Extruded polymer foam materials containing additives imparting refractory properties, based on bromated fatty acids

FIELD: chemistry.

SUBSTANCE: invention relates to a foamed refractory polymer material such as foamed polymers and copolymers of styrene which contain substances which impart refractory properties, based on bromated fatty acid, and a method for production thereof. The method involves production of a molten mixture of a combustible polymer, an additive which imparts refractory properties and a foaming agent. A molten mixture under pressure is brought to temperature of at least 200°C, after which it is extruded into a low pressure zone in which the mixture is foamed and cooled to form a foamed polymer with density of 16-480 kg/m3. The additive which imparts refractory properties used is at least one bromated fatty acid, an ester, an amide or an ester-amide of bromated fatty acid, a glyceride of one or more bromated fatty acids, a polymerised bromated fatty acid, or a mixture of any two or more substances from the above-mentioned in an amount which provides 0.1-30 pts.wt bromine per 100 parts of the combined weight of the combustible polymer, the additive which imparts refractory properties and the foaming agent.

EFFECT: foamed refractory polymer material made according to the invention exhibits excellent fire resistance.

13 cl, 3 tbl, 17 ex

 

This application has a priority based on Provisional Application for Patent of the United States 61/001579, filed November 2, 2007

The present invention relates to extruded polymeric foams such as foamed polymers and copolymers of styrene which contain substances, which impart flame-retardant properties, based on bronirovannoj fatty acids.

Additives, which impart flame-retardant properties (FR), usually added in the products of extruded polymer foams, which are used in construction and applications on the road (in applications in internal combustion engine). The presence of additives, which impart flame-retardant properties, allows the foam to pass through the standard fire test, which are required in various jurisdictions. In such proproduct as additives, which impart flame-retardant properties, use various brominated compounds with low molecular weight (<~1000 g/mol). Many of them, for example, hexabromocyclododecane, are subject to state regulation of production and social pressure, which can lead to restrictions on their use, and therefore stimulates the search for a replacement for them.

Alternative additive gives refractory properties for extruded polymer foams up is GNA to be able to allow the foam to pass through the standard fire test, when you enable it in the foam at acceptable low levels. As extruded foams processed at elevated temperatures, it is important that additive gives refractory properties, was thermally stable (thermally stable) when temperature conditions used in the extrusion process. For some foams, such as polystyrene and foams based on styrene copolymers, such temperatures are often 180°C or higher. Some problems arise if the additive gives refractory properties, decomposes during the extrusion process. These problems involve the loss additives, which impart flame-retardant properties, and, consequently, loss of refractory properties, and the formation of decomposition products (such as HBr), which are often corrosive and, therefore, potentially dangerous to people and harmful for working equipment. Additive gives refractory properties, should not cause a substantial loss of desirable physical properties in the polymer. Preferably, additive gives refractory properties, had low toxicity and was not vysokobyudzhetny.

Brominated vegetable oil have been described in U.S. patent No. 3359220, as additives, which impart flame-retardant properties for use in applications pen the material in the form of granules. As described in U.S. patent No. 3359220, brominated vegetable oil is added to the suspension polymerization process and thus introduce into the polymer particles, which are then foamed by contact with steam. Polymer particles are polystyrene, which copolymerization with Tung oil. Brominated vegetable oil is described in U.S. patent No. 3359220 as decaying in the temperature range of 140-180°C. the Process of obtaining a foam in the form of granules does not require high temperature processing, because the stage of polymerization and foaming is carried out at temperatures only up to about 115°C. This stage is carried out at temperatures significantly below the reported temperature decomposition of brominated vegetable oil, and thus there are problems associated with the decomposition of brominated vegetable oils when used in the applications of foams in the form of polystyrene granules.

The present invention relates to a method comprising receiving under pressure a mixture of (A) inflammable polymer, (B) increase the resistance number of at least one(th) bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, polymers the bathroom bronirovannoj fatty acids, or a mixture of any two or more substances of the above, and (C) foaming agents, and extruding the mixture into a zone of reduced pressure so that the mixture foams (expanding) and cooled with the formation of foamed polymer containing component (B). For the convenience of brominated fatty acids, esters, amides or ester-amides of brominated fatty acids, glycerides of one or more brominated fatty acids, and polymerized brominated fatty acids, and mixtures of two or more substances, sometimes referred to in this document as BFAB (based on brominated fatty acids)-additives, which impart flame-retardant properties.

In another aspect the invention relates to extruded vosplamenyaemostb polymeric foam having a density of from 1 to about 30 lb/ft3(16-480 kg/m3), extruded vosplamenyaemostb polymeric foam containing increasing resistance number bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, polymerized bronirovannoj fatty acids, or mixtures of any two or more substances of the above.

In another aspect, the invention relates to extruded foam is polistirolo or foam-based copolymer of styrene, having a density of from 1 to about 30 lb/ft3(16-480 kg/m3), to the extruded polystyrene foam or foam-based copolymer of styrene containing increasing resistance number bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, polymerized bronirovannoj fatty acids, or mixtures of any two or more substances of the above.

In some preferred embodiments of the invention the method is carried out in the presence of the promoter of the melt, for example, which is described in more detail below. The presence of a promoter melt in effective quantities, as it was discovered, quite significantly reduces the number BFAB-additives, which impart flame-retardant properties, which is necessary for passing standardized fire tests. Therefore, in another aspect, the invention relates to foamed vosplamenyaemostb the polymer containing increasing resistance number BFAB-additives, which impart flame-retardant properties, and the promoter of the fluidity of the melt. In this aspect, flammable polymer is preferably a polystyrene or copolymer of styrene.

Suddenly, extruded foam, from otoplenie in accordance with the invention, exhibits excellent flame retardant property, which is confirmed by various standard tests. Even if the mixture of polymer and additives on the basis of bronirovannoj fatty acids (BFAB) is subjected to temperatures much in excess of the decomposition temperature, which is shown in U.S. patent No. 3359220 for the brominated vegetable oil, I find that during the extrusion process, there is a small thermal decomposition BFAB-additive or not happening. Therefore, BFAB-additive gives refractory properties, is not consumed and does not decompose during the manufacturing process of the foam. BFAB-additives, which impart flame-retardant properties, are often surprisingly effective at small levels, especially when used in combination with the promoter of the fluidity of the melt. BFAB-additives, which impart flame-retardant properties, can be even twice as effective, based on the weight of bromine in the extruded polymer foam than hexaprotodon, especially when used in combination with the promoter of the fluidity of the melt. Many of BFAB-additives, which impart flame-retardant properties, are readily available materials which are inexpensive and have GRAS status (generally recognized as safe).

