CS201731B1 - Though polymere material based on ps withlower flammability and improved resistance to light - Google Patents

Description

The invention relates to a non-pigmented or pale pigmented tough polymeric material with reduced flammability and increased adolescence to aging.

The flammability of the polymeric material can be reduced by the addition of substances retarding the course of chemical reactions, which are the flame retardant. These substances, the so-called flame retardants, usually contain halogen, phosphorus or nitrogen in their molecule, possibly a combination of these elements. The effectiveness of these substances is generally increased by the addition of so-called synergistic agents.

A number of inorganic compounds, in particular antimony trioxide, have a synergistic effect in combination with halogen-containing flame retardants.

The addition of flame retardants has a negative effect on a number of important polymer properties. Significant decreases are observed mainly in impact and notch toughness, ductility, heat resistance and resistance to aging. Especially in the presence of brominated aromatic compounds, the light aging of the polymer is significantly impaired - material yellowing and impact resistance and other properties decrease rapidly, not only under the influence of sunlight and atmospheric effects in outdoor applications, but often by scattered daylight in indoor applications . Although undesirable color changes can sometimes be obscured by suitable pigmentation of the material, the pigment itself does not usually provide sufficient protection against aging, although, for example, the use of a black pigment in combination with other stabilizing agents may, under certain circumstances, improve light aging resistance.

In many cases, however, the nature of the application requires that the spent material be light colored, so that the addition of a dark pigment at a sufficiently high concentration is not possible. The light-colored palystyrene plastics produced therefrom are subject to very marked changes in color and the deterioration of the mechanical properties under the influence of light radiation in the presence of said flame retardants, while at the same time rendering the products of these plastics relatively low. For many products, such as various articles of consumption, housing equipment, building profiles, decorative materials, etc. should be marked discoloration caused by light material aging, considered an important aesthetic defect, 'rete in a number of applications was out the possibility of using light ⁰ »polystyrene of plastics with reduced flammability at all.

It has now been found that these drawbacks can be greatly reduced if a tough polymeric material according to the invention is prepared comprising 50-85 wt. tough polystyrene,

- 25 wt. chlorinated polyethylene containing 25-45 wt. bound chlorine, 5 - 15 wt. flame retardant, preferably halogenated organic compounds, 3-6 wt. synergistic additives, preferably with antimony trioxide, 0.1 - 1.5 wt. phenolic type entiexidant,

0.1 - 3.0 wt. 0.1 to 3.0 wt. organotin compounds and / or 0.1 - 3.0 wt. barium, cadmium, zinc or calcium salts of organic acids or mixtures thereof and 0.1-2.0 wt. a light stabilizer of the benzophenone or benztriazole type, or a compound of the class of sterically shielded cyclic amines, or mixtures of said light stabilizers. A further improvement in aging resistance can be achieved by adding epoxy compounds in an amount of from 0.1 to 3.0 wt%.

Tough polystyrene means polystyrene which contains an unsaturated elastomer, such as polybutadiene or its copolymers, polyisoprene or copolymers from below, as a modifying component. in the amount of 4 - 25% wt.

Chlorinated polyethylene is a product obtained by chlorination of low-pressure polyethylene to a content of 25 - 45% by weight. chlorine. Since the plasticized composition is subjected to elevated temperatures, it is desirable that the chlorinated polyethylene used be effectively stabilized against the effects of elevated heats.

A flame retardant is understood to mean an organic compound containing bromine, chlorine, phosphorus, or nitrogen, or the coabination of compounds of these elements. Particularly preferred is the use of halogenated organic compounds such as octabromodiphenyl, nonabromodiphenyl, decabromodiphenyl oxide, hexabromocyclododecane, tris-dibromopropyl phosphate, trisbromocresyl phosphate, chlorinated and brominated paraffins, and the like. with antimony trioxide.

