DE2050009A1 - Flame-retardant preparations and systems of additives used for their manufacture - Google Patents

Description

Dr. Michael Harm

Patent attorney 635 ViAQ Nauheim

Telephone {> i 60; .'-) 82 37

October 9, 1970

H / W (241) 20 601 H.

Phillips Petroleum Company, Bartlesville, OkIa., V.St.A.

FLAME RESISTANT PREPARATIONS AND SYSTEMS BY FOR THEM MANUFACTURING ADDITIVES USED

It is known that easily inflammable plastics are hardly inflammable due to the addition of halogen compounds can be made. Flame-retardant plastic preparations are particularly suitable for the production of electrically insulating coatings are important, as they are, for example, in electrical cables in houses small devices, for insulating wires in electronic devices, for sheathing and the like Purposes. However, it is desirable here that the physical properties of a Plastic that you want to make flame retardant or flame retardant by adding flame retardants not be changed much. Efforts are therefore strongly directed towards a means that is in very small quantities causes the desired flame retardancy of a plastic.

According to the invention you can have the flame retardancy of a Significantly reduce the amount of an additive that causes a plastic, if a normally flammable organic " Material is made flame retardant by adding a system or a combination of substances that essentially consists of the following components:

(A) a halogen-containing compound of the formula

X - (T) -R- (T) - X
η \ Zs ι \ 1 / η

X
η

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in which (s) a «Cycloalkylreet with 5 to 8 carbon atoms la ring, X on the carbon atoms of said radical is chlorine or bromine substituted and R is a saturated acyclic hydrocarbon radical with 1 to 4 carbon atoms and in which the Wer ^r for each η is chosen are that the total halogen content of the compound is in the range from 30 to 90 percent by weight, and

(B) a polymeric hydrocarbon of the formula

in which R is an alkyl hydrocarbon radical having 1 to about carbon atoms, preferably having 1 to 2 carbon atoms, RI is a hydrocarbon radical free of olefinic or acetylenic bonds, and n * is 0 to 4, preferably 0-2, and in which χ is at least 1 and also stands for a number up to 100 or more.

Of the halogens mentioned under (A), bromine is currently used with preference.

The size of the hydrocarbon radical denoted by R is not essential to the invention and there is no critical maximum size. If R ¹ radicals are present, however, then they are generally in the range from about 1 to 20 carbon atoms.

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Han came dl «called hydrocarbon additives according to b ·· known processes. An appropriate procedure is that nan is a starting material of the formula

H-C- (V / V-C-H

1 2 in which R, R and n * have the meaning given above, in Subjecting the presence of a diorganoperoxide, preferably a dialkyl peroxide, to a condensation reaction. Here can about equiraolecular amounts of the starting material and the peroxide in the presence or absence of a solvent at a temperature which is above the decomposition product of the peroxide, while allowing them to act on one another when the hydrocarbon additive is required to form in the desired amount and with the desired molecular weight.

According to the invention, a hydrocarbon additive of the formula can also be used as component (B)

2 2 R ^Z R ^ tt

-CCR R ^Z

\ J

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2 use «, in which R does not contain an alkyl hydrocarbon residue 1 bit about 4 carbon atoms, preferably 1 to 2 carbon atoms • toffateaen, Rl one of olefinic or acetylenic Free hydrocarbon radicals and n "are 0 to 5, preferably 0 to 2.

In every formula the co-component (B) contains Rl, if it contains is present, preferably 1 to 6 carbon atoms.

One can go to the one consisting of components (A) and (B) Add antirone trioxide as an additional component (C) to the system as desired. This way you can get the total salary of additives that are necessary to make the normally flammable organic material flame-retardant further reduce.

