DE2532070A1 - FIRE-RETARDANT POLYMER COMPOUND - Google Patents

Description

7 F 3 2 O / Π

Dipl.-Ing. H.Weickmann, Dipl.-Phys. Dr. K. Fincke

Dipl.-Ing. F. A. Weickmann, Dipl.-Chem. B. Huber H / KR / ZB

8 MUNICH 86, DEN

PO Box 860 820

MÖHLSTRASSE 22, CALL NUMBER 98 39 21/22

3532

HOOKER CHEMICALS & PLASTICS CORP., Niagara Falls,

N.Y./USA

Fire retardant polymer mass

US Pat. No. 3,403,036 describes polymer compositions which, as flame retardants or fire retardants, consist of Diels-Alder adducts a halogenated cyclopentadiene and polyunsaturated cycloaliphatic Connections included. There the diadducts of 1,5-cyclooctadiene, dicyclopentadiene, cyclopentadiene and Bicycloheptadiene described.

It has now been found that in certain areas of application for polymers, the diadducts of halogenated cyclopentadienes and the compound bicyclononadiene have surprisingly superior properties. The superior properties close a fire retardant effectiveness and a lower afterglow. The polymer compositions have improved heat deflection

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or heat bending properties and improved tensile and flexural properties compared to the known similar polymer compositions which contain the Diels-Alder diadducts.

According to the invention, flame-retardant or fire-retardant polymer compositions are now used provided which a polymer and an effective fire retardant ratio of Diels-Alder diadducts a halogenated cyclopentadiene and bicyclononadiene. The compounds of the present invention have the following formula

X X

X X X

where X is bromine, chlorine and / or fluorine, Y is bromine, chlorine, Fluorine, alkyl of 1 to 10 carbon atoms, alkoxy, the alkyl group containing 1 to 10 carbon atoms, haloalkyl and / or haloalkyloxy, where the alkyl group contains 1 to 10 carbon atoms and halogen is fluorine, chlorine or bromine.

The preferred fire retardant additive compound of the invention is the Diels-Alder diadduct of hexachlorocyclopentadiene and bicyclo (4,3,0) nona-3,7-diene. The chemical name for this compound is 1,2,3,4,6,7,8,9,12,12,13,13-dodecachlor-1,4,4a, 4b, 5,5a, 6,9,9a , 10.1Oa, 11a-dodecahydro-1,4: 6,9-dimethane-11-H-benzo (b) -fluorene.

The additive compounds according to the invention are prepared by bicyclononadiene with halogenated cyclopentadienes of the general formula

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X
i > ¹ Γ
X γ ^ Y

wherein X and Y have the meanings given above, is implemented. The diadduct of bicyclononadiene and hexachlorocyclopentadiene is in J. Gen. Chem. of the U.S.S.R. 29, p. 3552 (1959) described.

Halogenated cyclopentadienes which are suitable for the preparation of the adducts described above are, for. B. Hexahalogencyclopentadiene as hexachlorocyclopentadiene, hexafluorocyclopentadiene and Hexabromcyclopentadien, Monoalkylpentahalogencyclopentadiene such as 1-methyl-penta-chloro-cyclopentadiene, 1-Äthylpentabromcyclopentadien, 1-Hexylpentafluorcyclopentadien, 1-Decylpentachlorcyclopentadien, Dialkyltetrahalogencyclopentadiene such as 1,1-Dimethyltetrachlorcyclopentadien, 1,1-Dibutyltetrachlorcyclopentadien, 1-methyl, 1 -Hexyltetrabromocyclopentadiene, 1,1-dinonyl-tetrafluorocyclopentadiene, 1,1-didecyltetrachlorocyclopentadiene, alkoxyhalogenocyclopentadienes such as 1-methoxy-pentachlor- and 1,1-dimethoxytetraehloreyclopentadiene, 1-hexoxypentabromo-1-diene, 1-hexoxypentabromoxy-, 1-hexoxypentabromoxy-, 1-hexoxypentabromoxy-, 1-hexoxypentabromo-, 1-hexoxypentabromoxy- and pentachloro- and 1,1-didecoxy-tetrachlorocyclopentadiene, 1-ethoxy-pentafluoro- and 1-ethoxy-, 1-butoxy-tetrafluorocyclopentadiene, monohaloalkylhalocyclopentadienes such as 1-chloromethylpentachlorocyclopentadiene, 1,1-bis (chloropentachloradiene, 1-bromocyclopentadiene, 1,1-bis (chloropentadiene-1-bromocyclopentadiene) , 1-bis (bromohexyl ) tetrachlorocyclopentadiene, 1-pluordecylpentafluorocyclopentadiene, 1,1-bis (fluorodecyl) tetrafluorocyclopentadiene, 1-chloromethyl-, 1-bromopropyltetrabromocyclopentadiene. The preferred halocyclopentadiene is hexachlorocyclopentadiene,

The adduction stage is preferably carried out as a reaction in liquid Phase carried out.

