Halogen-free fire retardant

FIELD: chemistry.

SUBSTANCE: fire retardant contains at least ammonium polyphosphate(s) and/or derivatives thereof, an oligomer or polymer derivative of 1,3,5-triazine or mixtures of several such derivatives and at least one compound selected from zinc dihydroorthophosphate, zinc borate, zinc orthophosphate, zinc pyrophosphate, zinc polyphosphate, zinc hydroxystannate, zinc stannate, boron phosphate, aluminium dihydroorthophosphate, aluminium orthophosphate, aluminium metaphosphate and mixtures thereof. The fire retardant can contain pre-condensed malamine derivatives, melamine salts and adducts thereof, ethylenediamine phosphate, piperazine phosphate, perazine polyphosphate, 1,3,5-trihydroxyethylisocyanurate, 1,3,5-triglycidylisocyanurate and triallylisocyanurate. The invention also relates to a polymer material, specifically a thermoplastic elastomer containing said fire retardant in amount of 5-25 wt %, preferably 10-25 wt %. The fire retardant has low water-solubility, decomposes at higher temperatures and can be used in smaller concentrations with high fire retarding action at the same time.

EFFECT: polymer material containing the fire retardant has improved physical and chemical properties, high fire-resistance and water-resistance.

14 cl, 3 tbl, 14 ex

 

The technical field to which the invention relates.

The present invention relates to the halogen-free flame retardant for inclusion or introduction into the polymer matrix (basis), as well as containing proposed in the invention, the flame retardant polymers, especially thermoplastic elastomers.

Background of invention

Thermoplastic polymers including thermoplastic elastomers are used in a variety of areas, for example, in electrical equipment, electronics, construction, engineering equipment of buildings, automotive and vehicles for General use. Such polymers have optimal mechanical properties and exhibit good processability and high chemical resistance. One way of making such polymers resistance is the addition of halogenated flame retardants with antimony trioxide. Another possibility is to add halogen-free substances, such as metal hydroxides, organic or inorganic phosphates or phosphonates, e.g., ammonium polyphosphates, together with the synergistic action of substances, such as carbon sources and the pore.

Recently, the increasing importance halogen-free flame retardants because they are unlike what teperino, containing chlorinated or brominated organic compounds, fire generate less smoke and are usually classified as environmentally friendly. From a number of inhibiting the burning of substances in halogen-free flame retardants are used primarily derivatives of phosphoric acid, pyrophosphoric acid and polyphosphoric acid. Ammonium and melamine derivatives of the aforementioned substances, as well as piperazines and etilendiaminova have the ability to foam at high temperatures in the composition of the molding masses with the formation of bulky protective layers, thereby insulating from the heat source or heat. Such a property can be further increased by adding synergistic action of substances. Foaming or so-called swelling occurs in contrast to the principle of halogenated flame retardants without the formation of high amounts of smoke.

The use of the above flame retardants in polyolefins often can not give them sufficient fire resistance, and for this reason it is necessary to add synergistic action of substances, such as carbon sources and blowing agents. In order to ensure adequate performance of such fire proofing compositions of the flame retardant to the polymer must often add the manage in very large quantities, which leads to a change primarily mechanical and electrical properties of the polymer.

Currently, the most effective flame retardants are considered to be a mixture of ammonium polyphosphate with amines, for example, a mixture with melamine compounds and/or pentaerythritol. Other known intumescent mixtures include those based on ammonium polyphosphate in combination with 1,3,5-Tris-gidroksiiminobetulonovoi acid.

However, the disadvantage of such mixtures is that they even after their incorporation into the polymer have an extremely high water-solubility, which they partially washed out and therefore be more able to exercise its effect. In addition, they have low decomposition temperature, which is still in the process of molding plastic products of protected polymers there is a partial decomposition of the flame retardant additive. In addition, such mixtures in spite of their increased efficiency must be used in the polymer in high concentrations, which deteriorates the processability of the polymer and reduces its flexibility.

The objective of the invention

Based on the foregoing, the present invention was based on the task to offer halogen-free flame retardant, which would be the best in comparison with the prior art fire-retardant effect, would be the opportunity is the first application in polymer material in smaller concentrations with high flame retardant effect, would have a low solubility and is decomposed only at higher temperatures than the known flame retardants, preferably at temperatures higher than the temperature of the polymer processing. The objective of the invention was also to provide a polymeric material, especially a thermoplastic and elastomeric polymeric material, which would have high physical-chemical properties, high resistance and at the same time with this high resistance.

Description of the invention

According to the invention fixed in its basis the problem is solved by using halogen-free flame retardant that contains at least the following components a, B and C, as well as optional component G:

And: polyphosphate(s) ammonium and/or its(their) derivatives

B: oligomeric or polymeric derivative of 1,3,5-triazine or a mixture of several such derivatives of General formula

,

in which

X denotes morpholinopropan, piperidinium or group, a derivative of piperazine

Y denotes a divalent group derived piperazine and

n denotes an integer greater than 1,

In: compounds selected from dihydroorotate zinc, zinc borate, zinc orthophosphate, zinc pyrophosphate, zinc polyphosphate, hydroxystannate zinc, stannate zinc, boron phosphate, dihydroorotate state aluminum, orthophosphate aluminum, metaphosphate aluminum and mixtures thereof,

G: the received forcedevice derivatives of melamine salt of melamine and its adducts, etilendiaminova, piperazino, piperazinylmethyl, 1,3,5-trihydroxyethylrutoside, 1,3,5-tripyridyltriazine, triallylisocyanurate,

when this mass ratio between component a and component B is from 10:1 to 1:1 and the proportion of components a and B together account for 60 to 99 wt.%, while the share of components C and D together account for from 1 to 40 wt.% of the total weight of components a, B, C, and

Underlying the invention the task is solved by using a polymer, especially a thermoplastic elastomer containing proposed in the invention, the flame retardant in an amount of 5 to 60 wt.%, preferably from 10 to 40 wt.%.