In some embodiments, the implementation of the extruded foam is made with the use of the water or carbon dioxide (or use and and other) as foaming agents. Suddenly, BFAB-additives, which impart flame-retardant properties, as it was discovered, was found to be stable under the conditions of extrusion, even in the presence of water and/or carbon dioxide, both of which are capable of participating in reactions of hydrolysis with esters and bronirovannymi aliphatic compounds. No significant loss of molecular mass BFAB-additives, which impart flame-retardant properties, is not observed in the case when in the extrusion process are as foaming agents, water and/or carbon dioxide.

Another advantage of the invention is that excellent flame-retardant properties can be achieved even when the extruded foam contains no tin-containing compound stabilizer.

In this invention brominated fatty acids, esters, amides, ester-amides or glycerides of brominated fatty acids, and polymerized brominated fatty acids, ("BFAB-additives, which impart flame-retardant properties), are suitable additives, which impart flame-retardant properties, for foamed organic polymer. BFAB-additive gives refractory properties, suitably contains at least about 15% by weight of bromine. BFAB-additive, precausionary properties, may contain at least 20%, at least 25%, at least 35% or at least 40% by weight of bromine. BFAB-additive gives refractory properties, may contain up to 65%up to 60% or up to 55% by weight of bromine. BFAB-additive gives refractory properties, may have srednecenovogo molecular weight of 500 or more, preferably 750 or more, or more preferably 1000 or more.

Suitable brominated fatty acids contain from 12 to 30, in particular from 12 to 20 carbon atoms. Suitable bronirovannaja fatty acid may contain from 1 to 8 bromine atoms, provided that it contains at least 15% by weight of bromine. Suitable bronirovannaja fatty acid may contain other inert substituents, such as hydroxyl groups. Hydroxyl groups may be present in the original fatty acid or sometimes can be introduced by hydrolysis pencentage bromine atom during the process of manufacture. Bronirovannaja fatty acid may contain other inert substituents.

As used in this document, I assume that the Deputy is "inert"if it contains one or more heteroaromatic groups that do not adversely impact on the function of substances as additives, which impart flame-retardant properties in the extruded polymer PE is material. This function can be adversely affected by, for example, if the group is the cause of the incompatibility of substance with an organic polymer, if the group is a cause of reactive substances undesirable manner with an organic polymer, if the group is the cause of the decomposition at too low a temperature, or if the group is the reason that the substance becomes ineffective as additives, which impart flame-retardant properties, in terms of standard fire tests. Examples of inert substituents include, for example, hydroxyl, simple, ether, ester, carboxylic acid, urethane, urea, biuret, isocyanurate, ketone, aldehyde, amino, amide, fluoride, chlorine and the like.

Suitable esters of brominated complex acids include esters which correspond to the reaction product bronirovannoj fatty acids, which are described above, with monohydroxy alcohol or a compound having many hydroxyl groups (except glycerol). Similarly, suitable brominated amides of fatty acids include amides, which correspond to the reaction product bronirovannoj fatty acid with the compound having one or more primary or secondary amino groups. Suitable ester-amides of brominated fatty acids include esters of s is s, which correspond to the reaction product bronirovannoj fatty acids with aminosterol having at least one amino group and at least one hydroxyl group. In this context, the term "correspond" to the product of the reaction means that the structure of ester, amide or of ester-amide is such that can be obtained through the reaction bronirovannoj fatty acids with alcohol, amine or linesperson, depending on the specific case, although in practice to obtain this substance can be used and another method of synthesis. Ester, amide or ester-amide bronirovannoj fatty acids may contain one, two, three, four or more fatty acid chains, at least one of which is bronirovannoj. Ester, amide or ester-amide will contain at least 15% by weight of bromine.

Some suitable esters of brominated complex acids include esters of brominated complex acids represented by the structure I:

.

In structure I, R represents an unsubstituted or inertly substituted hydrocarbonous group, and each R1independently represents bronirovannui linear aliphatic group containing from 11 to 23 carbon atoms. R1may contain about which 1 to 8 or more bromine atoms. In structure I, each OR2represents independently a hydroxyl group or unsubstituted or inertly substituted ether or ester group, which does not contain bromine, in each case which is attached to the adjacent group R through an oxygen atom. In the case when the group-OR2is an ester, it can be a residue of fatty acid groups having from 12 to 24 carbon atoms. In the structure I, as well as at least one, and b is zero or a positive number, and/or b may represent a large number in the case where an ester is polymeric in nature. a and b are those in which the ester of the fatty acid contains at least 15% by weight of bromine, and preferably has a value from 1 to 4, and b preferably has a value from 0 to 3.

Some suitable amides of brominated fatty acids include brominated amides of fatty acids represented by the structure II:

.

In structure II, R, R1, a and b are the same as described for structure I. Each R3independently represents hydrogen, unsubstituted or inertly substituted alkyl, or unsubstituted or inertly substituted aryl. In structure II, each-NR3R4is a group that does not contain the rum. Each group-NR3R4independently represents (I) a primary amino group (in this case, R3and R4both are hydrogens), (II) a secondary amino group (and in this case, R3is hydrogen, and R4represents an unsubstituted or inertly substituted alkyl or unsubstituted or inertly substituted aryl), (III) tertiary amino group (and in this case, as R3and R4are unsubstituted or inertly substituted alkyl or unsubstituted or inertly substituted aryl), or (IV) unsubstituted or inertly substituted amide group (in this case, R3represents hydrogen, unsubstituted or inertly substituted alkyl or unsubstituted or inertly substituted aryl, and R4represents -(O)CR6where R6is unsubstituted or inertly substituted alkyl, or unsubstituted or inertly substituted aryl). The group R4can represent the residue (after removal of the group-OH of the carboxyl group of fatty acids having from 12 to 24 carbon atoms. In structure II, as well as at least one, and b is zero or a positive number. a and b are such in which the amide of the fatty acid contains at least 15% by weight of bromine, and preferably has a value from 1 to 4, b preferably has a value from 0 to 3.

Some suitable ester-amides of brominated fatty acids include esters-brominated amides of fatty acids, represented by structure III:

,

where R, R1, R3a and b are the same as defined above with respect to structures I and II, and each Y represents a group-OR2or the group-NR3R4where the group OR2and the group-NR3R4are the same as defined above with respect to structures I and II, respectively. Each and preferably has a value from 1 to 4, and b preferably has a value from 0 to 3.