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Although the reactants can be combined directly, the reaction is preferably carried out in the presence of a solvent carried out.

The solvent can be an excess of the stoichiometric amount of the halocyclopentadiene starting material or a solvent which is inert to the reactants and the reaction product. Preferably the solvent should boil above about 90 ° C. Suitable non-reactive solvents are e.g. B. toluene, xylene, Nitrobenzene, methylcyclohexane, perchlorethylene, acetylene tetrachloride and the same.

The temperature used in the adduction stage can range from about 75 ° C. to about 200 ° C., although temperatures outside this range can also be used. Preferably, the adduction reaction at about 85 ⁰ C is performed to about 170 ⁰ C. The time required for the adduction to be substantially completed may vary depending on the reactivity of the halocyclopentadiene, the presence or absence of a solvent, the reaction temperature, etc. Generally, a reaction period of between about 5 and 100 hours will suffice, but preferably about 10 to 48 hours.

The reaction is preferably carried out at atmospheric pressure conditions carried out, although you can also work with excess pressure. This may be preferred on certain occasions be e.g. B. if one of the starting materials has a low reactivity and / or a high volatility. In general If superatmospheric pressures are used, the autogenous pressure is sufficient, although pressures of 1.1 at to 100 at or more can be applied.

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The polymers contemplated in the present invention include the homopolymers and copolymers of unsaturated aliphatic, alicyclic and aromatic hydrocarbons. Suitable monomers are ethylene, propylene, butene, pentene, hexene, heptene, octene, 2-methylpropene-1, 3-methylbutene-1, 4-methylpentene-1, 4-methylhexene-1, 5-methylhexene-1, bicyclo ( 2,2,1) -2-heptene, butadiene, pentadiene, hexadiene, isoprene, 2,3-dimethylbutadiene-1,3, 2-methyl-1,3-pentadiene, 4-vinylcyclohexene, vinylcyclohexene, cyclopentadiene, styrene and methylstyrene and the same. Polypropylenes, ABS polymers, polystyrenes and high impact or rubber modified polystyrene are particularly suitable polymers. High impact polystyrene is a heterophase polymer in which a rubber-like polymer is dispersed in the form of small spheres in a continuous polystyrene matrix. The available volume of rubber can be only 10 to 15 % in medium impact strength grades and as much as 40 % in particularly high-impact types. The rubbery polymer used with the polystyrene is usually an elastomer with residual unsaturation, e.g. B. polybutadiene or a styrene-butadiene rubber. These tough grades of polystyrene can be made by mechanically mixing the rubber and polystyrene on a two roll mill or in an extruder. Conventional manufacturing techniques employ solution graft polymerization processes, although some specific types are made by blending or mechanically blending polybutadiene latex with the polystyrene which is made by bulk, suspension, solution, ionic or emulsion polymerization. The graft polymerization process begins by dissolving the rubber in the styrene monomer, whereupon the rubber solution is fed into the polymerization vessels. Other polymers useful in the invention are described in U.S. Patent No. 3,403,036.

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The polymers according to the invention can be in various physical Forms, e.g. B. as shaped bodies such as moldings, plates, rods and the like., Fibers, coatings, films and fabrics and the like.

The halogenated Diels-Alder adducts of the compositions according to the invention are conveniently incorporated into the polymeric materials in an effective fire retardant amount. In general are the halogenated Diels-Alder adducts in amounts of about 2 to about 50 weight-96 of the polymer mass, expediently of about 5 to about 40% by weight of the mass, preferably from about 10 to 35% by weight, mixed in. Improved fire retardant properties can be obtained by adding metal compounds of the metals antimony, arsenic and / or bismuth to the polymer masses in amounts of from about 1 to about 30% by weight of the polymer composition, preferably from about 2 to 25% by weight.