Part a covers and covered(s)and uncovered(s) polyphosphate(s) ammonium and/or their derivatives.

The term "coated ammonium polyphosphate" in this case means not only just covered ammonium polyphosphate, but covered and sewn ammonium polyphosphate. This cover adding a flame retardant to the polymer, in contrast to uncoated ammonium polyphosphate increases thermal resistance, reduces the solubility and improves compatibility with the polymer matrix, which is injected fire retardant. Part a-covered forms which can be obtained by coating particles of a powder or granular ammonium polyphosphate or its derivative.

Component a is added to the flame retardant in the form of a powder or granulate and when the fire causes the formation of smoke in much smaller quantities compared to halogen-containing flame retardant.

Component B is an oligomer or polymer of a derivative of 1,3,5-triazine or a mixture of several of such oligomers or polymers in combination with phosphates is also having a flame-retardant action of the substance. Component B when exposed to high temperatures or by contact with flame decomposes to carbon-containing residue with the formation of flammable gases, including water, carbon dioxide, ammonia and nitrogen. Component B in the proposed invention intumescent mixture serves as a carbon source.

The use of components a and B in a mass ratio of between 10:1 to 1:1 ensures optimum flame retardant effect. The use of component B at a smaller or larger number would reduce the effectiveness of the flame retardant. In this regard, the components a and B are preferably used in a weight ratio of between 6:1 to 2:1, particularly preferably from 5:1 to 3:1. It is preferable to continue to use components a and B together in an amount of from 85 to 99 wt.%, particularly preferably from 90 to 95 wt.%, and the components C and D together - in the amount from 1 to 15 wt.%, particularly preferably from 5 d is 10 wt.%, of the total weight of components a, B, C, and

As a component In the use of substances, primarily salts, present in the proposed invention the flame retardant leads to a further reduction in the smoke. Due to this, when the fires significantly reduced the secretion of toxic substances from the smoke and simultaneously improves the action of the flame retardant. In addition, this component increases the efficiency of the flame retardant and improves the mechanical properties of the polymer, which is used as a flame retardant.

As a component of G are obtained by forcedevice derivatives of melamine and/or a salt of melamine and its adducts, etilendiaminova, piperazino, piperazinylmethyl, 1,3,5-trihydroxyethylrutoside, 1,3,5-tripyridyltriazine, triallylisocyanurate or mixtures thereof. As an example, obtained by forcedevice derivatives of melamine can be called grind, melon, chalk, cyanurate melamine, melamine borate, melamine orthophosphate, melamine pyrophosphate, domelementforpath and melamine polyphosphate.

The compounds used as component G, serve as pore-formers. Received forcedevice derivatives of melamine and/or a salt of melamine and its adducts are so stable that in the process of recycling plastics containing flame retardant, no reaction occurs polycondensation or implement the function decomposition, dramatically improves the processability of plastics. Simultaneously retained fire-retardant effect, respectively the resistance.

The compounds used as component G are comparable with ammonium polyphosphate or a higher decomposition temperature and therefore increase the efficiency of ammonium polyphosphate or its derivatives. When used in plastic saved resistance, processability and mechanical strength.

These components proposed in the invention flame retardant contribute also proposed in the invention compositions to improve the mechanical properties of the polymer, which is used as a flame retardant.

Another advantage of the proposed invention the flame retardant is that compared with the traditional flame retardants can be used in smaller quantities in as good or even better effect, which reduces the cost of containing such flame retardant plastic and is less of an influence on its mechanical properties, so they do not deteriorate its mechanical properties. Proposed in the invention, the flame retardants even when applied at concentrations below 30% in thin plastic, such as high density polyethylene (HDPE), provide an exceptionally high flame retardant is action. In the application proposed in the invention as a flame retardant in polypropylene (PP) to achieve good flame retardant action can be sufficient to use a flame retardant in plastic concentration below 25%, or even below 20% without degrading the polymer processing AIDS.

In a preferred embodiment, component a represents or contains covered(s) polyphosphate(s) ammonium and/or its derivatives. The coating component not only significantly reduces the solubility, but also increases thermal stability of ammonium polyphosphate, reduces the chemical activity of the ammonium polyphosphate in relation to other components of the flame retardant, and also improves the compatibility with the polymer, which is used as a flame retardant.

In one embodiment, the component As proposed in the invention is a flame retardant selected from the coated ammonium polyphosphate crystalline modification I, II or V, and mixtures thereof.

In a particularly preferred embodiment, component a is a coated and/or uncoated ammonium polyphosphate crystalline modification II, which compared with other crystalline modifications almost not soluble in water. The concern powdered substance that even without the coating has good flame retardant effect at low odorant is ariosti. The advantage associated with the use of coated ammonium polyphosphate crystalline modification II, is that it has a high thermal stability and high compatibility with the polymer, thus improving the dispersion of the flame retardant in the polymer and its processability, respectively, technological properties and increases the effectiveness of fire protection.

Ammonium polyphosphate and/or its derivatives preferably be covered with melamine, melamine-formaldehyde resins, derivatives of melamine, silanes, siloxanes, or polystyrene. Between dispersed ammonium polyphosphate and/or its derivatives and the coating material forms an ionic bond with the replacement of ammonia associated with the ammonium polyphosphate, the coating material. This compound has an extremely high stability, and therefore, when processing plastic coating remains virtually unchanged.