The inventive systems of additives are in particularly suitable for flame retarding polypropylene, but they are widely applicable to normally Flammable organic substances such as polymeric substances, cellulose materials, natural fibers, regenerated fibers, man-made fibers and plastics. As examples of such materials be wood, linen, jute, flax, silk, wool and cotton fabrics as well as rayon, polyamide and vinyl or Called acrylic derivatives. Examples of other suitable polymeric compounds are the polymers and copolymers of Olefins such as ethylene and butene, polyisobutylene, the polymers of monomers containing at least one conjugated diene with preferably A to 10 carbon atoms in the molecule, of monovinyl-substituted aromatic compounds, preferably those with 8 to 12 carbon atoms in the molecule, of acrylonitrile, methyl acrylate and methyl methacrylate, preferably homopolymers of butadiene, isoprene, decadiene, styrenes, vinylnaphthalene, acrylonitrile, methyl acrylate and Methyl methacrylate and random, block and graft copolymers of butadiene and styrene, of butadiene, styrene and acrylonitrile, of acrylonitrile and vinyl pyridine and of acrylonitrile and vinyl chloride. Mixtures of the compounds mentioned can also be used in the context of the invention.

Examples of suitable compounds of the formula of component (A) are:

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Bis (2,5-dibromocyclopentyl) dibromomethane 1- (3,5-dibromocyclohexyl) -2- (3, S-dichlorocyclohexyl) ethane Bis (2,4,6-tribromocycloheptyl) methane

1,3-bis (3,5,7-trichlorocyclooctyl) 2,2-dibromopropane 2,3-bis (2,3,4,5, δ-pentachlorocyclohexyl) -1,4-dibromobutane l, 3-Bls (2,3,4,5,6,7,8-heptabromocyclooctyl) -l, 2,3,4-tetrahro'n-

butar l- (2,5-dichlorocyclopentyl) -2- (3,4-dibromocyclohexyl) -3-bromo-

propar »1,3-bis (3,4,5-tribromocyclohexyl) -2-dibromomethylpropane.

F. a preferably used group of compounds of the formula (A) is indicated by the formula

CCH H

Some examples of this group are

1,2-bis (3,4-dihomcyclohexy1) -1,2-dibromoethane 1,2-Bi8 (3,4-dit-omcyclohexyl) -l, 2-dichloroethane 1,2-bis (3,4-dichlorocyclohexyl) 1,2-dibromoethane 1,2-bis (3,4-dichlorocyclohexyl) -1,2-dichloroethane

and mixtures of these compounds.

Examples of polymeric compounds of the formula (B) which are necessary for the systems according to the invention and combinations of additives The condensation products that can be used are those that result from the reaction initiated by free kadikaie of raw materials such as

1,4-diisopropylbenzene

1,4-D1 ( 1-methylbutyl) benzene

1,4-di (l-ethylpropyl) ben7.ol

1,4-diisopropyl-2,6-dioctylbenzene

l-isopropyl-4- (l-methylpropyl) benzene

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1,4-Diieopropyl-2-benzylbenzene ! ^ • Diisopropyl ^ -cyclopentylbenzene l ^ -Dileopropyl-Z, 3,5,6-tetrabutylbenzene 1,4-diisopropyl-2- (p_-tolyl) benzene l-Ieopropyl-4- (l-bntylpentyl) -2-eicosylbenzene

and mixtures containing this compound.

For example, the following compounds can also be used for component (B) of the systems according to the invention and combinations of additives

2,3-di-ethyl-2,3-diphenylbutane (bicurayl) 2,3-dimethyl-2,3-di (4-isopropylphenyl) butane (4,4'-diisopropyl-

biciimyl)

2,3-dimethyl-2,3-di (4-benzylphenyl) butane 3,4-dimethyl-3,4-diphenylhexane

2-methyl-3-isobutyl-2,3-di (4-isobutylphenyl) butane 5,6-diiaethyl-5,6-di (4-cyclohexylphenyl) decane 3,4-diethyl-3,4-di (3,4,5-triethylphenyl) hexane 2,3-diraethyl-2,3-di (3-hexadecylphenyl) butane 2,3-dimethyl-2,3-di (2,3,4,5,6-pentaraethyl) butane 2,3-disaethyl-2,3-di (4-eicosylphenyl) butane

as well as mixtures of these compounds.

