weight Stirred water at room temperature. The pH of the solution is 11.3.

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example 1

The polymers obtained according to Examples A to K
are processed into staple fibers 1.7 dtex, length 4 cm, using known methods. This is followed by treatment with hydroxylamine solution from Example L, reaction with n / 100 hydrochloric acid solution at 90 ° C. until the samples are discolored and the samples are immediately complexed with various salt solutions according to the following conditions.

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a) Complexation using a 3% aqueous zinc sulfate solution

Skip out Response time / Duration of action / Metal content complex Flammability example temperature in temperature in in% by weight colour NH ₂ OH Saline solution A. 30 min / 90 ° C 5 min. / 20 ° C l ' ³ beige still ent flammable B. 25 min / 85 ° C 3 min. / 20 ° C 1.8 beige still ent flammable C. 25 min / 80 ° C 2 min. / 20 ° C 1.9 beige still ent flammable ρ 25 min / 70 ° C 2 min./30 ° C 2.1 beige still ent flammable E. 25 min / 70 ° C 2 min / 40 ° C 1.7 beige still ent flammable F. 15 min / 70 ° C 1 min. / 20 C 2.2 beige still ent flammable G 20 min / 75 ° C 1 min / 25 ° C 1.6 beige still ent flammable H 15 min / 70 ° C 1 Min./20 ⁰ C 2.3 beige still ent flammable I. 20 min./70 ° C 2 min./30 ° C 1.4 beige still ent flammable K 20 min./70 ° C 2 min / 25 ° C 2.0 beige still ent flammable

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b) Complexation using 5% aqueous copper (II) sulfate solution

Skip out Response time / _? 0H Response time / Min./30 ° C Metal content Complex color Flammability example temperature in Min / 90 ° C in% by weight NH.
4th temperature in Min./30 ° C A. 35 Min / 90 ° C Saline solution 2.7 light green glossy. difficult ent 5 Min./40 ° C flammable B. 25th Min./85 ° C 3.1 green glossy very difficult 2 Min./30 ⁰ C flammable C. 25th Min./80 ° C 3.6 green glossy very difficult 1 Min./30 ° C flammable D. 30th Min / 80 ⁰ C 3.8 green glossy not ent 2 Min./30 ° C flammable E. 30th Min / 80 ⁰ C 3.4 green glossy very difficult 2 Min./30 ° C flammable ν
not _ »
flammable ' P. 30th Min./80 ° C 3.9 green glossy very difficult 2 Min./30 ° C flammable G 25th Min./80 ° C 3.5 green glossy not ent 1 Min./30 ° C flammable H 20th Min./70 ° C 4.0 green glossy not ent 1 Min./30 ⁰ C flammable I. 35 Min./85 ° C 4.3 green glossy difficult ent 2 flammable K 20th 4.1 young 3

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c) Complexation using 3% aqueous iron (III) sulfate solution

Skip out Response time / Response time / Metallge Complex color Flammability example temperature in temperature in stop in NH ₂ OH Saline solution Wt% A. 35 min / 90 ° C 2 min./30 ° C 4.8 brown glossy difficult ent flammable B. 35 min / 90 ° C 2 min./30 ° C 5.3 dark brown not ent glzd. flammable C. 30 min / 80 ° C 2 min. / 20 ° C 5.1 dark brown very difficult glzd. flammable D. 25 min / 80 ° C 1 min. / 20 ° C 5.0 dark brown very difficult glzd. flammable E. 25 min / 80 ° C 1 min. / 20 ° C 4.4 brown glossy difficult ent flammable F. 30 min./70 ° C 1 Min./20 ⁰ C 5.9 dark brown not ent glzd. flammable G 30 ⁰ C Min./70 1 min. / 20 ° C 5.4 dark brown not ent glzd. flammable H 25 min / 70 ⁰ C 2 min. / 20 ° C 5.8 dark brown not ent glzd. flammable I. 25 min / 70 ° C 2 ⁰ C Min./20 5.3 dark brown glzd. K 20 min./70 ° C 3 ⁰ min./30 C 6.0 dark brown not ent glzd. flammable

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d) Complexation using 5% aqueous titanyl sulfate solution