Covered with melamine ammonium polyphosphate obtained when the temperature is over 250°C. the Duration of the reaction should be such that may present in excess melamine completely reacted with the surface of ammonium polyphosphate, replacing the ammonia and stronger contacting the ammonium polyphosphate.

Preferably next to cover particles of ammonium polyphosphate what elamin, melamine-formaldehyde resins, derivatives of melamine, silanes, siloxanes or polystyrene with subsequent stitching. Crosslinking melamine coating further reduces the water solubility of ammonium polyphosphate and is usually performed by interaction with formaldehyde. This method is well known to specialists in this field.

The share of coverage of ammonium polyphosphates and/or derivatives thereof, should preferably be from 0.1 to 20 wt.%, more preferably from 1 to 10 wt.%, in terms of the whole mass of coated ammonium polyphosphate and/or their derivatives. This ratio between ammonium polyphosphate and coating ensures optimal protection of ammonium polyphosphate, which is also the optimal capacity of the ammonium polyphosphate to contact the polymer, which should be used as a flame retardant. Simultaneously at the specified ratio of the coating is not in such great abundance, in which the Department free of the coating material, weaker associated with ammonium polyphosphate.

In a particularly preferred embodiment, the average size D50 of coated particles of ammonium polyphosphate or its derivative is, including the floor, from 5 to 30 μm, especially from 5 to 20 μm, most preferably from 7 to 18 microns. Particles larger sizes not p is Dauda quite homogeneous dispersion in the polymer and therefore, under certain conditions, adversely would affect its properties. The same particles of smaller sizes are also less preferred because it is difficult to ensure accurate dosing.

The coated ammonium polyphosphate and/or its derivative average size D50 of the particles of ammonium polyphosphate and/or its derivatives in the form of a core covered with particles in the preferred embodiment, is approximately 7 μm. The advantage associated with such a particle size primarily consists also in the fact that proposed in the invention, the flame retardants are compared with the previously known flame retardants high decomposition temperature and thus have an extremely high thermal resistance.

As component B, it is preferable to use oligomeric or polymeric derivative of 1,3,5-triazine, in which n is an integer from 2 to 50, particularly preferably from 2 to 30, especially from 3 to 9. Upon receipt of such oligomers or polymers are usually formed by mixture with chains of different length. In the proposed invention the flame retardant can be used and those formed by polymerization of the mixture, with more than 70%, more preferably 80%, especially preferably more than 90%used oligomers and polymers should have a chain length n from 2 to 50, preferably from 2 to 30, particularly preferably from 3 to 9. This includes the possible use and heteropolymers, and homopolymers.

the preferred monomers derived 1,3,5-triazine as component B include 2-piperazinyl-4-morpholino-1,3,5-triazine and 2-piperazinyl-4-piperidino-1,3,5-triazine. You can also use mixed oligomers or polymers of the above substances. The synergistic effect of the application of these polymers or oligomers in combination with ammonium polyphosphate and/or its derivatives is primarily manifested in increasing the effectiveness of the flame retardant.

Compounds that are used as a component in and which additionally increase the efficiency of the flame retardant and above all allow you to add a flame retardant in small quantities, are salts of metals selected from dihydroorotate zinc Zn(H2PO4)2, borate zinc orthophosphate zinc Zn3(PO4)2, pyrophosphate zinc Zn2P2O7, zinc polyphosphate of General formula oZnO·pP2O3·qH2O, where o and p represent integers from 1 to 7, and q denotes a number from 0 to 7, hydroxystannate zinc ZnSn(OH)6, stannate zinc ZnSnO3phosphate boron BPO4, dihydroorotate aluminum Al(H2PO4)3, aluminum orthophosphate AlPO4, metaphosphate aluminum [Al(PO3)3]n, octamolybdate ammonium (OMA) and mixtures thereof. In respect of these salts unexpectedly, it was found that as a result of their interaction with components a and B is achieved exceptionally high flame retardant action, which even with the addition of flame retardant for polymers in small to is icestar can be attributed to their higher class ognezashita.

Among the received forcedevice melamine derivatives, salts of melamine, and adducts of melamine as a component G preferred grind, melon and chalk. Other preferred compounds as component G are cyanurate melamine, melamine borate, melamine orthophosphate, melamine pyrophosphate, domelementforpath and melamine polyphosphate. The addition of such substances provides further improvement in the efficiency of the flame retardant, and these substances have the effect of pore-even when applied in small quantities.

The object of the invention is also a polymer material, especially a thermoplastic elastomer containing proposed in the invention, the flame retardant in an amount of preferably from 5 to 60 wt.%, particularly preferably from 10 to 40 wt.%. Polymers with given to them in this way resistance even at a small thickness of the layer comprising, for example, only 0.8 mm, satisfy the highest requirements for fire protection (ognezashita)that even applies to flammable plastics, such as PP or HDPE and other flammable copolymers. In this case, thanks to the application of the proposed invention in flame retardants is possible to improve the flexibility and processability of fire protective of their plastics in comparison with plastics containing known the flame.