The systems according to the invention and combinations of Additives by mixing compounds of the formulas (A) and (B) with one another in such amounts that the weight ratio of the compound of the formula (A) to the compound of the formula (B) is 0.5: 1 to 4: 1, preferably 1: 1 to 2: 1. If the system also includes antimony trioxide as Component (C) is to be added, the components are used in such amounts that the weight ratio from (A) to (B) plus (C) 0.5: 1 to 4: 1, preferably 1: 1 to 2t1 and the weight ratio of (B) to (C) 0.1: 1 to 10: 1.

For use in practice there is no specific amount of the total system of additives to be used upper limit set. As a rule, the system is used in the smallest possible amount that gives the material to be treated the desired degree of flame retardancy and its physical properties as little as possible changed.

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In general, one uses, based on 100 parts of / · ι material to be treated in the following amounts;

I. In the case of the compounds of the formulas (A) and (B) containing Systems:

in wide
Limits

preferably

(A) halogen compound

(B) polymeric hydrocarbon

Complete system of flame retardant additives

0.5-20 parts
0.1-20 parts

1-3 part ·. 1-3 parts

0.6-40 parts 2-6 parts

II. In the compounds of formulas (A) and (B) and the Systems containing component (C):

in wide
Limits ,: -20 parts preferential
way Parts 0 , 1-20 parts 0.8-3 Parts 0 , 1-20 parts 0.2-3 Parts 0 , 7-50 parts 0.2-3 Parts 0 1.8-6

(A) halogen compound

(B) polymeric hydrocarbon

(C) Sb ₂ O ₃

Complete system of flame retardant additives

The upper limit of the amount of one of the systems of the invention to be added to a normally combustible material Additives is determined by the material to be treated. The preferred ones mentioned in the tables above Quantities have been found to be very suitable for a preferred polypropylene-directed embodiment of the invention.

One can use the above for flame retarding organic substances use different working methods. For example, you can have an intimate mixture of a thermoplastic Material and one of the flame-proofing agents according to the invention produced by the fact that the material and mixing the bromine compound at an elevated temperature in an extruder or a kneader. You can use the components (A) and (B) also dissolve in a common solvent the

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Mix the solution with the polymers and the solvent lan remove. Know about granular or pearl-shaped plastics the grains or pearls with a coating from the flameless «Respecting means are provided.

The substances treated according to the invention can fill levels. Dyes, pigments, plasticizers, antistatic agents, stabilizers and other agents are added. Means of this type are known for their relevant use.

The parts mentioned in the following examples are parts by weight, based on 100 parts of the polymer (THT).

example 1

50 g of a freshly distilled p-diisopropylbenzene which has been purified by H So washing and 36.5 g are filled Dl-tert-butyl peroxide in a 200 ml provided with stirrers Flask in, stir the solution and heat it for about 50 hours at about 120 ° C. The one obtained after this time is removed white precipitate by filtering, washing it with 95Tig Ethanol and dry it. 10 g of a solid white substance which melts at 177 ° -197 ° and a mixture are obtained represented by the following formula:

In this formula, χ stands for the numbers 1 to 3.

Commercially available polypropylene, which has a melt flow value of about J (ASTM D 1238), is treated with 0.3 THT of a known antioxidant (Irganox 1010 " Tetrakis £ 3- (3,5-di-tert-butyi-4-hydroxyphenyl) propionyloxymethyl3 methane), mixes a number of samples of the flaky polymer in the dry state with different amounts of flame retardant additives and continues mixing in a conventional Brabender Plastograph for 10 minutes in a nitrogen atmosphere at 185 ° C and 50 rpm.

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INSPECTED

205Q009

The fully mixed polymer preparation d-nn is pressed in the usual way to form sheets of size 13 × 20 × 0, ■ et, /.er·, cut the sheets into pieces of size Ij χ 1.3 \), λ cm and checked these according to ASTM D 635 for their flammability. ¹ Ue of preparations used and those obtained with them can be seen from the following table:

Additives THT

BrBCÄ * Sb 0 Hydrocarbon total Classification? substance additive additive 0.00 0.00 0.00 0.00 burns 0.80 0.40 0.00 1.20 burns 0.80 0.40 0.25 1.45 self-extinguishing 0.80 0.40 0.40 1.60 self-extinguishing 0.80 0.40 0.50 1.70 self-extinguishing 0.80 0.40 0.75 1.95 not burning

* = 1,2-bis (3,4-dibro! I! Cyclohexyl) -1, 2-dibromoethane.

