DE1026951B - Flame-proofing of translucent or clear transparent resins, condensates, polymers - Google Patents

Description

GERMAN

The invention relates to the use of flame-retardant making agents as an admixture to resins or plastics, such as condensates, polymers which it is important to maintain the transparency or at least good light transmission, the color stability and meltability matters.

Those in the translucent or clearly transparent, inherently inflammable basic masses, such as Resins, condensates, polymers, copolymers, agents to be incorporated according to the invention are a set Mixture of a highly chlorinated organic substance and the arsenic, antimony or bismuth salt a carboxylic acid or a phenol.

The poor or non-flammable effect of the agents is due to both components. If necessary, either a stabilizer can be added to the flame-retardant agents, or a stabilizer is worked into the plastic base materials beforehand or at the same time. the at normal use and in the manufacture and use of the flame retardant end products chlorinated organic substances have a stabilizing effect, but care must be taken to ensure that that at the ignition temperature, on the contrary, a decomposition of the chlorine products is desired. According to According to the invention, the flameproofing agents can also contain additional substances from the outset contain color-stabilizing effect of the end products, or you can incorporate such substances into the substances to be made flame-resistant yourself. Possibly In addition, substances with softening, smoothing and defoaming properties can be added to the flame-retardant end products or lubricating effect. Dyes can also be added will.

It is known per se to use organic metal salts, e.g. B. bismuth tartrate, chlorine-containing plastics on vinyl or add vinylidene base to stabilize it against decomposition during processing or storage. However, such an effect does not meet the purpose of the invention in which such Metal salts in combination with chlorinated salts which are relatively easily decomposable with elimination of hydrogen chloride Hydrocarbons or waxes which are easily flammable without this addition or added to clear transparent masses to prevent their flammability. Here it is in In contrast to the purpose of the well-known addition, there is a downright condition that the metal salts should decompose of the chlorine-containing constituents ■ - · at least at the ignition temperature for the base materials - do not prevent, since the flame-proofing effect is largely based on the fact that in the event of danger released hydrogen chloride in a fire

or clear transparent resins,

Condensates, polymers

Applicant:

Diamond Alkali Company,

Cleveland, Ohio (V. St. A.)

Representative: Dr.-Ing. F. Wuesthoff and Dipl.-Ing. G. pulse, Patent Attorneys, Munich 9, Schweigerstr. 2

Claimed priority:
V. St. v. America January 20, 1954

John E. Dereich, Painesville, Ohio (V. St. A.),
has been named as the inventor

will. It is therefore not only - as is known - added metal salts, but additives are used that also contain components that lead to the development of hydrogen chloride if there is a risk of ignition. Furthermore, it has already been proposed to make plastic, resin-like or polymeric substances flame-resistant, by z. B. in U.S. Patents 2,590,211 and 2,658,880 with effective for these purposes Agents made from highly chlorinated, aliphatic compounds with 50 to 85% chemically bound Chlorine and an inorganic metal compound, such as antimony trioxide, mixed. For many purposes it is in addition to the prevention of fire hazard, the simultaneous preservation of the transparency of the Flameproof masses of great, sometimes decisive importance, which is why the use such purely inorganic additives, which the clear transparency or the light transmission affect, prohibits.

United States patent 2664411 provides for masses, in which the transparency should be retained, to protect against inflammation in addition to chlorinated paraffins Add triphenylstibine. The high cost price for this hard-to-reach body, however, the practical evaluation of this proposal prevented while the inventively to be used

709 957/433

the metal salts in an economical manner for bulk or aromatic nature. Such acids can products are usable. ■ be monobasic monooxy acids, such as

The use of the agents according to the invention, glycolic, lactic and salicylic acid. as well offers the possibility of using plastic materials for various salts of polybasic monooxy acids, such as other purposes that were previously out of the question are those of citric, malic and tartronic acid, turn, in which they are used to the extent that they have been made flame retardant; in addition, salts are more polybasic must that they stop burning. The term polyoxyacids, e.g. B. mucic and tartaric acid, In this context, »do not continue to burn« means particularly suitable. Also the salts are polybasic that the substances in question, if one uses an acid such as oxalic, fumaric, malonic and adipic acid, Flame, e.g. ß. the flame of burning wood io can be used. Furthermore, the Od. Like., act on them and so long in contact with derivatives of various aromatic substances, such as the You can use gallic and oxybenzoic acid with them until they seem to burn themselves. Suitable Distance from the flame no longer than about 3 Se- are also the derivatives of oxyphenols, e.g. B. des announce (usually less than 1 second) catechol and pyrogallol. The Verunter too Flames continue to burn. Known 15 use of other acids as well as their various

lent plastics or synthetic resins such as derivatives such as amino, amido and halogen acids ignite, Polystyrene and polyester resins, very light and burn. is provided. Is it a polybasic one? after removal of the flame continues independently. An acid, the hydrogen can be one of the carboxyl