Preferred polymeric materials selected from filled and unfilled polyolefins, vinyl polymers, olefin copolymers, thermoplastic elastomers based on olefins, crosslinked thermoplastic elastomers based on olefins, urethanes, polyesters and spoliation, copolymers of styrene, polyamides and copolyamids. The application of the proposed invention the flame retardant primarily in thermoplastic elastomers based on olefins, crosslinked thermoplastic elastomers based on olefins and copolymers of styrene can positively influence the mechanical properties of these plastics, mainly for their resistance to abrasion. Therefore, these thermoplastic elastomers with attached proposed in the invention flame retardant fire resistance, flame resistance, respectively can primarily be used in place of polyvinyl chloride (PVC) cables, wiring, pipes for laying electric cables and pipelines and sewer systems. Proposed in the invention thermoplastic elastomer in the most preferred embodiment is selected from copolymers of styrene, preferably such copolymers of styrene as a styrene-butadiene-styrene, styrene-etensuren-styrene, styrene-ecoprobe-styrene, styrene-Eten-ecoprobe-styrene and methacrylate-butadiene-styrene

Thermoplastic elastomers, especially copolymers of styrene, are relatively flammable materials, which are usually ignite easier than polymers of many other types, which among other things is due to the high relative content of oils that increase Flammability. It is therefore particularly surprising is the fact that the proposed invention in the solution as a whole and primarily offered in the invention, the flame retardants can achieve highly effective fire protection of thermoplastic elastomers. Although to achieve good flame-retardant action of fire retardants in polymeric matrix should normally be somewhat higher than in polymers some other types, however, the presence of flame retardants in such increased quantities, in thermoplastic elastomers are very many types does not lead to a significant deterioration in their mechanical and other properties.

In another preferred embodiment, the polymeric material along with the proposed invention the flame retardant contains also other fillers selected from calcium carbonate, silicates, such as talc, clay or mica, silica, calcium sulphate and barium, aluminum hydroxide, glass fibers and glass beads, as well as wood flour, cellulose powder, carbon black and graphite. Such fill is eating allows us to give plastics other required properties. The use of such fillers allows first of all to reduce the cost of plastics, paint it or to improve its mechanical properties, for example, by reinforcing fibers.

In the following embodiment of the invention, the chlorine content of the component B halogen-free flame retardant is less than 1 wt.%, preferably less than 0.8 wt.%. In such a low chlorine content is of particular advantage over the prior art because of known flame retardants are payable undesirable too much chlorine in the form of Neorganicheskie and organically bound chlorine.

In yet another embodiment of the invention, the total content of chlorine in the polymer material is less than 1500 miscast./million, preferably less than 900 miscast./million this is a special advantage over the prior art because of known flame retardants are payable undesirable too much chlorine in the form of Neorganicheskie and organically bound chlorine. The term "halogen-free" in accordance with the present invention allows for the presence of chlorine as impurities in small amounts, not exceeding the above maximum number. In General, however, the chlorine content, respectively halogen generally should be maintained at a low level in order to avoid negative influence Gal the genes.

In the following embodiment of the invention, halogen-free fire retardant contains a dispersant in an amount of from 0.01 to 10 wt.%, preferably from 0.1 to 5.0 wt.%, these dispersers in a preferred embodiment, selected from fatty acid amides, including monoamide, diamides and alkanolamide fatty acids, such as oleamide and erucamide, esters of fatty acids, including esters of glycerol esterified waxes, fatty C16-C18acids, alcohols derived from fatty acids, including cetyl and stearyl alcohols, natural and synthetic waxes, polyethylene wax and oxidized polyethylene waxes and metallic stearates, preferably stearates of calcium, zinc, magnesium, barium, aluminum, cadmium and lead. Adding the above dispersant improves desirement flame retardant, extraterrest polymer material and the uniformity of dispersion of the flame retardant in the polymer matrix.

In yet another embodiment of the invention, the content of free water in the halogen-free flame retardant (moisture content) is less than 0.6 wt.%, preferably less than 0.4 wt.%. At low water content also improves desirement flame retardant, extraterrest polymer material and the uniformity of dispersion of the flame retardant in the polymer matrix.

Examples

Below is some examples in which considered proposed in the invention and is not relevant to the invention polymers, respectively, used in the fire retardant.

In the examples, samples for various tests were prepared in plasticators "Brabender". To do this, first the polymer without the addition of flame retardant melted in motion. After that, in the melt at one stage in the form of a mixture or sequentially added to components a, B, C, and/or, After homogenization for 10-15 minutes polymeric material was recovered from him on the heated press extruded plate with a thickness of 0.8 mm and 1.6 mm From pressed wafer saw, cut out the appropriate samples, which are then subjected to the following tests.

The composition of different samples, respectively comparative samples are shown below in table 1. As a triazine derivative used polymer 2-piperazinyl-4-morpholino-1,3,5-triazine. In addition, used uncoated ammonium polyphosphate (product FR CROS 484), covered with melamine ammonium polyphosphate (product FR CROS C40) or covered with melamine and sewn ammonium polyphosphate (product FR CROS 498) (all products of the company Chemische Fabrik Budenheim). As melamine polyphosphate used the product Budit 3141 (company Budenheim Iberica) or product Melapur 200 (the company CIBA). As aluminum phosphate used the product Fabutit (firm Chemische Fabrik Budenheim), and as cyanurate chalk is Mina used the product Budit 315 company Budenheim Iberica. The abbreviation "HDPE" means high density polyethylene, and the abbreviation "PP" means polypropylene.

Examples, only identified by a serial number without the letter "C"represent the respective invention examples. Examples of the same designated sequence number with the letter "C", are not relevant to the invention and comparative examples.

The fire test with a vertical position of the sample according to standard UL94

For testing according to standard UL94, below referred to as UL94 V, five samples with a thickness of 1.6 mm, respectively 0.8 mm fixed at one end in a vertical position. Each sample with its lower free end of the double-10 was subjected to the flame of Bunsen burner. In each case, the measured time during which the sample after removal of the torch continued to burn or smolder. At the same time it was registered, whether falling from the burning sample flaming drops igniting below a sample of cotton fabric. The results are shown in table 2.

In this table, the abbreviation "TW" means the total time for all 5 samples in seconds.