Glycerides of brominated fatty acids are of particular interest due to their relatively high molecular masses (especially in the case when the glycerides is a di - or triglyceride) and, as these substances can be easily obtained from some cheap vegetable oils and animal fats. Glycerides can contain one, two or three brominated fatty acid group. If the glycerides contain only one or two brominated fatty acid group, it may consequently contain one or two free hydroxyl (or glycerol portion of the molecule), and/or may be substituted by one or two dibromononane fatty acid groups. In the case where the glycerides contain only one or two brominated fatty acid group, there can be different positional isomers. Any of these positional isomers are the two which is appropriate. Glycerine compounds containing one bronirovannui fatty acid group can exist in the form of two positional isomers, which are represented by structures II:

and,

where R1described above, and R5represents hydrogen or the residue dibromononane fatty acid group. Just glyceride compounds containing two brominated fatty acid group may be in the form of two positional isomers, which are represented by the structures V:

and,

where R1and R5are the same as previously described. Glycerine compounds containing three brominated fatty acid group may be represented by the structure VI:

,

where R1again, is the same as described above.

A mixture of glycerides corresponding to the structures IV and V, IV and VI V and VI, and IV, V and VI, are all suitable in this invention.

Can also be used polymerized brominated fatty acids. The average degree of polymerization of up to 1.1 to 50 or more, where the average degree of polymerization of about 1.5 to 5 is usually preferred. Such substances may be obtained, for example, (1) a hydroxyl-containing polymerization is, unsaturated fatty acids, with subsequent bromirovanii, (2) bromirovanii hydroxyl-containing fatty acids, with subsequent polymerization or (3) the introduction of hydroxyl groups in bronirovannui fatty acid, with subsequent polymerization. Methods of polymerization of hydroxyl-containing fatty acids are described, for example, in GB 1469531 and GB 1373660. Bronirovannaja fatty acid can also be polymerized by reaction with chain extension or other agent of combination reaction, for administration, for example, acetylenic, urethane or similar connecting links between bronirovannymi fatty acid molecules. As before, this type of polymerization reaction can be carried out to synthesized or after synthesized.

Additive gives refractory properties that deserves special attention in this invention is a brominated vegetable oil or octabromodiphenyl animal fat. Such substances usually contain a high proportion of triglycerides, and often contain, in addition to them, some amount of free fatty acids, monoglycerides, diglycerides or any mixture of two or more substances. All fatty acid groups can contain one or more bromine atoms, but usually some part of the fatty acid groups is dibromononane. Brominated vegetable oil or bromer the bath animal fat preferably contains from 25 to 65% by weight of bromine. Preferred brominated oils include, for example, brominated soybean oil, brominated safflower oil, brominated cottonseed oil, brominated linseed oil, brominated soybean oil, brominated olive oil, brominated sunflower oil, brominated canola oil, brominated rapeseed oil, brominated corn oil, brominated castor oil, brominated palm oil, brominated hemp oil, or a combination of any two or more oils. More preferably, the brominated oil is a brominated soybean oil, brominated sunflower oil, brominated canola oil, brominated linseed oil, brominated corn oil, brominated rapeseed oil, or a combination of any two or more oils. Vegetable oil can be obtained from the genetically modified organism, such as genetically modified soybean, genetically modified sunflower seed or genetically modified canola. Vegetable oil or animal fat can contain CIS - and/or TRANS carbon-carbon double bond. Any type double bonds, or both types of double bonds can be bromirovanii. Can be used vegetable oils or animal fats that have been processed with PR the rotation of CIS-double bonds in the TRANS-double bond, as well as can be used fatty acids, esters, amides, ester-amides and polymers of fatty acids that have been processed in this way (or derived from vegetable oil or animal fat, thus processed). Methods of performing this transformation is described, for example, in the publication: Snyder et al., J. Am. Oil. Chem. Soc. 1982, 59 (11), 469-470.

Suddenly, BFAB-additives, which impart flame-retardant properties typically have thermal stability (thermal stability), which is determined by analyzing the temperature of 5%weight loss. The temperature of 5%weight loss measured by thermogravimetric method of analysis as follows: ~10 milligrams BFAB-additives, which impart flame-retardant properties, analyze with the use of Instruments for thermal analysis model Hi-Res TGA 2950 or equivalent device, with a stream of gaseous nitrogen 60 milliliters per minute (ml/min) with a heating rate of 10°C/min in the range from room temperature (nominally 25°C.) to 600°C. the mass Loss of the sample track during the stage of heating, and the temperature at which the sample has a weight loss of 5% of its the initial mass is taken as the temperature of 5%weight loss (5%-WLT). This method provides the temperature at which the sample has undergone a cumulative weight loss of 5 wt. %based on the initial sample mass. BFAB-additive, PR is giving refractory properties, preferably shows a 5%WLT equal to at least the temperature at which the flammable polymer is processed in the melt, or to mix it with BFAB-additive, giving refractory properties, or for processing of the mixture in the product, such as foam, extruded item (product), formed part (the product), or the like. the 5%WLT for BFAB-additives, which impart flame-retardant properties, is often above 200°C, preferably above 220°C. and more preferably above 240°C. a 5%WLT for the brominated sunflower oil is approximately 273°C (depending in some way on the degree of the synthesized), and the same for hexabromobiphenyl stearic acid is about 246°C.

Brominated glycerides of fatty acids, such as brominated vegetable oils and animal fats, can be obtained directly bromirovanii vegetable oil or animal fat, which contains at least some component of the unsaturated fatty acids. This is easy to do in a solvent with a source of elemental bromine as brainwashes agent. The solvent is one that does not react with the fatty acid and which does not participate in free-radical reactions with a source of bromine or bromine. Suitable solvents include, the example carbon tetrachloride, methylene chloride and n-heptane. Suitable conditions the synthesized well-known and described, for example, in the publication: McCutcheon, Org. Synth. Vol. 3, E.C. Horning, Ed., John Wiley and Sons, Inc. London 1955, pp. 526-528. Brominated fatty acids can be obtained by hydrolysis of the brominated vegetable oil or animal fat or bromirovanii the corresponding fatty acids. Other esters, amides and ester-amides of fatty acids can be prepared by obtaining a complex ester or amide by reaction of the alcohol (or polysperma), primary or secondary amino compounds or amerosport with the corresponding fatty acid, with the corresponding vegetable oil or relevant animal fat, with subsequent bromirovanii. Instead, bromination can be performed on the original fatty acid, a source of vegetable oil source or animal fat.