The table shows that very curdling amounts of the Flameproofing system of additives according to the invention enough to make the embers firmer.

Example 2

Treating commercially available polypropylene having a melt flow value of about 'has i (ASTM η 1238), with 0.3 THT a known Oxydationsverhinderers (Triranox 1010 ■ tetrakis [3- (3,5 · di-tert-butyl-4-hydroxy -phenyl) propionyloxymethyl3-methane), mixes various amounts of flame retardant additives with a number of samples of the flaky polymer in the dry state and continues mixing in a conventional Brabender Plastograph for 10 minutes in a nitrogen atmosphere at 185O Γ.

The fully mixed polymer preparation is then compressed in the usual way to sheets of the size 13 χ 20 χ 0.3 cm, cut the sheets into pieces of the size Ij χ 1.3 χ 0.1 cm and tests them for their flammability in accordance with ASTM D 635.

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The preparations used and the results achieved. ** "" can be seen in the following table:

Bicumyl

(b)

Classification

0.0 0.0 0.8 1.0 1.0 1.0 1.2 1.2

burns

self-extinguishing non-burning non-burning

(a) 1,2-bis (3,4-dibromocyclohexyl) -1,2-dibromoethane

(b) 2,3-dimethyl-2,3-diphenylbutane

The table shows the low quantities of flame retardant Additives to the plastic samples or self-extinguishing can be made non-breeding. From maybe still Of greater importance is that the non-burning pattern is clear and transparent and of the non-flameproof Medium treated patterns are almost indistinguishable.

Example 3

A number of further polypropylene preparations are prepared in essentially the same manner as in Example 2, from which each 0.3 THT of the antioxidant contains different amounts of flame-retardant additives. The results can be seen from the following table:

Additives (THT)

BrBCÄ Sb.O Bicumyl Total additive Classification Z J according to ASTM D 635 0.0 0.0 0.0 0.0 burns 0.0 3.0 6.0 9.0 burns 1.5 0.75 0.0 2.25 self-extinguishing 1.5 0.75 0.50 2.75 not burning 0.75 0.38 0.00 1.13 burns 0.75 0.38 0.75 1.88 not burning 0.75 0.38 0.25 1.38 not burning 0.50 0.38 0.50 1.38 self-extinguishing

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BATH ORIGINAL

The information contained in the table above makes d3 Effectiveness clearly that the flame retardants according to the invention Systems of additives even in extremely small quantities. In the case of the small amounts mentioned, the physical Properties of the polymer to be made flame-retardant are not or only slightly changed.

Example 4

Polypropylene preparations are prepared and set in essentially the same manner as in the previous examples to each preparation a different flame-retardant combination of additives from that of the other preparations. Every Preparation contains 0.3 THT of the antioxidant and one Total amount of 1.8 THT of the flame-retardant combination. the Components of the combination and the results obtained are listed in the following table:

Additives (THT) Bicumyl Sb ₂ O ₃ Classification 1.8 according to ASTM D 635 BrBCÄ - - 0.9 1.8 burns 1.8 0.9 burns - - 0.9 burns - 0.8 0.9 self-extinguishing 0.9 0.6 0.2 burns - 0.4 0.4 burns 0.9 0.2 0.6 not burning 0.8 0.0 0.8 not burning 0.8 1.0 1.0 η non-burning 0.8 0.6 0.0 self-extinguishing 0.8 0.6 burns 0.8 self-extinguishing 0.8 self-extinguishing 0.6

The information contained in the table clearly shows that the bromine-containing compound, bicumyl and antiraon oxide in surprising and work together in an unpredictable way and impart flame-retardant properties to the polypropylene samples. The information also makes it clear that you can use the combination of the three additives generally achieved better results than with the combination of two of the additives. The table also shows that in order to achieve effective flame retardancy, the three additives can combine with each other in different proportions.