The tests were carried out in accordance with the recommendations of the standard UL 94V developed industrial Association standard is rtizatio "Underwriters Laboratories". "UL94" denotes a class of ognezashita sample, with V0 means that the total combustion duration of 5 samples tested was less than 50, and the cotton fabric is not ignited, the incident with sample Claudine or burning drops. Class V2 means that the total combustion duration of 5 samples tested was a total of less than 250, but cotton was ignited the incident with sample Claudine or burning drops.

Determination of oxygen index of

The lowest concentration of oxygen in a mixture of N2/O2at which the sample after igniting it still continues to burn yourself, called oxygen index (LOI). The higher the KI, the higher the resistance of the sample. The values of KI more than 30% are considered very good. High KI particularly important for compliance in the cable industry.

The tests were carried out in accordance with DIN EN ISO 4589 part 2. The samples had dimensions of 1.25×3,0×6,5 mm

The results of this test are also shown in table 2, where KI in each case expressed as a percentage.

Determining the temperature of decomposition of the flame retardant

As another test, the flame retardant was subjected to heating separately without its introduction in the polymer and thus determined the temperature at which the origin is of Odilo decomposition of the flame retardant. Usually for such a decomposition temperature take the temperature at which the loss or reduction of weight of the sample reaches 2% of its original mass.

These tests were carried out by the method of thermogravimetry. For this sample flame retardant in an amount of 10 mg was placed in a crucible and was heated therein to a temperature above 350°C, increasing the temperature at a rate of 10 K/min During heating of the sample was measured by the change in its mass.

The results are presented in table 3.

In General, this test were subjected to 14 different proposed in the invention compositions (examples No. 1-14) and 4 comparative compositions (examples No. C1-C4).

Obtained primarily for samples with a thickness of 0.8 mm results indicate that proposed in the invention, the flame retardants, respectively containing polymers are clearly the best performance compared to similar, previously retardants. Almost all offered in the invention polymers when the thickness of the samples, equal to 0.8 mm, the test standard UL94 reach in contrast to the samples of comparative examples top class ognezashita V0.

Even when the relative content of the flame retardant in plastics, accounting for only 20%as in samples from examples 3 and 4, in the test standard UL94 still achieved class ognezashita V2.

Thanks, first turn is the attainment of the highest class ognezashita with extremely small thickness of the test pieces of plastic and relative content of flame retardant is less than 30%, or less than 25% and a high enough class ognezashita even when the relative concentration of the flame retardant is less than 20% there is an opportunity to confer with the use proposed in the invention of fire retardants even having a very small thickness of the plastic products, primarily from thermoplastic polyolefins and elastomers, thereby expanding the possible range of applications, halogen-free intumescent flame retardants. Thus, in particular, proposed in the invention, the flame retardants can be used in the composition of materials for manufacturing of cables, for the manufacture of cable channels for producing films for the manufacture of electronic components, for the manufacture of housings of electric and electronic devices and for making other subtle, respectively, of thin-walled products. Another advantage, which is manifested in the manufacture of such materials is that proposed in the invention, the flame retardants are used to obtain a used thermoplastics exceptionally high resistance while maintaining together with the mechanical properties of modified such flame retardants polymers due to the low dosage and the specific interaction of components a and B with component b and component D when using it. Proposed in the invention, the flame retardants are also extremely low smoke emission.

The results, Paul is obtained when the test samples of examples 5, 6, 7 and 8, first of all indicate that the addition of component D although it increases slightly the total duration of combustion, but also increases the decomposition temperature or the oxygen index, i.e. further self-combustion of the sample, respectively proposed in the invention polymer is possible only at higher concentrations of oxygen.

The sample of example No. 5 in total contains only 25% of the flame retardant, which is 76% of covered melamine ammonium polyphosphate, 16% - from triazine compounds, 4% of pyrophosphate zinc and 4% from cyanurate melamine. Such a component has the most balanced properties, which include good flame-retardant effect, the extremely high oxygen index and also an extremely high decomposition temperature.

Add a component G allows, as evidenced by the test results of the samples from examples, to raise the temperature of the decomposition proposed in the invention is a flame retardant. Therefore, depending on the purpose of adding flame retardant component G or its non-use allows you to enhance certain desired property.

All offered in the invention, the flame retardants, respectively containing polymers, and thus proposed in the invention of the polymerase is s along with a short combustion duration are also characterized by extremely high oxygen index and extremely high decomposition temperature. In addition to this are proposed in the invention polymers have the ability to process and therefore allow you to use them instead of polluting PVC.

Table 1
Structures
Example No.1234567891011121314C1C2C3C4
Component
AndFR CROS 489191915,215,21919
AndFR CROS 401919191919191920191919
And19
Bthe triazine compound443,23,244444444445444
Inthe zinc pyrophosphate1 1111122
Inthe zinc borate2211
Inthe aluminum phosphate1 11
Gcyanurate melamine0,6112
Ggrind12/td>
Gmelon12
Gmelamine polyphosphate0,61
Additivemagnesium hydroxidethe 1
PlasticHDPE7575
PlasticPM758080757575 75757575757575757575

Table 2
The results of the fire test
Example No.1234567891011121314C1C2C3C4
TestThe thickness of the sample
TVT1.6 mm9517131211101313177121325232019
UL941.6 mmV0V0V0V0V0V0V0V0V0V0V0V0 V0V0V0V0V0V0
TVT0.8 mm2517>50>501715171815208>50>509>50>50>50>50
UL940.8 mmV0V0V2V2V0V0V0V0V0V0V0V2V2V0V2V2V2 V2
KI1.25 mm313333343737373134332831323532302829

Table 3
The decrease in mass of flame retardant (no plastic) 2%
Example No.1234567891011121314C1C2C3 C4
Temperature in °C312312309308322322317326310290286313329314319325330319