All unsaturated centers or some part of them may be bromirovanii. If the original oil or the original fat contains a component of a saturated fatty acid, commercially available brominated product will contain the appropriate component from bromirovannyih fatty acids. Some brominated vegetable oils are commercially available. Such commercially available brominated vegetable oil can be used in this image is hetenyi.

Brominated fatty acids can be obtained by conducting hydrolysis of the brominated vegetable oil or animal fat, or by synthesized fatty acids. Esters, amides and ester-amides can be prepared in a similar manner, or by conversion of the brominated vegetable oil or animal fat ester, amide or ester-amide (reaction with alcohol, amine or linesperson, respectively) or by the synthesized complex ester, amide or of ester-amide. Acids, esters, amides and amide-esters can be bromirovanii similar to the usual way can be bromirovanii vegetable oils or animal fats.

BFAB-additive gives refractory properties, is suitable as additives, which impart flame-retardant properties, in the manufacture of extruded polymer foam of inflammable polymer. "Flammable" means simply that the polymer is capable of burning. Flammable polymers of interest include polyolefins, such as polyethylene (including copolymers of ethylene such as ethylene-α-olefin copolymers, polypropylene and the like; polycarbonates and mixtures of polycarbonates, for example a mixture of polycarbonate with a complex polyester; polyamides; polyesters; epoxy the malls; polyurethanes; vinyl aromatic polymers (including vinyl aromatic homopolymers, vinyl aromatic copolymers, or mixtures of one or more vinyl aromatic homopolymers and/or vinyl aromatic copolymers), as well as other flammable polymers which can be dissolved or dispersed BFAB-additive gives refractory properties. "The vinyl aromatic polymer is an aromatic polymer compound having a curable unsaturated in the ethylene type group associated directly with the carbon atom of the aromatic ring. Vinyl aromatic monomers include unsubstituted substances such as styrene, divinylbenzene and vinylnaphthalene, as well as compounds that are substituted in on unsaturated ethylene type group (such as, for example, alpha methylsterol), and/or are substituted in the ring. Substituted in the ring vinyl aromatic monomers include substituted in the ring vinyl aromatic monomers having a halogen, alkoxygroup, the nitro-group or unsubstituted or substituted alkyl group, directly attributable to the carbon atom of the aromatic ring. Examples of such substituted in the ring vinyl aromatic monomers include 2 - or 4-Postira, 2 - or 4-chloresterol, 2 - or 4-methox is styrene, 2 - or 4-nitrostyryl, 2 - or 4-methylsterol and 2,4-dimethylstyrene. Preferred vinyl aromatic monomers are styrene, alpha-methylsterol, 4-methylsterol and mixtures thereof. Foamed polymers of any of these types are of interest.

Flammable polymer noteworthy is a polymer or copolymer of a vinyl aromatic monomer such as styrene polymer, or a copolymer of styrene, such as styrene and acrylic acid, a copolymer of styrene and Acrylonitrile (SAN), or a copolymer of styrene, Acrylonitrile and butadiene (ABS plastic). Polystyrene, copolymer of styrene and acrylic acid and a copolymer of styrene and Acrylonitrile are particularly preferred. Other flammable polymer noteworthy is a statistical, block - or graft-copolymer of butadiene and at least one vinyl aromatic monomer. Additional another flammable polymer noteworthy is a Polyphenylene oxyde.

Foamed polymer foam of the invention is made extrusion method. In the extrusion method, the molten mixture containing flammable(re) polymer(s), BFAB-additive imparting flame-retardant properties, foaming(e) agent(s) and optionally other substances, prepared under pressure is observed sufficient for holding the molten mixture from foaming. BFAB-additive gives refractory properties, can be introduced into the molten mixture by pre-mixing it with the polymer(s) to the melting temperature of the polymer(s), with separate production of concentrated "masterbatches" BFAB-additives, which impart flame-retardant properties, and parts of polymer(s), and mixing the "masterbatches" with the rest of the polymer(s) before or after their melting, or by introducing BFAB-additives, which impart flame-retardant properties, in the form of liquid or molten substance in the molten polymer. In this way, the molten mixture containing flammable polymer and BFAB-additive imparting flame-retardant properties, is usually brought to a temperature of at least 180°C., often at least 190°C. or at least 200°C. before subjecting the molten mixture to extrusion. Usually, this corresponds to the point in the extrusion process, when the flammable polymer is mixed with other substances, such as a foaming agent and/or BFAB-additive gives refractory properties. Usually (but not necessarily) the molten mixture is subsequently cooled slightly to the right temperature extrusion and then it is passed through an extruder die into a zone of lower pressure, so when mixture while the military is cooled and foams with the formation of the cellular polymer foam. Foamed polymer may be open pores, closed pores, or may contain both open and closed pores. The preferred extruded foamed polymer contains at least 70% closed pores. Foamed polymer may be a sheet material having a thickness of not more than ¼ inch (6 mm), or may be a material in the form of strips, having a thickness from ¼ inch to 12 inches (0.6 to 30 cm), preferably from 0.5 to 8 inches (1.2 to 20 cm). The preferred extruded foamed polymer is a polymer or copolymer of styrene, most preferably polystyrene, copolymer of styrene and acrylic acid, a copolymer of styrene and Acrylonitrile or a mixture of two or more substances.

The blowing agent used to deliver gas, which forms pores and spanaway molten mixture after it passes through the extrusion head. The blowing agent may be physical (endothermic) or chemical (exothermic) type, or a combination of both types. Physical blowing agents include carbon dioxide, nitrogen, air, water, argon, C2-C8 hydrocarbons, such as the various cyclic and acyclic isomers of butane and pentane, alcohols, such as ethanol, and various ethers, esters, ketones, hydro is troperty, chlorofluorocarbons, hydrochlorofluorocarbons, and the like. Chemical foaming agents include the so-called foaming agents "azo type, some hydrazides, seven-carbazide, and nitroso compounds, sodium bicarbonate, sodium carbonate, ammonium bicarbonate and ammonium carbonate, and mixtures of one or more of these substances with citric acid. Another suitable type foaming agent is encapsulated within a polymeric shell.

The amount of foaming agent used is sufficient to give the desired density of the foam. Extruded polymer foam is suitably has a density "foam" from about 1 to about 30 pounds per cubic foot (pcf) (16-480 kg/m3), in particular from about 1.2 to about 10 pcf (19,2-160 kg/m3and most preferably, from about 1.2 to about 4 pcf (19,2-64 kg/m3).