As the phenolic antioxidants, mononuclear, sterically shielded phenols such as 2,6-diterobutyl-4-methylphenol, ectadecyl-3 (3,5-diterobutyl-4-hydroxyphenyl) propienate, a mixture of phenol alkylation products and the like can be used. , or substituted polyhydric phenols, such as non- 2,5-di-tert-amylhydrochinen, hydroquinone monobenzyl ether or substituted bisphenols and thiobisphenols such as 2,2-methylene-bis- (4-methyl-6-tert-butylphenel), 2,2'-methylene-bis (4-methyl-6) (n-phenylphenol), 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4'-methylene-bis (2-methyl-6-tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-terbutylfenol) and the like., and vícejoderné phenols like e.g. l _l l, 3-tris (2-methyl-4- hydroxy-5-tert-butylphenyl) butane,

201 731

1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) -benzene, pentaerythritol-tetrakia (3-C35-diterebutyl-ε-hydroxyphenyl · propionate) and the like, and single or in combination.

Phosphite type stabilizers are phosphoric acid esters, which are not known to be stabilizers. tris (nonolfenyl) phosphite, tris (phenylethylphenyl) phosphite, 2,4-dinonylphenyl-di (4-monolylphenyl) phosphite, distearylpentaBtithritol diphosphite and the like.

Suitable erganecin compounds are dibutyltin maleate, diektyltin maleate, dibutaltin dileurate, di-n-ectyltin (mone-2-ethylhexyl maleate), di-ectyltin mercaptide, dibutyltin dilauryl mercaptide, dibutyltin dilal mercaptide, dibutyltin dilal mercaptide, dibutyltin dicllyltinate, dibutyltin dicllyltinate.

Examples of organic salts include the barium and cationic salts of lauric acid, calcium and zinc pellets of stearic acid, barnatau, cationic and zinc salts of caprylic acid and pad.

Examples of benzafenan-type light stabilizers are, for example, 2,4-dihydoxybenzophenone, 2-hydroxy-4-n-ectylexybenzephenene, 2-hydroxy-4- (2-ethylhexyloxybenzophenone), 2,2-dihydroxy-4-methoxybenzophenone, 2Thydrexy-4-n -butylexybenzephenene, bis (4-etexy-2-hydroxybenzephenene) and the like.

Suitable light stabilizers of the benztriazalavéhe type are not. 2- (2fíydroxy-5-methylphenyl) benztriazel, 2- (2-hydroxy-3, 5 '-ditercbutylfenyl) 5-chlorbenztriazel, 2- (2iíydrexy-5-34ercbutyl ^of -nietylfenyl) 5-chlarbenztriazal like.

Examples of light stabilizers of the class of compounds, referred to as sterically shielded cyclic amines, are bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate or 2,2,6,6-tetramethyl-4-4salicylaliminapiperidine-1. -Acid and falsely.

Light stabilizers can be used individually, or in libaval combinations.

As suitable epexidic compounds, epaxidated brewing alley, epoxystearic acid butyl ester, 2-ethylhexyl epoxystearic acid ester, phenylglycidyl ether, epichlarhydrin and bisphenal A pelykendenzation products, and the like can be used.

The flame retardant polyelectric material of the present invention has substantially more favorable fire-technical characteristics, such as flame and heat resistance, oxygen numbers, flame retardancy, and the like, which have been verified by the use of tests such as UL-94, ASTM D 635,

CSN 64 0756 and the Herpala Padle Index.

In contrast to conventional low flame retardant polymeric materials, including tough polystyrene and flame retardants, the presence of chlorinated polyethylene allows a reduction in the amount of flame retardants in the mixture. Chilled polyethylene also acts to some extent as a flame retardant and is likely to also synergize between the chlorinated and brominated compounds. However, in addition to the economic benefits, this partial replacement of the accumulated flame retardants with chlorinated polyethylene has a further positive impact in that the initial values of the mechanical properties of the materials as well as its resistance to aging are less deteriorated.