1. Halogen-free flame retardant for inclusion or introduction of a thermoplastic elastomer containing at least the following components a, B and C, and, optionally, component G:
And: polyphosphate(s) ammonium and/or its(their) derivatives
B: oligomeric or polymeric derivative of 1,3,5-triazine or a mixture of several such derivatives of General formula
,
in which
X denotes morpholinopropan, piperidinium or group, a derivative of piperazine
Y denotes a divalent group derived piperazine and
n denotes an integer from 2 to 50,
In: a compound selected from dihydroorotate zinc, zinc borate, zinc orthophosphate, zinc pyrophosphate, zinc polyphosphate, hydroxystannate zinc,stannate zinc, phosphate boron, dihydroorotate aluminum, aluminum orthophosphate, metaphosphate aluminum and mixtures thereof,
G: the received forcedevice derivatives of melamine salt of melamine and its adducts, etilendiaminova, piperazino, piperazinylmethyl, 1,3,5-trihydroxyethylrutoside, 1,3,5-tripyridyltriazine, triallylisocyanurate,
when this mass ratio between component a and component B is from 10:1 to 1:1 and the proportion of components a and B together account for 60 to 99 wt.%, while the share of components C and D together account for from 1 to 40 wt.% of the total weight of components a, B, C, and

2. Halogen-free flame retardant according to claim 1, characterized in that component a represents or contains covered(s) polyphosphate(s) ammonium and/or its derivatives.

3. Halogen-free flame retardant according to claim 1, characterized in that component a represents or contains coated and/or uncoated ammonium polyphosphate crystalline modification II.

4. Halogen-free flame retardant according to claim 1 or 2, characterized in that the ammonium polyphosphates and/or their derivatives as a component And are covered with melamine, melamine-formaldehyde resins, derivatives of melamine, silanes, siloxanes or polystyrene particles and/or covered with melamine, melamine-formaldehyde resins, derivatives of melamine, silanes, siloxanes is whether the polystyrene and crosslinked particles.

5. Halogen-free flame retardant according to claim 4, characterized in that the share of coverage of ammonium polyphosphates and/or their derivatives as a component And accounts for from 0.1 to 20 wt.%, preferably from 1 to 10 wt.%, in terms of the whole mass of coated ammonium polyphosphate and/or their derivatives.

6. Halogen-free flame retardant according to claim 2, characterized in that the coated ammonium polyphosphate and/or their derivatives as a component And have an average size D50 of the particles, including the floor, from 5 to 30 μm, preferably from 5 to 20 microns.

7. Halogen-free flame retardant according to claim 1 or 2, characterized in that a derivative of 1,3,5-triazine as a component B selected from oligomers and polymers of 2-piperazinyl-4-morpholino-1,3,5-triazine and 2-piperazinyl-4-piperidino-1,3,5-triazine, and combinations of these compounds.

8. Halogen-free flame retardant according to claim 1 or 2, characterized in that component D is selected from malema, melon, melam group, cyanurate melamine, melamine borate, melamine orthophosphate, melamine pyrophosphate, timelinedorothea and melamine polyphosphate.

9. Halogen-free flame retardant according to claim 1 or 2, characterized in that it also contains a dispersant in an amount of from 0.01 to 10 wt.%, preferably from 0.1 to 5.0 wt.%, such dispersing agents are preferably chosen from fatty acid amides, including monoamide, diamides and alkanolamide fatty acids, such as eumida and erucamide, of esters of fatty acids, including esters of glycerol esterified waxes, fatty16-C18acids, alcohols derived from fatty acids, including cetyl and stearyl alcohols, natural and synthetic waxes, polyethylene wax and oxidized polyethylene waxes and metallic stearates, preferably stearates of calcium, zinc, magnesium, barium, aluminum, cadmium and lead.

10. Halogen-free flame retardant according to claim 1 or 2, characterized in that the content of free water (moisture content) is less than 0.6 wt.%, preferably less than 0.4 wt.%.

11. Polymeric material such as thermoplastic elastomer containing flame retardant according to one of claims 1 to 10 in an amount of 5 to 25 wt.%, preferably from 10 to 25 wt.%.

12. Polymeric material such as thermoplastic elastomer according to claim 11, characterized in that it is selected from filled and unfilled polyolefins, vinyl polymers, olefin copolymers, thermoplastic elastomers based on olefins, crosslinked thermoplastic elastomers based on olefins, urethanes, polyesters and spoliation, block copolymers of styrene, polyamides and copolyamids.

13. The polymeric material according to claim 11 or 12, characterized in that it is a thermoplastic elastomer selected from block copolymers of styrene, preferably, such as stiro the-butadiene-styrene, styrene-etensuren-styrene, styrene-ecoprobe-styrene, styrene-Eten-ecoprobe-styrene and methacrylate-butadiene-styrene.

14. Polymeric material such as thermoplastic elastomer according to claim 11 or 12, characterized in that it contains fillers selected, preferably, calcium carbonate, silica, talc, clay, mica, silica, calcium sulfate, barium sulfate, aluminum hydroxide, glass fibers, glass beads, wood flour, cellulose powder, carbon black and graphite.



 

Same patents:

FIELD: textiles, paper.

SUBSTANCE: treatment method includes the stage of emission treatment with irradiation of cellulose fiber material with irradiation, the stage of treatment with phosphorus with addition of phosphorus compound capable to radical polymerisation to the material of cellulose fibers, and the stage of treatment with amine with addition of amine compound to the material of cellulose fibers. The phosphorus compound capable to radical polymerisation is a vynil-phosphate compound. The amine compound is a polymer containing amino group, which is capable to form an ammonium ion in water. The cellulose fiber treated with this method is used to obtain fire-retarding material. In the fire-retarding material the cellulose fiber is connected with the phosphorus compound capable to radical polymerisation by the additive reaction, and the amine compound is bound with ion bond to the phosphorus compound combined and capable to radical polymerisation.