Other substances may be present during the extrusion process and in the resulting extruded polymer foam. They include promoters melt, other additives, which impart flame-retardant properties, including hexabromocyclododecane, other halogenated additives, which impart flame-retardant properties, and/or not halogenated additives, when the surrounding refractory properties, the synergistic additives, which impart flame-retardant properties, the attenuation of infrared radiation, corrosion inhibitors, colorants, stabilizers, nucleating agents, preservatives, biocides, antioxidants, fillers, reinforcing agents and the like. These and other additives can be used, if desirable or necessary for a particular product from extruded foam or for a specific process. Preferably, tin-containing compounds was largely absent in the extrusion process and in the resulting extruded foam. Unexpectedly, in the absence of these tin-containing compounds can be obtained excellent performance refractory properties and thermal stability.

The promoters of the melt are substances in the combustion conditions help to reduce the molecular weight of the organic polymer and, thus, allow him to "escape" from the front of propagation of combustion or other sources of heat. Also I believe that the promoters melt promote the release of HBr from BFAB-additives, which impart flame-retardant properties, under conditions of high temperature and thereby increase the efficiency BFAB-additives, which impart flame-retardant properties. Examples of promoters melt flow include 2,3-dimethyl-2,3-given Votan, 2,2'-dimethyl-2,2'-isobutane; bis(alpha-phenylethyl)sulfon; 1,1'-diphenylmethylene; 2,2'-dichloro-2,2'-isobutane, 2,2'-dibromo-2,2'-isobutane, 2,2'-dimethyl-2,2'-isobutan-3,3',4,4'-tetracarbonyl acid, 1,1'-diphenylstilbene, 2,5-bis(tribromophenyl)-1,3,4-thiadiazole, 2-(bromophenyl-5-tribromophenyl)-1,3,4-thiadiazole and poly-1,4-diisopropylbenzene. The presence of from 0.05 to 0.5 parts by weight of promoter melt on 100 parts by weight of inflammable polymer additionally improves the characteristics of the refractory properties at a given level of bromine, or allows equivalent to improve the characteristics of the refractory properties that must be achieved at a lower bromine content, if not attended the promoter melt.

Other synergists additives, which impart flame-retardant properties, can be an inorganic or organic substances. Inorganic synergists additives, which impart flame-retardant properties include metal oxides (e.g. iron oxide, tin oxide, zinc oxide, aluminum trioxide, aluminum oxide, antimony trioxide and antimony pentoxide, bismuth oxide, molybdenum trioxide and tungsten trioxide), metal hydroxides (e.g., aluminum trihydrate, magnesium hydroxide, zinc borate, antimony silicates, stannate zinc, hydroxystannate zinc, ferrocene, and mixtures thereof. Organic synergistic additives,which impart flame-retardant properties, include halogenated paraffin, phosphorus compounds, and mixtures thereof. The synergistic additives, which impart flame-retardant properties, can be applied in amounts of from 0 to about 6 parts by weight per 100 parts by weight of the polymer.

BFAB-additive gives refractory properties, is present in the extruded polymeric foam in number, increase the resistance, which is a quantity sufficient to improve the performance of polymeric foam in one or more standard tests for fire resistance in comparison with characteristics similar extruded foam, which does not contain additives, which impart flame-retardant properties. The number BFAB-additives, which impart flame-retardant properties, conventionally expressed through the content of bromine in the polymer foam. Usually BFAB-additive of the invention, which impart flame-retardant properties, is present in sufficient quantity to provide the polymer composition with at least a 0.1 part by weight of bromine per 100 parts combined weight inflammable polymer and BFAB-additives, which impart flame-retardant properties. Enough BFAB-additives, which impart flame-retardant properties, can be used to provide the polymer composition with at least a 0.5 part by weight of bromine, with at least 0.8 hours is followed by weight bromine, or, at least, and 1.0 part by weight of bromine, based on the same. Enough BFAB-additives, which impart flame-retardant properties, can be used to provide polymeric compositions with up to 30 parts by weight of bromine, with up to 20 parts by weight of bromine, with up to 10 parts by weight of bromine, with up to 5 parts by weight of bromine or with up to 3 parts by weight of bromine, based on the same.

Any one or more of several tests can be used to confirm the improved performance of refractory properties. Appropriate standardized tests include measuring the limiting oxygen index (LOI), in accordance with ASTM D2863; and various tests with the time dimension of the residual combustion (flame extinction) or testing with measurement of the rate of flame propagation, such as test, known as FP-7 (described additionally below), and tested according to DIN 4102 part 1, NF-P 92/501/4/5, SIA 183 or EN ISO 11925-2, which are used respectively in Germany, France, Switzerland and Europe.

Improved install method LOI if the limiting oxygen index extruded polymer foam is increased by at least 0.5 units, preferably at least 1.0 unit and more preferably, at least 2 is denizi, compared with other similar foam that does not contain additives, which impart flame-retardant properties. Characteristics of refractory properties in the test with measurement of LOI may be increased by up to 8 units or more. Extruded foam-based polymer or copolymer of styrene containing BFAB-additive of the invention, which impart flame-retardant properties, can show LOI of at least 21%, preferably at least 22% and more preferably at least 24%. It was found that BFAB-additive gives refractory properties, can give very high values of LOI extruded polymer foams, especially the extruded foams based on polystyrene or copolymers of styrene, even when using relatively small quantities. In many cases LOI extruded polystyrene foam is between 27% and up to 33% in the case when BFAB-additive gives refractory properties, is present in such quantity, in which the bromine content in the foamed polymer is from 0.5 to 2.5 parts by weight per 100 parts combined weight inflammable polymer and BFAB-additives, which impart flame-retardant properties.

Another fire test is a measurement of the time residual flame time of extinction of the flame), f is e as FP-7, which is defined in accordance with the method described in the publication: A.R. Ingram J. Appl. Poly. Sci. 1964, 8, 2485-2495. This test measures the time required for extinction of the flame, when the polymer sample is exposed to ignition of the flame in the special conditions, and then the ignition source is removed. To improve the performance in this test specifies a shorter time required for extinction of the flame. The time required for extinction of the flame in the conditions of this test when extruded polymeric foam contains BFAB-additive imparting flame-retardant properties, preferably reduced by at least one second, more preferably, for at least 3 seconds and even more preferably for at least 5 seconds, compared with when extruded polymeric foam contains no additives, which impart flame-retardant properties. The time to extinction of the flame in the test FP-7 is preferably less than 15 seconds, preferably less than 10 seconds and more preferably less than 5 seconds.