In terms of mechanical properties, the presence of chlorinated polyethylene manifests itself primarily in higher values of impact and notch toughness and heat resistance of the material.

The aging abrasion is substantially higher in the inventive polymer material. Here, the presence of chlorinated polyethylene has a positive effect, and the combination of phenolic-type antioxidants with substances referred to as hydrogen halide acceptors is essential.

201 731

These are the above-mentioned types of erganecin compounds or the above mentioned compounds of barium, cedemous, zinc or calcium, optionally in combination with epoxy compounds.

Particularly effective for combining stabilizers is in those cases where the polymer is protected from light exposure by the addition of suitable non-green or benztriezel-type light stabilizers or a compound of the class of sterically shielded cyclic amines or alternatively mixtures of said light stabilizers. Where, for various reasons, the polymer cannot be protected against the effects of light radiation by suitable pigmentation, or if the pigment or dye used does not have the necessary absorption in the short-luminous region of the light radiation, the use of these light stabilizers is essential.

A further improvement in the resistance to aging, in particular as regards the color change during aging, can be achieved if the use of a fenblic entioxidant is combined with the addition of stabilizers of phosphate type (phosphate acid esters).

The advantages of using the polymeric material of the invention are demonstrated by the following examples.

Example 1

8 polymer blends with reduced flammability were prepared, blend A being shown for comparison, blends B to H correspond to their polymeric material according to the invention.

The mixtures were prepared as follows.

Per 100 wt. 14.5 wt.% of polymer (either tough polystyrene alone, containing 6% polybutadiene, or a mixture of tough polystyrene with chlorinated polyethylene containing 36 wt.% bound chlorine) were added. parts of decabromodiphenyloxide and 6.0 wt. parts of antimony trioxide, which corresponded to a content of about 12 wt. decabromodiphenylexide and 5% antimony trioxide in the mixture. To this masterbatch, longer additives were added in the amounts shown in Table I. The additive polymer was homogenized in a Henschel quick mixer and then plasticized in a screw extruder. Test specimens were prepared from the granulate and used to determine the properties of interest. Notch and impact strength were determined according to ČSN 64 0612, thermal resistance according to Vicat according to ČSN 640 521. Flammability was evaluated according to text UL-94 and determination of oxygen number. ° dolnest versus aging was evaluated in a vetometer according to CSN 64 0772 and is expressed in the following table by the relative life index of material R, defined as the ratio of exposure time% needed to decrease the impact value to 70% of the original value for evaluated (X) and reference (A) ) sample r = * * 70% (X)

TlQ%

The yellowness index was evaluated according to ASTM D 1925-70 and the relative values shown in the table represent the change in the yellowness index of the material by 32 hours of irradiation with a 400 W mercury vapor lamp through a Fyrex filter (X) relative to the yellowness index of the reference sample (A). l.Ž.

(X)

Relative change in yellowness index = —----------—.....

l.Ž.

(AND)

Sample A, stabilized in a conventional manner (antioxidant and light stabilizer) and containing no chlorinated polyethylene, was selected as the reference sample.

201 731 of the results reported in the table, it is apparent that the polymer blends prepared according to the invention have initial mechanical properties, resistance to aging (both in terms of changes in mechanical properties and yellowing) or fire performance characteristics significantly better than the comparative sample. The combination of all components of the invention, ie chlorinated polyethylene, phenolic antioxidant, hydrogen halide acceptor, light stabilizer and phosphite stabilizer, greatly improves all important properties of the polymeric material. Of the properties not listed in Table I, the fire performance characteristics determined by the “Erpel” test are significantly affected. Thus, for materials containing chlorinated polyethylene, the infusibility of the heat emitter decreases up to 10 wt. and more chlorinated polyethylene, the material according to said method is already non-combustible. In addition to the difficult ignitability of the material, other fire safety-relevant characteristics will also be improved: a decrease in the amount of heat generated during combustion, a reduction in smoke formation and a decrease in the temperature during combustion.