EFFECT: material has sufficient flame proofing and excellent tactile perception of the fabric.

6 cl, 4 tbl, 44 ex

FIELD: chemistry.

SUBSTANCE: polyamide-based composition contains melamine cyanurate and novolac. The composition is suitable for moulding articles which are used in electrical and electronic connections such as circuit breakers, switches and connectors.

EFFECT: high stability of the size of articles.

6 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to fire- and bioprotective preparations for wood and wood-based materials. The preparation for protecting wood and wood-based material from fire contains a solvent - water, boric acid, diammonium phosphate and amino alcohol of general formula: (CnH2n+1)k NH3-(k+m) (CnH2nOH)m, where: n, m=1-3, k=0-2, k+m≤3.

EFFECT: obtaining a preparation with high fire-protective efficiency and protective capacity with respect to the most common mould and wood-staining fungi.

5 tbl

FIELD: medicine, fire-fighting means.

SUBSTANCE: invention refers to fire-protective compositions and fireproof fabrics with low smoke generation and toxicity of combustion products. The composition for fibre-blend textile fabric fire protection contains nitrilomethylene phosphonic acid, ammonium bicarbonate as a nitrogen-bearing compound in the ratio 1.1:1.0 with acid and zinc acetate in amount 20-40 g/l or 0.25-0.4 weight fractions. A method for producing a textile fabric of the low combustibility, smoke generation ability and low toxicity of combustion products, involves impregnation of the textile fabric with said composition followed by wringing thereof, drying and heat treatment at 140-160°C. The technique described above may be used for treating the textile fabrics from natural and synthetic fibres.

EFFECT: group of inventions provides low smoke generation abilities of the fabrics and reduced toxic gas flow after their thermal decomposition.

6 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a fire-retarding composition with intumescent action for metal structures. The composition contains a film-forming agent, hardener OSA-1, an ionic surfactant and thickener. The film-forming agent used is an aluminophosphate or aluminochromophosphate film-forming agent. The thickener used is crushed basalt fibre, glass microspheres or mixture thereof. The fire-retarding composition has improved process characteristics, particularly intumescence capacity at high temperatures.

EFFECT: use of the composition increases fire-retarding efficiency.

1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to 3,3'-bis-(3,4-dihydro-3-phenyl-2H-1,3-benzoxazin-6-yl)-1(3H)-isobenzofuranone and analogues based on phenolphthalein, formaldehyde and a primary amine of formula 1: , in which R independently represents allyl or phenyl, and to a method of synthesising the said compounds. The invention also pertains to a method of making a refractory cast or layered material based on the said compounds and laminating compositions since through thermal hardening, these compounds form a net which does not catch fire easily and is resistant to high temperatures. The said compounds can be particularly useful in making printed circuit boards.

EFFECT: obtaining fire-resistant compounds.

5 cl, 4 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention concerns obtaining antipyrenes and can be applied in woodworking industry for production of fireproof slab items, as well as in fire protection of metal constructions. Method of obtaining fire-retardant composition of bulging effect for wood and metal constructions involves mixing of metal phosphate and composition containing solidifier, ionogenic surfactant and HOTEX product, where solidifier is AM-1 amine modifier, amino alcohols or fire-retardant composition obtained by reaction of carbamide-containing compound with ammonium water during heating in weak alkali medium in the presence of amino alcohol, with further decondensation with carbide and neutralisation by orthophosphoric acid to pH 6.0-8.0ionogenic surfactant is PO-6 TS foaming agent of A and B grades, at the following component content, wt. %: metal phosphate 40-90, solidifier 5-30, ionogenic surfactant 0-15, HOTEX product 0-20.

EFFECT: enhanced fire protection and sustenance of moderate hardening speed of obtained antipyrene.

1 tbl

FIELD: production of antipyrines, applicable in wood-working industry, as well as in building at carrying-out of preventive maintenance measures in fireproofing of products made of dry wood.

SUBSTANCE: the method consists in mixing of alumochromophosphate, non-ionogenic surface-active agent and polyamine, preliminarily neutralized by ortho-phosphoric acid to pH 6.0-8.0, used as polyamine is the aqueous solution of a product of general formula: , where: n=0.1 and m=0.1 at the following mass relation of components: alumochromophosphate: non-ionogenic surface-active agent: polyamine equal to (20-90):(0.01-0.5):(10-80).

EFFECT: produced wood materials of the first group of fireproofing efficiency at reduced consumption of antipyrine.

4 ex, 1 tbl

The invention relates to a fire retardant composition and method of reception

The invention relates to the chemistry and technology of additives to thermoplastics, reduce the Flammability of polymers, and can be used in the chemical industry

FIELD: chemistry.

SUBSTANCE: present invention relates to a low-flammability moulding composition based on polypropylene as well as fibre and a film made from said composition.

EFFECT: invention reduces flammability of polypropylene without deterioration of physical and mechanical properties of the obtained low-flammability polypropylene granulate as well as articles based thereon.

3 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to fire- and bioprotective preparations for wood and wood-based materials. The preparation for protecting wood and wood-based material from fire contains a solvent - water, boric acid, diammonium phosphate and amino alcohol of general formula: (CnH2n+1)k NH3-(k+m) (CnH2nOH)m, where: n, m=1-3, k=0-2, k+m≤3.

EFFECT: obtaining a preparation with high fire-protective efficiency and protective capacity with respect to the most common mould and wood-staining fungi.

5 tbl

FIELD: chemistry.