The improvement shown in other tests measure the duration of the extinction of the flame, or by measuring the propagation velocity of the flame, such as tested according to DIN 4102 part 1, NF-P 92/501/4/5, SIA 183 and EN ISO 11925-2, through assessment of the key "passing" the tests, or, alternatively, to decrease the flame height, time of extinction of the flame and/or education burnable inclusions that are specified in the ways of carrying out individual tests, in comparison with a similar foam that does not contain additives, which impart flame-retardant properties.

It was found that in many cases BFAB-additive gives refractory properties, provides a significantly greater improvement of the characteristics of the refractory properties in one or more of the above tests, when the bromine content in the extruded foam than it does even hexabromocyclododecane, which is a substance that meets the requirements of industrial standards for extruded polystyrene foam. Often, the content of bromine in the polymer can be reduced by up to 50% without loss in performance when hexabromocyclododecane replace BFAB-additive imparting flame-retardant properties, especially in the case when there is also the promoter of the melt flow.

In addition to a surprisingly effective action BFAB-additives, which impart flame-retardant properties, in providing refractory properties of the extruded foam, BFAB-additive gives refractory properties, manifests itself amazing stabiles the ü during the extrusion process. As BFAB-additive gives refractory properties, it is not bromine or HBr to any significant extent at temperatures of extrusion, equal to at least 180°With at least 190°C., at least 200°C, at least 220°C or even 240°C or higher, the risk of damage to people when their exposure to the impact of these decomposition products is minimal. Particularly unexpected is the fact that BFAB-additive gives refractory properties, hydrolyses very little or not hydrolyzed during the extrusion process, even in the case when the foaming agent is water or carbon dioxide. Equipment damage is also reduced, as these corrosive by-products are produced in a minimum amount, or not produced during the extrusion process. This allows the manufacture of technological equipment using relatively inexpensive constructions materials such as carbon steel, not a special, highly corrosion-resistant steel grades. The inclusion of a corrosion inhibitor in the molten mixture, if desired additional protection from possible corrosion of the equipment, of course, is within the scope of the invention.

In some embodiments of the invention, the extruded foam content is t one or more attenuators infrared radiation. Attenuation of infrared radiation are substances that block the passage of infrared radiation through the foam, and thus reduce the heat transfer through the foam. The action of these substances is usually manifested through lower thermal conductivity compared to other similar foam, which is not present attenuator infrared radiation. Attenuators infrared radiation often represent certain solids, such as aluminum oxide, titanium dioxide or, preferably, carbon black or graphite, which is dispersed throughout the matrix polymer. The particle size of such materials usually range from 10 nm (nanometer) to 100 microns. Attenuators infrared radiation is often used in quantities of from about 0.5 to about 8 parts, preferably from 2 to 5 parts by weight per 100 parts by weight of polymer in the extruded foam.

The use of attenuators IR radiation in the traditional foams, which was associated with a decrease in pore size increases the density of the foam and increases the proportion of open pores. Such effects are usually undesirable, especially in the manufacture of foams with a large area of the cross section, since they increase the cost and reduce the quality of the surface layer. Suddenly it was about naruhina, such effects are reduced or even eliminated in the case when there is BFAB-additive gives refractory properties in the extruded foam.

The following examples are provided to illustrate the invention and not to limit its scope. All proportions and percentages are given by weight, unless otherwise indicated.

The samples of Examples 1-7 and Comparative Samples C1 and C2

Samples of foamed polystyrene of Examples 1-7 and Comparative Samples C1 and C2 are made using plant including, in series connection, an extruder with a single screw with a diameter of 2 inches (initial temperature (temperature immediately after the start of the extruder) in the 1st zone of the extruder - 125°C, in the 2nd area of 175°C. in the third zone - 200°C), gear pump, mounted on 200°C, in a separate mixer, set at 200°C. for all Samples, except for Samples of Example 4 and Comparative Sample C2, for which the zone 3 of the extruder, gear pump and faucet foaming agent, all set at 220°C), two flat plate cooler and mixer with fine adjustment set at 160°C, 135°C and 120-123°C, respectively, the adapter, and an adjustable slit extrusion head. Polystyrene is mixed in the dry state with technological additive for improving the extrusion, with a stabilizer, with prophetic is STV, regulating the pore size, with a coloring substance, and with the promoter melt flow (if any), and fed into the extruder at a total feed rate of polystyrene 60 kg/hour. Brominated sunflower oil (BSO) serves in the process in the form of pure (pure) liquid, that is, before the introduction't spend no mixing or dilution. BSO is a commercially available brominated sunflower oil, which contains approximately 36% by weight of bromine. It is a mixture mostly of triglycerides, with some mono-, diglycerides, as well as some free fatty acids, where all have different degrees of substitution by bromine. BSO is stored in a storage bin with maintaining the temperature at 50°C by external electric heating. The bunker is placed at two meters above the process line receiving the foam so that the BSO is served on the side of the piston pump low pressure created when the hydrostatic pressure. Side of the high-pressure pump feeds the mixer foaming agent on the production line of the receipt of the foam through a separate inlet, which is used for foaming agents. The temperature and pressure in the mixer for the foaming agent, which is injected BSO, respectively pillar is t 200°C (unless otherwise noted above) and approximately 150 bar (15 MPa). Feed rate BSO controlled by the mass loss over time in the collection hopper. Foaming agent in the form of a mixture consisting of 4 parts of carbon dioxide and 0.8 parts of isobutane per 100 parts of polystyrene, is injected into the melt polymer in the mixer with getting capable of foaming gel. Capable of foaming gel is cooled and ekstragiruyut through slit extrusion head into a zone of lower pressure to obtain the structure of the foam. The pressure in the extrusion head is approximately 80-100 bar (9-10 MPa); the pressure drop between the entrance to the mixer and the entrance of the extrusion head of 50-80 bar (5-8 MPa). The foam is formed between the two forming plates with getting forms in the form of rectangular strips with a thickness of approximately 25 mm and a width of approximately 140 mm, the residence Time on the production line of the receipt of the foam is approximately 40 minutes. For each composition collected approximately 6 meters of foam for testing properties.

Testing of the physical properties and fire properties hold for each foam, where the results are presented in Table 1.

The data presented in Table 1 show that brominated sunflower oil is an effective additive, which gives about neuborne properties. As shown by Examples 1-7, brominated sunflower oil (in some cases in combination with a small amount of promoter melt), provides an equivalent fire-resistant properties, which are measured by the above tests, even with much lower concentrations of bromine (Examples 1-4), in comparison with hexabromocyclododecane. Brominated sunflower oil does not have a significant impact on the processing of foam and has a positive effect on pore size, thermal conductivity and density of the foam.