Fibers Response time / 2 ^0H Response time / Min./30 ° C Metallge Complex color gj.zd, Flammability example temperature in Min./90 ⁰ C temperature in stop in NH Saline solution Min./30 ° C Wt% glzd. A. 35 Min./90 ⁰ C 3 3.9 golden yellow very difficult Min./30 ° C glzd. flammable B. 30th Min / 90 ° C 3 4.1 golden yellow not ent Min./25 ° C glzd. flammable C. 25th Min./85 ° C 3 3.8 golden yellow not ent Min./25 ° C glzd. flammable D. 25th Min./70 ° C 2 4.0 golden yellow not ent Min./30 C. glzd. flammable ε 30th Min / 70 ⁰ C 2 3.6 golden yellow very difficult Min./30 ° C glzd. flammable P. 25th Min./75 ° C 2 4.2 golden yellow not ent Min./25 C. glzd. flammable G 30th Min./70 ° C 3 3.7 golden yellow very difficult Min./25 ° C glzd. flammable H 20th Min./70 ° C 2 4.4 golden yellow not ent Min./30 ° C yellow, glossy. flammable I. 25th Min./75 ° C 2 4.0 golden yellow not ent flammable K 20th 3 4.9 not ent flammable

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e) Complexation using 5% aqueous methanolic antimony trichloride solution (Volume ratio 40:60)

Fibers Response time / Response time / Metallge Complex color Flammability ro example temperature in temperature in stop in CD NH ₂ OH Saline solution Wt% cn A. 35 min / 90 ° C 5 min. / 20 ° C 3.0 pale yellow glossy. difficult ent OO flammable CO B. 30 min / 85 ° C 5 min. / 20 ° C 3.3 light yellow glossy. very difficult O flammable C. 25 min / 85 ° C 5 min./30 ° C 3.7 yellow, glossy. not ent flammable D. 30 ⁰ C Min./80 5 min./30 ° C 3.4 yellow, glossy. not ent flammable E. 25 min / 75 ° C 3 min / 25 ° C 3.4 yellow, glossy. not de- ^ flammable ^ F. 25 min / 70 ° C 3 min. / 20 ° C 3.7 light yellow very difficult flammable G 30 min / 75 ° C 3 min; / 20 ° C 2.9 light yellow very difficult flammable H 20 min / 70 ⁰ C 3 min. / 20 ° C 3.8 yellow not ent flammable I. 20 min / 70 ⁰ C 2 min./30 ° C 3.5 yellow not ent flammable K 20 min / 75 ° C 5 min. / 20 ° C 3.5 yellow difficult ent flammable

Example 2

The polymer from Example F was processed into a yarn using conventional techniques and then further processed into a knitted piece. The knitted piece was treated with the hydroxylamine solution from Example L, followed by a 2-minute treatment Wash with 2N acetic acid. After a short rinse in distilled water, a 5% aqueous solution of Titanyl sulfate complexed at 20 ° C for 10 minutes and dried. The burning test according to DIN 53 906 gave the following values:

Burning time / jsecTJ Burning distance £ cmj Burning time / sec_J7 incl. 3 see. Ignition time max. 35 cm incl. 15 seconds. Ignition time

3 under 0.5 23

3 under 0.5 19

3 under 0.5 21

Assessment: The material is incombustible according to DIN 53 906. Example 3

The polymer from Example F was treated immediately for 40 minutes with the hydroxylamine solution from Example L, with Washed water until neutral and then with a 5% antimony trichloride solution in methanol / water 60:40 for 5 minutes implemented at 30 C. After drying, a powder compact is made from the polymer complex and after the oxygen test examined. A LOI value of 39.5 was found (LOI test described in "Modem Plastics", (1970) p. 124).

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Claims (1)

Claims T. Halogen-free, flame-retardant acrylonitrile polymers or molding compositions therefrom, containing at least 0.1% by weight Metal ions that are bound in complexes via groups which, through reaction of the polymer with hydroxylamine: came about. 2- Halogen-free, flame-retardant acrylonitrile polymers or molding compounds therefrom, obtainable through implementation of the polymers or of the molding compositions with a hydroxyl lamin solution, treatment with an acid and subsequent reaction with complex formation with a metal salt solution. 3. Process for the production of halogen-free, flame-retardant acrylonitrile polymers or molding compounds from them, characterized in that the polymers or the molding compositions with a hydroxylamine solution, then treated with an acid and then with a metal salt solution. Le A 17 722 - 18 - 80982Ϊ / 0189