SUBSTANCE: composition for fire-proof treatment of polyether fibres contains the following in pts.wt: phosphorus-boron-containing methacrylate 45.0, water 55.0, ammonia 8.0, sodium persulphate 0.225-0.45 and ground 23KNTS polycaproamide fibre 0.045-0.225.

EFFECT: high fire-resistance, strength, adhesion to chloroprene rubber.

2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition consists of 1 part citrate ion source per 12.7-20 parts ammonium phosphate and 0.8-2.2 parts benzoate ion source. Alternatively, the composition consists of 1 part citric acid per 12.7-20 parts ammonium phosphate and 0.8-2 parts sodium benzoate.

EFFECT: composition can be granular or liquid with further addition of water and ingredients which are not harmful to humans and the environment.

17 cl

FIELD: chemistry.

SUBSTANCE: composition for fire-proof treatment of synthetic fibres contains the following in pts. wt: methylphosphite borate 20.0-35.0, water 65.0-100.0, ammonia 15.0-25.0, polyacrylamide 15.0-25.0 and potassium persulphate 0.5-1.5.

EFFECT: high fire-resistance, strength, resistance to thermal-oxidative decomposition and endowing synthetic fibre with high strength of binding with isoprene rubber.

2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention refers to constructional composites based on ultra-high molecular polyethylene (UHMPE), used in industrial production of fire-resistant multipurpose products with compaction method. Fire-resistant material contains powdered ultra-high molecular polyethylene of powder particle size 20-50 microns and molecular weight within 1.0 million to 25.0 million, and ammonium polyphosphate of powder particle size not exceeding 10 microns and degree of polymerisation not less than 1200. Material is made by stirring the mixed powdered UHMPE and ammonium polyphosphate in ratio as follows, wt %: ultra-high molecular polyethylene - 80, ammonium polyphosphate - 20.

EFFECT: produced fire-resistant material is characterised with fire resistance "ПВ"-0 and ensures reduced degree of flammability of constructional composites.

1 tbl, 1 ex

FIELD: synthesis of phosphorus-containing derivatives of organic compounds.

SUBSTANCE: invention relates to method of preparing polyphosphates of organic compounds, to mixture of polyphosphates of organic nitrogenous bases, and to use of polyphosphates and mixture of polyphosphates as fire retardants for plastics, preferably thermoplastics and, more particularly, polyamides and polyesters. Polyphosphates of organic compounds are prepared via exchangeable decomposition of mixture of phosphorus pentoxide and at least one organic nitrogenous base with a compound releasing water when decomposed under reaction conditions, the latter compound being used in such molar proportion that water would release in amount corresponding to essentially two moles of water per one mole of phosphorus pentoxide. Water-releasing compound can be compound forming, along with water, only volatile decomposition products and this compound can be selected from group including anhydrous oxalic acid, oxalic acid dehydrate, and formic acid. Exchangeable decomposition reaction is conducted at 100 to 250°C. Mixture of polyphosphates of organic nitrogenous bases is characterized by following properties: when heated to 320°C it looses less than 2% of its mass; pH value of its 10% water suspension exceeds 5 at 25°C, preferably from 5.2 to 7.7 and, more preferably, from 5.8 to 7; its solubility in water is less than 0.1 g and preferably less than 0.01 g per 100 mL water.

EFFECT: expanded synthetic possibilities.

6 cl, 5 ex

FIELD: inorganic chemistry, aluminum silicates, composition for fireproofing of building and construction materials.

SUBSTANCE: invention relates to water resistant aluminum silicate with softening temperature more than 900°C for fireproofing of wood, polymer, and other building and construction materials. Water resistant aluminum silicate has general formula of Na2O*kSiO2*nAl2O3*pP2O5*rMA*mH2O, 1, wherein k = 3.25-11.5; m = 3.5-12; n = 0.052.7; p = 0-0.1; r = 0.3.5; M is K, Ca2+, Mg2+, Zn2+, 1/2Ti4+; A is Cl-, O2-, SO42-, CO32-. Aluminum silicate represents hardening product of water dispersion containing 1) sodium silicate of general formula Na2O*xSiO2*yH2O, 2, wherein x = 2.9-3.1; y = 17-22; 2) cross-linking agent based on alkali soluble silicium and/or aluminum compound; 3) at least one a) hardening agent (alkali soluble zinc, titanium, magnesium and/or calcium oxide (hydroxide)); b) opener; c) filler (e.g. kaolin, chipped glass fiber, milled sand, etc.); d) modifier in the next component ratio (mass %): sodium silicate 31-83.8, preferably 58-75; alkali soluble silicium compounds 0.05-39.2, preferably 10-15; alkali soluble aluminum compounds 0.4-26, preferably 5-8; hardening agent 0.74-19.9, preferably 3-8; opener 0.013-9.7; filler 1.9-33, preferably 5-15; modifier 0.01-6.3, preferably 0.35-0.75.

EFFECT: composition for production of non-cracked coating with low thermal conductivity and increased fire resistance.

28 cl, 116 ex, 52 tbl

The invention relates to compositions for protection against fire wood and can be used in woodworking and construction for wood processing

The invention relates to a method for onebusaway compositions for wood and egabiosafety composition, which can be used in the construction of country houses, furniture and other industries

FIELD: chemistry.

SUBSTANCE: flame retardant composition contains perchlorovinyl resin, an organic solvent and a blowing agent. The organic solvent is a mixture of butyl acetate and acetone in ratio of 1:1. The blowing agent is a phosphorus-, boron- and chlorine-containing oligomer. The oligomer is obtained by reacting methylphosphite borate with epichlorohydrin in weight ratio of 3.5:3.0.

EFFECT: invention provides high flame retardation of coatings for fibre glass.

3 tbl

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