Resin or plastic mass, which can be identified in the same groups by a large number of substituents, Way a flame from burning wood act 20 for example by alkali and alkaline earth metals,

leaves, but expires almost immediately if you use an alkyl, alkylene, aryl, aralkyl, aralkylene, alkaryl and

Flameproofing agent according to the invention, other more saturated substances, such as Cvclohexen and Cyclo-

is absorbed. The flame retardant can be replaced in hexane. In the same way, the

the masses are used in the unpolymerized, partially polymeric ammonium and amine salts. Be it or, in the case of thermoplastics. 25 added that the various to replace the

be incorporated in the ready-polymerized state. Hydrogen in one of the carboxyl groups one

In this way, it can el> enso with a fully polymerized, thermally polybasic acid suitable substituent

curable material are connected, that you can sit on other parts of the organic matter

the latter in particle form with the flame retardant can.

united the means and then the whole thing with 30 With regard to the organic substituents of the bc-

binds with a binding agent and there are no inputs to the desired organic substance

Forms products. The flame-retardant restrictions, as these generally do not control

Ingredients according to the invention will have an expedient influence on the effectiveness of this proportion

wisely have by very intensive mixing with the resins of the flame retardants. Only in mixed. A rubber grinder can be used for mixing, or 35 cases in which the additives are

any other mixing device can be used. mimg temperature are so stable that the metallic

For the mixing together of the constituents of the additive or metal oxide portion, do not

Substitutes among themselves do not have any particular interaction with those from the chlorinated organic fraction

driving steps necessary; you can either use everyone for developed hydrochloric acid to be released, Difficulties arise with respect to each other or all of the plastic material 40 at the same time.

can be added as a base. It can be assumed that the metal-containing part Use according to the invention of the above-mentioned agents with that in the decomposition of the chlorinated ones mix from a chlorine product and an antimony, substance evolved hydrogen chloride together-arsenic- or bismuth salt of a carboxylic acid or one acts when the mass is exposed to high heat from phenol Can be made flame retardant, come 45 is set. This interaction must be considered real all inherently flammable against chlorine-containing by-chemical effects are to be considered between Mixtures of insensitive resins or plastics to the hydrogen chloride and the metal-containing leg Ask if it is translucent or partly through. It follows that the reaction appears are. time has a certain influence on the speed. The flame-proofing agent 50 to be used with which a burning material is extinguished, and consist aas a mixture of a chlorinated higher- that further, if a short extinction time is required Molecular hydrocarbon or wax with is said to be highly reactive with hydrogen chloride an antimony, arsenic or bismuth salt of a known substance can be used. The opposite is the case Carboxylic acid or a phenol. The chlorine compound use less reaksoll with hydrogen chloride at least 50%, preferably 50 to 80% chlorine 55 tionable substances to be preferred, if a longer one contain. Connections with at least 8 up to about trigger time comes into question. Tm general be-35 Carbon atoms have proven to be particularly suitable as a metal-containing substance of higher molenet proven. Particularly useful are the chlorinated bulk weights, necessarily the plastic material Paraffin waxes in which the paraffin molecule is more than to a greater extent, so that if the resinous one Has carbon atoms. A relatively large proportion was added to the resinous solid substance Bulky chlorinated wax should contain between 50, lower molecular weight substances and 80%. especially about 70% chlorine. are preferable.

It has been found that antimony, arsenic and substances that are particularly suitable are to be regarded as Bismuth compounds of a carboxylic acid or of one are soluble in the resinous mass, in particular Phenols are especially suitable for the intended purpose, since they form clear, colorless solutions, as in suitable. For practical purposes, it is preferred that no coloring effects occur. Where it The metal antimony, since it is readily available and depends on complete transparency, should be used Compounds have a particularly high flame retardant agent regardless of its solubility unfold making effectiveness. Particularly suitable are essentially the same refractive index the salts of organic oxyacids of aliphatic 70 have the same properties as the basic mass.

The metal derivatives of various organic substances are irrespective of the metal in theirs Flame-restraining effectiveness generally similar. So if in the following only If reference is made to antimony derivatives, in particular to antimonyl derivatives, the same apply here cited aspects in the same way for the other corresponding metal derivatives. It also applies what, for the sake of simplicity, about the derivatives of tartaric acid and its monosalts and esters, in particular it is said of the antimonyl derivatives of tartaric acid and potassium tartrate, also of the antimonyl derivatives other acids and compounds.