The samples of Examples 8-10 and Comparative Sample C3

Prepare a mixture of 2% by mass converted into a powder of the stabilizer on the basis of ORGANOTIN carboxylate and 98% of exapostilarion acid and loaded into the device, the feed powder in a twin screw extruder. Polystyrene resin is melted in the extruder combined with a mixture of stabilizer/exapostilaria acid and ekstragiruyut obtaining strands. The strand is cooled in a water bath and cut into pellets "masterbatches" (masterbatch pellets) with a length of approximately 5 mm

Expandable polystyrene is produced at the facility, including, in series connection, a 25 mm single screw extruder with three heating zones, with a mix section proobraz is his agent, with section cooler and with the 1.5 mm adjustable slit extrusion head. Three zone heating operate at set temperatures of 115°C, 150°C and 180°C, and the mixing zone operates at a set temperature of 200°C. Pellets "masterbatches" is mixed in the dry state with additional granules of polystyrene and from 0.05 mass. percent, based on the weight of the mixture in the dry state, technological additives. The ratio of pellets "masterbatches" and additional granules of polystyrene, is one in which the resulting foam contains 2.5 or 5.0 masses. % exapostilarion acid. The dry mixture was fed into the extruder with a speed of 2.3 kilograms per hour. In one case (case 10), during the extrusion process also added 0.5 part of promoter melt on 100 parts by weight of polystyrene.

Carbon dioxide serves in section mixing a blowing agent into the extruder using a syringe pump RUSKA (Chandler Engineering Co.). 4.5 parts by weight of carbon dioxide serves to 100 parts by mass of the mixture in the dry state. The pressure in the mixing section is supported above 1500 pounds per square inch (psi) (10.4 MPa) to provide a uniformly mixed polymer gel. A polymer gel is cooled to 120°C-130°C and ekstragiruyut through the extrusion head. The diameter of the orifice of the extrusion head reg is leraut to maintain the pressure in the extrusion head, at least 1000 pounds per square inch (psi) (6,9 MPa). Capable of foaming gel foams and solidifies with the formation of the foam while it is in the extrusion head.

For comparison, a foam is produced in a similar way, replacing exapostilarion acid 2.5 parts of hexabromocyclododecane on 100 parts by mass of the resin (pphr). This sample is designated as C3.

Foams evaluated for density, limiting oxygen index (LOI) and characteristics of the refractory properties in accordance with the test method FP-7, as described above. The results are presented in Table 2.

Table 2
Arr. Approx. or Compare. sample No.C3*8910
HBCD1, pphr2,5000
HBST2, pphr02,552,5
% The content of bromine is 1,91,53,01,5
The promoter melt, pphr0000,5
The test according to the standard FP-73seconds01,00,20,2
The test according to the standard FP-73the number drops0201
LOI, %30,529,329,829,5
The density of foam, kg/m341,639,155,352,9
*Not an example of the invention. "Pphr" means parts per 100 parts of resin.1Hexabromocyclododecane.2Exapostilaria acid.3The average time to extinction of the flame and the number of burning drops (burnable inclusions), which is passed are formed in accordance with the test FP-7.

The samples of Examples 11-13 and Comparative Sample C4

Following the General method described in relation to Examples 1-7, extruded polystyrene foam manufactured using 2.5 parts by weight of BSO on 100 parts by weight of polystyrene and foaming agent in the form of a mixture containing 3 parts of carbon dioxide, 1.5 parts of isobutane and 0.6 parts of water, all per 100 parts by weight of polystyrene. This foam is designated as the Sample of Example 11. Bromine content in it is 1.1% by mass.

Another foam is produced analogously to Example 11, except that 4 parts by weight (pphr) carbon black with a particle size of 250 nm embedded in the foam by mixing in a dry state with polystyrene to the stage of melting. The resulting foam is designated as the Sample of Example 12, and it contains a 1.2 weight percent bromine.

Preparation of the Sample of Example 11 is repeated again, this time with the addition of 2 parts by weight (pphr) graphite foam instead of carbon black and with a small reduction in the number of the brominated sunflower oil. The resulting foam is designated as the Sample of Example 13, and he contains to 0.8 weight percent bromine.

Another foam is produced in a manner analogous to the method of Example 11, except for the fact that that brominated sunflower oil is replaced by hexabromocyclododecane. Bromine content in the foam product is 1.7%. This foam is designated as Comparative Sample C4.

Measuring the density of the foams, pores size, test according to DIN 4102 and test according to EN ISO 11925-2 "Class E" is carried out on each of the Samples of the foams of Examples 11-13 and Comparative Sample C4. The results are listed in Table 3.

Table 3
Obrazec Example or Comparative Sample No.
Additive gives refractory properties, pphr111213C4*
BSO2,52,52,30
HBCD0002,5
The attenuator IR radiation type04, carbon black 2, the graphite0
Properties of foam
Wt.% Br11,11,20,81,7
The pore size of2mm0,400,420,230,48
Density3kg/m332,830,835,134,0
thermal conductivity, EN 8301-01, at 10°C after 30 days, mW/(m·K)33,931,729,433,7
Test for Flammability
Test according to DIN 41024Successful preharden the e/unsuccessful passing PassingPassingUnfortunate passingPassing
Test according to EN ISO 11925-2 Class E5, Successful/unsuccessful passingPassingPassingPassingPassing
LOI, % O227,0--28,0

Pphr means "parts per 100 parts by weight resin".1Bromine content as a percentage by weight of polymer foam. BSO (brominated sunflower oil) or HCBD (hexabromocyclododecane) is the only source of bromine in these experiments.2Vertical direction.3ISO 845-95.4To obtain an estimate of "successful" it is necessary that the height of the resulting flame was less than 15 cm for all test samples, and that no ignition of the paper, below the sample that burnout is limernyh inclusions. 5To obtain an estimate of "successful" it is necessary that the height of the flame was below 15 cm for all test samples, and that no ignition of the paper, below the sample, resulting in the burnout of the polymer droplets.