Antimony oxide is the antimony compound that is currently preferred for purposes of the invention. However, there are many Antimony compounds suitable. Suitable antimony compounds are, for. B. the sulfides of antimony, the salts of the alkali metals Group I of the periodic table, the antimony salts of organic acids and their pentavalent derivatives and the esters of antimony Acids and their pentavalent derivatives. It is convenient to use sodium antimonite or potassium antimonite when it is desired to use an alkali metal salt of antimony for the compositions of the invention. U.S. Patent 2,996,528 suitable antimony salts of organic acids and their pentavalent derivatives are described. Compounds of this class are z. B. antimony butyrate, antimony valerate, antimony caproate, Antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, Antimony cinnamate, antimony anisate and their pentavalent ones Dihalide derivatives. Also suitable products are the esters of antimony acids and their pentavalent derivatives like them in U.S. Patent 2,993,924. Examples of this

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are tris (n-octyl) antimonite, tris (2-ethylhexyl) antimonite, tribenzylantimonite, Tris (ß-chloroethyl) antimonite, tris (ß-chloropropyl) antimonite, Tris (ß-chlorobutyl) antimonite and its pentavalent ones Dihalide derivatives. Finally, other suitable organic antimony compounds are the cyclic antimonites such as trimethylolpropane antimonite, pentaerythritol antimonite and glycerin antimonite. The corresponding arsenal can also be and bismuth compounds can be used, in particular the oxides of arsenic and bismuth.

The components of the compositions according to the invention can be mixed together by several methods. The additives can be incorporated into the polymer while the latter is dissolved in a suitable solvent. This procedure is particularly useful when it is desired to mix in the additives during the polymer production process. When the polymer is then separated from the solvent, the additives are intimately mixed with the polymer. Usually the additives are mixed with the polymer in the molten state at temperatures ranging from the melting point to the decomposition point of the polymer, e.g. B. from 70 to 60O ⁰ C, can extend. Alternatively, the additives and the polymer can be dry mixed in a finely divided state so that an intimate mixture is obtained after the subsequent molding or extrusion.

The invention is illustrated in examples. This contains all information regarding the parts and percentages on the Based on weight.

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- η -

example 1

Preparation of the diadduct of bicyclononadiene

(A) had been heated to 1230 g (4.5 mol) of hexachlorocyclopentadiene, .the to 150 ⁰ C, were in the course of two hours, 180 g of bicyclo (4,3,0) nona-3,7-diene (1, 5 mol) dissolved in 410 g of hexachlorocyclopentadiene. The reaction mixture was heated to about 150 ° C. for 12 hours and then cooled, whereby a solid product precipitated. About 752 g of the solid product was filtered off from the reaction mixture and the solids were refluxed with xylene. It was filtered and washed with benzene to obtain 542 g of a product having a melting point of 338 - 34O ⁰ C were obtained.

(B) To 1,230 g (4.5 mol) of hexachlorocyclopentadiene, which was heated to 16O ⁰ C, was added dropwise in the course of two hours, a solution of 180 g of bicyclo (4,3,0) nona-3,7-diene (1.5 mol) dissolved in 410 g of hexachlorocyclopentadiene. The reaction mixture was heated to 160 to 170 ° C. for 12 hours and then cooled, whereby a solid product precipitated. The solid product was filtered off from the reaction mixture and washed four times with 300 ml of acetone, whereby 696 g of a product having a melting point of 339-342 ° C was obtained. The resulting 694 g of product was refluxed with 500 ml of xylene for 1 hour, cooled, filtered and washed with xylene.

(C) The product of Example 1 (B) was combined with the solid product of Example 1 (A). The united products were refluxed with xylene, cooled, filtered and washed with benzene to give 912 g of purified 1,2,3,4,6,7,8,9,12,12,13,13-dodecachlor-1,4,4a, 4b, 5,5a, -6,9,9a, 10,10a, 11a -dodecahydro-1,4: 6,9-dimethane-11-H-benzo- (b) -fluorene were obtained.