Example 2

Using the procedure described in Example 1, a polymeric material was prepared having a composition consistent with Sample C except that the dosage of decebromodiphenyl oxide was reduced ns 9 ha. 8 parts by weight of polymer mixture (corresponds to a content of about 8% by weight in the mixture). Compared to Sample C, this sample improved its toughness by 20-30 as a result of a reduction in the content of the compound, the aging resistance improved compared to Sample 0 (R - 6.2), while the fire performance characteristics were better than the samples not containing chlorinated polyethylene (ie A). This example demonstrates that in the presence of chlorinated polyethylene, it is possible to reduce the amount of flame retardant in the polymer blend while maintaining satisfactory fire performance characteristics

201 731 Table 1

Sample identification AND (B) C D E P G H Polymer blend composition (wt%) Tough polystyrene 100 ALIGN! 76 76 76 76 76 76 88 chlorinated polyethylene 0 24 24 24 24 24 24 12 Additives (ha parts per 100 parts of polymer) 2,6-di-tert-butyl-4-ethyl-phenel - - - - 0.60 0.6 - - ektadecyl-3- (3, ^{<5-tertbutyl-4-hydroxy} «y- Phenyl prepienate e, 3 0.3 0.3 0.3 - - 0.3 0.3 dibutyltin oleate - 0.3 0.3 0.3 0.3 0.3 - 0.3 Ba-Cd salt of lauric acid - - - - - - 0.3 - Butyl ester of epexystearic acid - - - - - - 0.3 - tris (nenylphenyl) fesfit - - 0.25 0.25 0.6 0.6 0.25 0.25 distearylpentaeriythritel digosfit - 0.25 - - - - - - 2 (2 'hydroxy-5-astylphenyl) benzotriaz 0.6 0.6 0.6 0.6 - - 0.6 0.6 b β (2,2,6,6-tetraacetyl-4-piperidyl) sebacate - - 0.6 - 0.6 - - bis (4-ethoxy-2-hydroxybenzafenane) - - - 0.6 0.6 - - Table 1 (stunt) Sample identification AND (B) C D E F G H Properties Notched heuzevnatest (kJ / m) 9.2 12.2 12.7 H, 9 12.3 12.5 12.9 10.0 Shock Impact (kj / ra ^) 52.0 56.3 51.2 53.0 55.6 56.0 55.0 48.0 Vicat Thermal Edelnest (* C) 91 90 90 89 90 91 90 89 Test UL-94 vertical V-l V-0 V-0 V-0 V-0 V-0 V-0 V-0 Oxygen number 24.0 29.8 28.8 29.5 30.1 29.0 29.8 26.1 Relative lifetime (in veterinary) 1.0 9.1 8.3 12.2 5.8 8.9 8.5 7.8 Relative change in yellow index 1.00 0.45 0.47 0.37 0.66 0.49 0.46 0.59

SUBJECT OF THE INVENTION

Claims (2)

1. Tough Pelyaeric Material ee reduced flame retardancy and improved edalnest PS aging resistance, characterized in that ee consists of 50-85% play. heuževnetéhe polystyrene, 1-25% game. of polyethylene containing 25 - 45% ha. bound chlorine, 5 - 15% game. a flame retardant, preferably halogenated ergenic compound, of 3-6% ha. eynergic additives, with antiaenitéhe oxide, 0.1 - 1.5% ha. phenelic type entiexidant, 0.1 - 3.0 wt. stabilizer foefiteveh type, 0.1 - 3.0% ha. argenecin compounds and / or 0.1 - 3.0% ha. barium, cadeanate, zinc or calcium sele organic acids or mixtures thereof and 0.1 - 2.0% ha. the light stabilizer of the benzopheneal sky or the benztriazelone of the sky of the class of sterically shielded cyclic amines, or the light stabilizers. 2. The polymer material of claim 1, which also contains epoxy compounds in an amount of from 0.1 to 3.0% ha.