It has been found that the antimonyl derivatives of tartaric acid, especially the readily available potassium antimonyl tartrate (Emetic tartar), are particularly suitable as a metal-containing component of the agents according to the invention. The same are special suitable the ammonium antimonyl tartrate. the barium antimonyl tartrate and the ethylenediamine antimonyl tartrate as well as antimonyl catechol. When using these substances of relatively low Molecular weight will be the properties of the end product that has become flame resistant, in particular its light permeability is hardly affected at all.

The agents found are suitable for use in a very large number of areas, particularly also for production of translucent panels reinforced with fiberglass. Such plates are largely today in use and for a great many purposes they must be flame retardant. In the manufacture of such panels or panels, a suitable form is lined with a release agent and a prefabricated mat nus glass fibers inserted. The fibers of the glass mat are preferably pretreated in some way, so that they accept the resinous mass easily and uniformly or are wetted by it. the Pretreatment can be done by soaking the fibers with a dilute resin solution, e.g. B. a styrene-polyester solution, which is then polymerized on the fiber itself exist. Once the mat has been placed in the mold, so a polymer or a polymer-forming mixture, according to the invention a corresponding Part of a flame-proofing agent is added, poured over the fiberglass mat. the the other half of the form is slipped over, whereupon it is hardened by heat and pressure or, if so, If it is a thermoplastic material, it is allowed to cool. Is the polymer mixture whole or partially unpolymerized, as is the case, for example, in the case of panels made of a polyester resin a suitable polymerization catalyst is of course added.

Some of the above-mentioned highly chlorinated substances are known to have the property of becoming in use to decompose, which already at relatively low temperatures or with prolonged exposure the weather, especially the sunlight, can take place. This leads to the discoloration of the flame retardant End product and a decrease in its flame resistance. In such cases one adds to the Flameproofing agents or the plastic material a stabilizer for the chlorinated substances.

Premature decomposition of the chlorinated additive, which will reduce its effectiveness by developing Eliminates hydrogen chloride must be avoided, but the stabilizer must be chosen with care be that the chlorinated portion is not over-stabilized to the point where there is no decomposition if there is a risk of ignition, more occurs. In any case, the stabilizer may be at or near the Inflammation temperature no longer have a stabilizing effect.

Examples of known stabilizing substances are the high-melting derivatives of ethylene oxides; in the In general - as is known - compounds which contain an ethylene oxide bond can be used and also have a boiling point so high that at temperatures at which all of the material is mixed together and deformed, their vapor pressure does not appear. Particularly useful Substances from this group are the aroxyl-substituted propylene oxides, among which the phenoxypropylene oxide occupies a special position.

It is understood by those skilled in the art that the means according to the invention either before or the known plasticizers can be added during their incorporation into the plastic material. In addition, a small percentage of a lubricant can be added, which causes the material can be molded by injection without sticking too tightly to the molds, so that it can be removed more easily.

The amount in which the flame retardant mixture is added to the resinous substance can be within further limits fluctuate, but taking into account the influence on the properties of the product is to be taken. In certain cases, the additives can be up to about 60 to 63 percent by weight of the Represent the end product, however, it is more appropriate if the total amount of flame retardant Average is about 10 to 35, preferably 20 to 30 percent by weight of the mass.

The mixture can contain the two flame-retardant constituents in a wide variety of proportions contain. For certain purposes, the mixture can contain 2 to 6 parts of chlorinated organic matter per part Contain metal salt. In particular, especially in cases where the mass is 20 and 30% of its total weight of flame retardants are added, a mixture is preferably used which contains about 3 to 5 parts by weight of chlorinated organic material per part of metal salt. How out According to the examples, a mixture of 80% chlorine product and 20% metal salt is particularly suitable. Of the Stabilizer can be added to the chlorine product in proportions of 1 to 10%, preferably about 5% Added weight. The plasticizer can optionally be added to the flame-proofing additive and then exerts its effect in the entire end product of which it is in general should be less than 10 ° / o. Affected in this amount the plasticizer does not noticeably make the flame-retardant effect. The lubricant can also be incorporated into the additive and should amount to about 1 to 5% of the end product.

In the following examples, "polyester resins" are mentioned variously, with this Expression is meant in its broadest scope. Such substances are, for example, in the United States patents 233 639 and 2 445 553. Those described in the latter patent Polyester resins are formed from esters of polyhydric alcohols with polybasic carboxylic acids, e.g. by esterifying 1,2-propylene glycol with an acid such as sebacic or maleic acid.