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Example 2

27 parts of the diadduct of hexachlorocyclopentadiene and bicyclononadiene, prepared according to Example 1 (C), were mixed with 13 parts of antimony trioxide and 60 parts of polypropylene and added Test specimens deformed, which tests were subjected to fire resistance and mechanical properties! the Results of these tests are summarized in Table I along with the results of similar tests performed with the Diadducts of hexachlorocyclopentadiene and dicyclopentadiene and 1,5-cyclooctadiene, respectively. The table contains also the results of a control test that was carried out only with polypropylene. The test results show that the invention Mass were superior in terms of the values for heat deflection or heat curvature.

Example 3

18 parts of the adduct of hexachlorocyclopentadiene and bicyclononadiene, prepared according to Example 1 (C), 6 parts of antimony trioxide and 76 parts of ABS polymer (Blendex 101) mixed and shaped into test specimens, subjected to tests for fire resistance and mechanical properties became. The results obtained are shown in Table II. Table II also contains the results of similar tests carried out on the diadducts of hexachlorocyclopentadiene and dicyclopentadiene and 1,5-cyclooctadiene, respectively as well as the results of control tests with the ABS polymer alone.

It can be seen that the composition of the present invention is superior in flame retardancy and tensile strength is.

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Composition of the mass, wt. -%

Polypropylene Bicyclononadiene Diadduct Dicyclopentadiene Diadduct Cyclooctadiene diadduct antimony trioxide d

properties

Fire delay according to ASTM D-635 escape time, seconds Post-glow time, seconds drops

Notched impact strength according to Izod, sprue "deduction

^M average

Tensile strength, kg / cm

Tensile strength at break, kg / cm elongation when flowing, % elongation at break, %

Table I. A. B. C. D. 100 65 60 60 27 25th 27 10 13th 13th

burns 5.0 3.1 15.3 86 92 > 52. Yes no no no 1.21 0.63 0.70 0.52 0.69 0.50 0.41 0.48 0.95 0.56 0.56 0.50 374.7 300.2 286.1 284.7 161.7 257.3 261.5 239.0 7.7 4.5 6.3 2.83 45.0 16.0 21.5 22.0

Table I (continued) properties

CD CO 00 CO

Flexural flow, kg / cm

Bending cdul, kg / cm

Heat deflection 66 kg / cm "264 kg / cm ²

Shore hardness D Rockwell hardness L Rockwell hardness R Thermal stability Cloud formation 653.1 ⁵⁴² ' ⁷ , 570.8 543.4 18.6x10 ⁵ 22.4x10 * 25.4x10 ^ 25.9x10 *

7.33 7, i p £ z. 7 3 3.99 3.68 4.99 5.40 7S, 0 82.0 77.2 80.2 βΛ, β cA ρ 68.2 61.7 103.3 96.8 - 97.4 - Well Well Well no

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Example 4

15 parts by weight of the diadduct of hexachlorocyclopentadiene and bicyclononadiene, prepared according to Example 1 (C), were with 5 parts of antimony trioxide and 50 parts of polystyrene mixed and shaped into test specimens, the tests for fire retardancy and subjected to mechanical properties. The results of these tests are shown in Table III along with the results of similar tests with test specimens made of polystyrene with the diadducts of hexachlorocyclopentadiene Dicyclopentadiene or 1,5-cyclooctadiene and control tests composed with polystyrene alone.

It can be seen that the composition according to the invention in terms of the afterglow properties and the tensile strength and flexural properties is superior. The adduct considered according to the invention is opposite to the diadduct of 1,5-cyclooctadiene superior in terms of impact resistance.

Favorable results are obtained if the diadduct of Example 1 (C) is converted into rubber-modified high-impact Polystyrene incorporated.

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OO OD CD

Composition, wt. -%

SECTION

Bicyclononadiene Diadduct Dicyclopentadiene Diadduct Cyclooctadiene diadduct antimony trioxide

properties

Fire retardation according to ASTM D-635

Flame time, seconds

Post-glow time, seconds

drops

Notched impact strength according to Izod, sprue "deduction

" average

Tensile strength, kg / cm

Tensile strength at break, kg / cm

Table II B. C. D. A. 70 70 76 100 18th 22nd 22nd 8th 8th 6th

burns

8.10

6.75

7.43

402.1

317.1

17th

no
1.09
1.03

1.09

326.9

309.3

2.8

3.3

no

0.71

0.60

0.66

338.8

345.9

4.5 0

1.39 1.48 1.44

343.1 308.1

Table II (continued)

cn o co

properties

Elongation on flow, % "at break, % flexural flow, kg / cm '