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Example 5

Another polypropylene preparation is made, containing 0.3 THT of an oxidation inhibitor, 0.8 THT BirBCA, 0.8 THl Sb 0.1.0 THT bicumyl and 0.25 THT of a commercial heat ^{stabilizer containing dibutyl J} tin maleate (Advastab T-290 , Advance Chemical Co.). A test according to ASTM D 63 shows that the preparation does not burn. The result of this test shows not only the effectiveness of the inventive flame-resistant system of additives, but also that other substances known as additives for polymers can be added to the system while maintaining the same effectiveness.

Example 6

In order to investigate the effect of 4.4 ^I -Diisopropylbicumyl as a component of a flame retardant system of additives to another combination is more THT 0.3 Oxydationsverhinderers a polypropylene-containing preparations each of the additives and performs testing in the described manner discussed in the preceding examples by. The correlations and the results obtained are shown in the following table:

Additives (THT)

BrBCÄ

Sb ₂ O ₃

Substituted
B i cumy1

Total additive

Classification

1.5
1.5
0.75
0.75

0.75 0.75 0.38 0.38

0.0

0.50 0.50 0.75

2.25 2.75 1.63 1.88

self-extinguishing non-burning self-extinguishing not burning

The table shows that the bicumyl derivative with an initial result as a component of the flame-retardant according to the invention System of additives can be used.

BATH ORIGINAL

Claims (6)

Claims; in which (s) is a cycloalkyl radical having 5 to 8 carbon atoms in King, X on the carbon atoms of said radical substituted chlorine or bromine and R is a saturated acyclic hydrocarbon radical with 1 to 4 carbon atoms and in which the values for each η are chosen so that the total halogen content of the compound is in the range from 30 to 90% by weight and (B) a polymeric hydrocarbon of the formula H - R ι R ² CR ² or a hydrocarbon of the formula in ik-ru'ii V, ~ finen \ I! · «, I see WihleriWnsserstof f rost with 1 to Ί l'.ohl cnyiofTni ornt-n, r '" -inen from ο Lef ini or acetyl en i r.chi 'M bh «lum', '' n fn-ien Koh Lenwa-sserst.of frest, n 'a' whole / ah! from f) to 4, χ a gan.ee /> ahl from 1 to 10 · "· Lind n ^ einn i '^ nizt /.ahL from 0 to ^r j mean, where! ili ■ if, η .rhi * - ν rhaJiiiis vr> n ίΛ) to (B) in the Ik-kingdom of Ί, '-!' bi-, 4: 1) i '. i ΟΊΒ, -0 / J l'J 2. A system of additives according to claim 1, characterized in that component (B) is a polymeric hydrocarbon of the formula tj
C. CH CH, ι - C - CH- CH t 3
C -ι I. T I CH. CH where χ is an integer from 1 to 3. 3. A flame-retardant system according to claim 1 or 2, characterized in that the additional component (C) used is antiraon trioxide and that the weight ratio from (A) to (B) plus (C) in the range of 0.5: 1 to 4: 1 and that . Weight ratio of (B) to (C) in the range from 0.1: 1 to 10: 1. 4. A preparation of a normally flammable synthetic or natural resin or a normally combustible synthetic or natural fiber or one made therefrom Textile material and a small amount of a flame-retardant system of additives incorporated into it, characterized in that this preparation is one of those characterized in the preceding claims contains flame retardant systems. 5. A preparation according to claim 4, characterized in that the amount of component (A) in the range from 0.5 to 20, the amount of component (B) in the range of 0.1 to 20 and the total amount of the flame retardant system used, ranging from 0.6 to 40 parts by weight to 100 parts by weight of the normally combustible material lies. 6. Fine preparation according to claim 4, characterized in that (ILe Mens ^ e of component (A) in the range of 0, ^ Ms 20, the Meriee of components (B) \\\ v \ (C) in each case in the Bern i from 0.1 Mm 20 utiii the Cii'snmt iruMire of the used f lamniwi clr i : ■ - tri'u-henden system in the Tu -reich from 0.7 h I. <$ '> () f'.ew! cht st el .1 en, \ ) ti Ί. !! ff it κ ■ ! • ti on
i.-il «! Ii iil.st ν i! t: dt .-, · normal ert / ii se brenr.har; ti ] 0 y B l (J / 2 I Ί 0 BATH ORIGINAL