The sample of Example 11 shows the characteristics of fire resistance equivalent to the characteristics of the Comparative Sample C4, even if the Sample of Example 11 contains only about 2/3 the amount of bromine in comparison with Comparative Example C4. The density of the foam is significantly lower for the Sample of Example 11, and the pore size is also slightly smaller. The sample of Example 12 demonstrates the effect of adding 4 parts by weight (pphr) carbon black. On the characteristics of fire resistance is not significantly affected, while the density decreases and the pore size increased slightly. A lower density and a slight increase in the size of the pores are beneficial and unexpected. The sample of Example 13 demonstrates the effect of adding 2 parts by weight (pphr) of graphite. There is some loss of resistance due to the reduction of the content of bromine in the foam. However, the Sample of Example 13 was also successfully tested for fire resistance according to EN ISO 11925-2, even if it does not contain any promotion is R fluidity of the melt. BSO, as it was discovered, is stable in such conditions, the extrusion process. Not observed any significant loss of molecular weight, nor the products of hydrolysis in the case when water is present as a blowing agent in the extrusion process. Two samples of Examples 12 and 13 show improved thermal insulation properties compared with the Sample of Example 11.

1. A method of obtaining a foamed polymer material, including the production of pressurized molten mixture (A) combustible polymer, (B) at least one(th) bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, polymerized bronirovannoj fatty acids, or mixtures of any two or more substances from the above, in a quantity which provides from 0.1 to 30 parts by weight of bromine in 100 hours combined weight of the compounds (A)and (B)and (C) foaming agents, in an amount which provides obtaining foamed polymeric material having a density of from 16 to 480 kg/m3and then extruding the mixture into a zone of reduced pressure so that the mixture foams and cooled with the formation of foamed polymer containing component (B)where prior to the extrusion mixture nahodyaschuyusya pressure of the molten mixture is brought to a temperature, at least 200°C.

2. The method according to claim 1, where the combustible polymer is a polystyrene, a copolymer of styrene and acrylic acid, a copolymer of styrene and Acrylonitrile or a mixture.

3. The method according to claim 1 or 2, where component (C) has a temperature of 5%weight loss of at least 200°C.

4. The method according to claim 3, where component (C) includes brominated vegetable oil.

5. The method according to claim 4, where brominated vegetable oil is a brominated sunflower oil.

6. The method according to claim 3, where under the pressure of the molten mixture further comprises a promoter melt.

7. The method according to claim 3, where the molten mixture further comprises at least one thermal stabilizer.

8. The method according to claim 3, where the amount of component (C) is sufficient to ensure the foamed polymer from about 0.5 to 10 o'clock by weight of bromine in 100 hours combined weight of components (a) and (B).

9. The method according to claim 3, where the foamable substance comprises water.

10. The method according to claim 3, where the molten mixture is free of tin-containing compounds.

11. Extruded refractory foamed polymeric material containing a mixture of bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, the floor is narisovannoi bronirovannoj fatty acids, or a mixture of any two or more substances from the above, in a quantity which provides from 0.1 to 30 parts by weight of bromine in 100 hours combined mass of combustible polymer and bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, polymerized bronirovannoj fatty acids, or mixtures of any two or more substances of the above, and from 0.05 to 0.5 parts by weight of promoter melt on 100 parts by weight of a combustible polymer.

12. Extruded refractory foamed polymeric material according to claim 11, where the combustible polymer is a polystyrene, a copolymer of styrene and acrylic acid, or a copolymer of styrene and Acrylonitrile, or a mixture of two or more substances.

13. Extruded refractory foamed polymeric material according to claim 11 or 12, where bronirovannaja fatty acid, ester, amide or ester-amide bronirovannoj fatty acids, glycerides of one or more brominated fatty acids, polymerized bronirovannaja fatty acid, or a mixture of any two or more of the substances present in a quantity sufficient to provide from 0.5 to 10 hours of bromine in 100 hours combined mass of combustible polymer and bronirovannoj fatty acids, complex, ester, amide or of ester-amide bronirovannoj fat is Oh acid, glycerides of one or more brominated fatty acids, polymerized bronirovannoj fatty acids, or their mixtures of any two or more substances.



 

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7 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is self-extinguishing foamed polystyrene with low content of bromated antipyrene, obtained from pre-foamed or foaming styrene polymer which contains bromated antipyrene and a phosphorus compound, characterised by that the phosphorus compound is a product of the reaction of mono- or diammonium phosphate with urea, taken in ratio phosphate: urea equal to (1.0-2.3) - (1-3), respectively, with the following ratio of components (pts. wt): styrene polymer 100, bromated antipyrene 1.0-1.5, product of reacting mono- and diammonium phosphate with urea 4.0-8.0.

EFFECT: endowing self-extinguishing polystyrene with higher fire resistance with low content of antipyrene.

4 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention describes a method of producing a polystyrene granulate capable of foaming, involving a step for feeding a foaming agent into a mixing zone, mixing the foaming agent with molten polystyrene, homogenisation of the obtained mixture, cooling it to extrusion temperature, extrusion and granulation under conditions which prevent foaming. The method is characterised by that molar ratio of the foaming agent being fed to the specific carrying capacity of the apparatus in the mixing zone (Ks), which is the ratio of the amount of the passing stream of molten material, including polystyrene in kg/h to stirring rate in rpm, is kept in the range between 0.08 and 0.23, while maintaining temperature difference between the input and output at the homogenisation and cooling step in the range between 30 and 70°C.

EFFECT: obtaining polystyrene granulate through a continuous method with a narrow grain-size composition, which enables to obtain foamed articles with range of apparent density values 10-40 kg/m3 which have satisfactory application properties.

3 cl, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: mixture contains carbamidoformaldehyde resin, acid hardener, surface active substance, modifying additive and water. The modifying additive is a solution of natural bischofite mineral of formula MgCl2·6H2O with density of 1.24-1.40 t/m3.

EFFECT: obtained a raw mixture provides for fluidity of the foam mass, its resistance to pathogenic flora, reduces percentage of shrinking deformation and bulk weight, increases resistance to combustion, reduces release of toxic substances.

1 cl, 3 ex, 11 tbl, 1 dwg

FIELD: packing industry.

SUBSTANCE: method is described for manufacturing of container with walls of foamed material, including injection moulding of premold from melt of polyethylene terephthalate (PETP), containing gas that is non-reactive relative to PETP, at partial pressure sufficient for changeover of dissolved gas from polymer into gas phase, where it creates microporous foam structure. Then premould is cooled down to temperature below temperature of polymer softening, premould is repeatedly heated up to temperature that is higher than temperature of polymer softening, and blown moulding of premould is carried out for manufacturing of container.

EFFECT: produced container prevents diffusion of carbon dioxide between layers and has low heat insulation properties.

7 cl, 1 ex

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