Flexural modulus, kg / cm heat deflection 66, kg / a "264, kg / cm ²

Shore hardness D Rockwell hardness L Rockwell hardness R Thermal stability Cloud formation

A. B. C. D. 4.2 3.3 2.6 3.2 12.0 5.6 3.0 9.0, 634.4 580.0 636.2 583.5 17.6x1O ³ 18.2x1O ³ 22.9x1O ³ 20.0x10 6.43 6.57 6.43 6.32 5.60 5.68 5.71 5.43 78.8 80.6 77.6 79.2 39.4 28.2 39.6 21.5 86.2 83.4 too hard 78.8

no

CO tSJ O

Composition,

Polystyrene Bicyclononadiene Diadduct Dicyclopentadiene Diadduct Cyclocctadiene diadduct antimony trioxide

properties

ASTM D-635 flame delay time, seconds Post-glow time, seconds drops

Notched impact strength according to Izod, sprue "deduction

" average

Tensile strength, kg / cm

Tensile strength at break, kg / cm

Table III B. C. D. A. SO 80 80 100 15th 15th 15th Ul 5 UI

burns 1.2 6.3 i, S Ul
I. 14th 22nd 3.1 Yes no no 1.063 0.55 0.41 0.58 0.517 0.40 0.37 0.36 0.757 0.48 0.39 0.47

553.2

221.4

372.6

421.1

Table III (continued)

O (O OO CS O5

properties

Elongation when flowing, % "when breaking, %

Flexural flow, kg / cm

Flexural modulus, kg / cm

Heat deflection 66 kg / cm "264 kg / cm ²

Shore hardness D Rockwell hardness L Rockwell hardness R Thermal stability Cloud formation

3.30 1.46 1.27 1.7 1176.1 805.6 773.2 890.0 67.6x1O ³ 35.1x1O ³ 35.1x1O ³ 36.5x1C ³ 6.28 6.28 6.35 6.12 5.65 5.60 5.72 5.47 84.6 90 86.2 91.4 98.2 19.8 98.2 97.9 121.8 98.2 - too hard Well Well mediocre no no

CJI OJ K) O

Claims (10)

Claims 1. Flame-retardant polymer composition, characterized in that it is a polymer and an effective Flame-retardant proportion of a compound of the general formula wherein X is bromine, chlorine and / or fluorine, Y is bromine, chlorine, fluorine, alkyl having 1 to 10 carbon atoms, alkoxy, where the alkyl group contains 1 to 10 carbon atoms, haloalkyl and / or haloalkyloxy, where the alkyl group contains 1 to 10 carbon atoms and halogen, fluorine, chlorine or Bromine is, means, contains 2. Composition according to claim 1, characterized in that it is a fire-retardant compound 1,2,3 * 4,6,7,8,9,12-12,13, ^ -Dodecachlor-1,4,4a, 4b, 5,53,6,9 ^, 10,103,113- ^ 0-decahydro-1,4: 6,9-dimethano-11-H-benzo (b) fluorene contains. 3. Mass according to claim 1 or 2, characterized in that it is the fire-retardant compound in an amount of about 2 to about 50 weight percent based on the polymer composition contains, and that it further contains an antimony compound in an amount of from about 1 to about 30% by weight, based on the polymer mass. 9 3 9: Π 'ι ι Γ 7532070 - ie - 4. Composition according to claim 3, characterized in that the antimony compound is antimony oxide. 5. Composition according to one of claims 1 to 4, characterized in that g e k e η η ■ draws that the polymer is polypropylene. 6. Composition according to one of claims 1 to 4, characterized that the polymer is polystyrene. 7. Composition according to one of claims 1 to 4, characterized in that the polymer is rubber-modified Is polystyrene. 8. Composition according to one of claims 1 to 4, characterized in that the polymer is an ABS polymer. 9. Composition according to one of claims 1 to 4, characterized in that the polymer is a homopolymer or Is an unsaturated hydrocarbon copolymer. 10. Fire retardant polymer composition, characterized in that it is an ABS polymer, about 10 to about 35% by weight of the Diels-Alder diadduct of hexachlorocyclopentadiene and bicyclononadiene, based on the weight of the polymer composition, and about 2 to about 25% by weight Contains antimony trioxide. ^r 09886/1161