If translucent or transparent copolymers are to be made flame-resistant, so can

Claims (1)

7 8 Polyester resins diluted with styrene and only mixed are only slightly changed. The product is fully polymerized while they are already seeming with the. flame-retardant substances and the other accessories, Mixtures are mixed. £> e ι s ρ ι e 1 4 To stabilize the flameproof end product, 5 The following mixture is in the usual with both the decomposition of the highly chlorinated rubber mill and grinding into a sheet of stand-off part shaped like that of the matrix prevented. First of all, the resinous cellulose is if stabilizers are added in a known manner, acetate butyrate is ground until it becomes plastic, whereupon the flame-proofing additive in those of the ultraviolet component, protect. For this io shares of about a third at intervals of Purpose can be added up to 5% of any known about 10 minutes. The finished mixture Light stabilizer can be used. Suitable for this is composed as follows: especially phenyl salicylate or other salt cellulose acetate butyrate .... 65 parts by weight cylate the α- and / Wmbelh eron, the methylumbelli- chlorinated paraffin wax feron, methylacetylumbelliferone; also the methyl 15 (70 0 / ru] \ ? S anthranilate or the substituted benzophenones sodium antimonyitarian stock "'. 10 ]', as well as other stabilizers are suitable. ^J The end product is absolutely resistant to Example 1 ^ as inflaming. It does not burn, it is charred An intimate mixture is prepared from ²⁰ only. Polyester resin 78 parts by weight Example 5 Chlorinated paraffin wax (70% chlorine) 10 ^ ^{s w} ' ^{ir (} ^ ^em mixture prepares Kalmantimonyl tartrate. . 10 "polyester resin 137.0 g Benzoyl Peroxide Tricresyl ²⁵ Chlorinated Paraffin Wax phosphate catalyst '.. 2 "(70% chlorine and styrene) 53.0 g Ammonium antimonyl tartrate 10.0 g The mixture is made over a phenyl salicylate (light stabilizer). 1.6 g Panel form spread glass fiber mat cast and benzoyl peroxide tricresyl phosphate at about 116 ° C to a fully polymerized product 30 catalyst 4.0 g hardened. The glass mat represents about 35 percent by weight of the finished product. The finished panel The mixture is applied to a panel according to Example 1 was tested for flame resistance with a flame, processed with 35% glass fiber content. The received it was found that the product extinguishes itself in a few seconds when ignited, whereby itself goes out. It is translucent. The physika- 35 the flame disappears in less than 2 seconds. The properties of the product correspond to this. those of a board made of untreated polyester resins. ß e 1 s ρ 1 e 1 A mixture formed according to Example 5, which at Example 2 Place of the ammonium salt barium antimonyl tartrate The following mixture is contained in the usual 40, but otherwise the ingredients are the same Grind the rubber mill and form a film from the weight ratio as in Example 5, shows shaped. The polyethylene content is initially essentially the same properties as those of the grind until it becomes plastic, whereupon the flame-resistant products from Example 5 are identical. The extinguishing one Mixing in proportions of about a third of the time is about 1 second, is added at intervals of about 15 minutes. 45 ". . , _ The finished mixture has the following composition: I _n the mixture according to Example 5, the am- Polyester resin 50 parts by weight of monium antimonyl tartrate through the ethylenediamine Chlorinated paraffin wax replaces antimonyl tartrate, whereby the weight ratio (70% chlorine) 25 “50 nits stay the same. The product is almost Potassium antimonyl tartrate .. 25 “completely transparent; its extinction time is very short, although this time is improved, The product is translucent and flame retardant. _{if you have a slightly larger} proportion flame-retardant mixture than when using Example 3 ^ application of Ammoniumantimonyltartrat. In the pre- A pasty mixture of the approximate coherent example it took about 3 seconds, composition: Polyester resin 73 parts by weight Patent claims: Chlorinated paraffin wax * Use of a chlorinated higher molecular weight (70% chlorine) 20 ^6o laren hydrocarbon or wax with a Potassium antimonyl tartrate .. 5 "content of at least 50% chlorine and one Benzoyl peroxide tricresyl antimony, arsenic or bismuth salt one phosphate catalyst .. 2 ,, carboxylic acid or phenol for flame retardancy of translucent or clear, is treated analogously to Example 1, so that sheets of 65 inflammable, against chlorine-containing admixtures the fully polymerized polymer, in sensitive resins, condensates, polymer which incorporated about 35 percent by weight of glass fiber or copolymers, are tet. In the test for flammability, the result of 2. embodiment according to claim 1, characterized that the product is characterized within 2 seconds of that as a salt of a carboxylic acid itself goes out; its physical properties 70 such an oxyacid is used. 9 10 3. Embodiment according to claim 1 and 2, documents considered: characterized in that the chlorine compound is used in an amount required for the Swiss patent specification no. 275 161, used amount by weight of metal salt in 261981; the ratio is 1: 1 to 10: 1. 5 U.S. Patent Nos. 2,664,411, 2,658,880. © 709 957/433 3. 58