Fire-resistant polymer material

FIELD: chemistry.

SUBSTANCE: invention relates to a polymer material, particularly a thermoplastic elastomer, which contains a halogen-free fire-retardant which is included in a polymer matrix. The fire-retardant contains (A) coated ammonium polyphosphate(s) in a crystalline modification II and/or derivatives thereof and (B) an oligomer or polymer derivative of 1,3,5-triazine or mixtures of several such derivatives. The fire-retardant also contains at least one compound selected from (C) phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphonates and phosphinates, stannates, molybdates or borates of elements of main subgroups II, III, IV or elements selected from Fe, Zn, Ti, Mn, Zr, Mo and (D) pre-condensed malamine derivatives, melamine salts and adducts thereof, ethylenediamine phosphate, piperazine phosphate, piperazine polyphosphate, 1,3,5-trihydroxyethylisocyanurate, 1,3,5-triglycidylisocyanurate and triallylisocyanurate. The weight ratio of component A to component B ranges from 10:1 to 1:1 and content of components A and B together ranges from 60 to 99 wt %, and content of components C and D together ranges from 1 to 40 wt % of the total weight of components A, B, C and D. Content of chlorine in component B is less than 1 wt % and/or content of chlorine in the entire polymer material is less than 1500 ppmw.

EFFECT: fire-retardant can be used in lower concentrations with high fire-retardant action, has low water-solubility and decomposes at higher temperatures compared with existing fire-retardants.

13 cl, 3 tbl, 11 ex

 

The technical field to which the invention relates.

The present invention relates to a polymeric material containing halogen-free flame retardant is included in or introduced into a polymer matrix (basis).

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 above all halogen-free flame retardants because they unlike flame retardants containing chlorinated or brominated organic is their connection, when you 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 kislotalimonnaya 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 be added in very large quantities, which leads to a change before ever the 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-threat-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 a polymeric material containing halogen-free flame retardant is included in or introduced into a polymer matrix, such halogen-free flame retardant must have the best in comparison with the prior art fire-retardant action is the Viy, to prevent the possibility of its application in polymer material in smaller concentrations with high flame retardant effect, have low solubility and decompose only at higher temperatures than the known flame retardants, preferably at temperatures higher than the temperature of the processing of the polymers, and the like polymeric material should have a high physico-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 a polymer material containing incorporated or introduced into the polymer matrix halogen-free flame retardant that contains at least the following components a and B:

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, and also contains at least one selected from among the following components b and G connection:

In: phosphates, pyrophosphates, polyphosphates, the organic and inorganic phosphonates, organic and inorganic phosphinate, stannate, molybdates or borates of the main group elements II, III, IV or items of auxiliary groups from among Fe, Zn, Ti, Mn, Zr, Mo,

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 D, and represents a thermoplastic elastomer (TPE).

In one of the embodiments of the invention the polymeric material contains a halogen-free 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, as well as Ulu which increases the compatibility with the polymer matrix, in which is injected fire retardant. Part a-covered form 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 which options 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 5 to 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 melamine salt and as the product is so stable, in the process of recycling plastics containing flame retardant is not the polycondensation reaction or decomposition reaction, which substantially 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 3% in thin plastic produce extremely high flame retardant effect.

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 water solubility. 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 PE is ernatively, accordingly 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 melamine, 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 is a procedure 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 of large size can not be sufficiently 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 the polyphosphate ammo the FL 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.

For your 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 Oli is the Windows 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 metal salts, especially dihydroorotase zinc Zn(H2PO4)2, zinc borate, zinc phosphate (Zn3(RHO4)2the 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)6stannate zinc ZnSnO3the boron phosphate VRO4dihydroorotase aluminum Al(N2RHO4)3the aluminum orthophosphate lO4metaphosphate aluminum [Al(RHO3)3]n, octamolybdate ammonium (OMA), and mixtures thereof. In relation to the first 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 quantities 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 from Osada cyanurate melamine, the 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.

Proposed in the invention the polymeric material is 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. 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 compared with plastics, containing a known flame retardants.

Preferred polymeric materials, namely, thermoplastic elastomers selected from filled and unfilled thermoplastic elastomers based on olefins, crosslinked thermoplastic elastomers based on olefins, urethanes, polyesters and spoliation, copolymers of styrene, poly the ministries of foreign Affairs 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/many other types that among other things due to the high relative content of oils that increase Flammability. Therefore, this item is unexpected is the fact that what is proposed in the invention 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 fillers allow you to make 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 next version proposed in the invention polymer material, the chlorine content of the component of the 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 parts per million, preferably less than 900 parts by weight of/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 the negative impact of Halogens.

In the next version proposed in the invention polymer material halogen-free flame 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, yet is how oleamide 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. 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 variant proposed in the invention polymer material 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 are some examples that are 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 RASplus is 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 tabular form. 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 melamine used the product Budit 315 company Budenheim Iberica.

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 comparative example is s.

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.

In the table below with the results of the tests according to standard UL94 reduction "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 by an industry consortium for standardization "Underwriters Laboratories". "UL94" denotes a class of onesidedness 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 5 is ispytannyj samples amounted to a total of less than 250, however, cotton fabric 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 testing are presented below in tabular form. KI in each case expressed as a percentage.

Determining the temperature of decomposition of the flame retardant

As another test of various flame retardant composition was subjected to heat separately without their incorporation into the polymer and thus determined the temperature at which occurred the 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 tempo is the temperature at a rate of 10 K/min During heating of the sample was measured by the change in its mass.

The results of this testing are presented below in tabular form.

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

Thanks primarily to the achievement of the highest class ognezashita with extremely small thickness of the test pieces of plastic and with a low relative concentration of flame retardant becomes possible to impart flame retardant having a very small thickness products from thermoplastic elastomers and 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 manufacturer for the housings of electric and electronic devices and for making other thin, accordingly, 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 retardant polymers. Proposed in the invention, the flame retardants are also extremely low smoke emission.

All offered in the invention, the flame retardants, respectively containing polymers, and thus proposed in the invention polymers 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.1234567 891011C1C2C3C4C5C6
Component
AndFR CROS 48934343434343434343434
AndFR CROS 403420
AndFR CROS 48434
Bthe triazine compound8888 88888885
Xpentaerythritol (comparative flame retardant)8
Inthe zinc pyrophosphate1,5
Inthe zinc borate1,5
Inthe aluminum phosphate1,5
Gcyanuret the chalk is on 333331,51,51,53
Ggrind3
Gmelon3
Gmelamine polyphosphate3
Additivemagnesium hydroxide454545 45
PlasticTPS555555555555555555555545
PlasticTPA5555
PlasticTVE55
PlasticPM75
PlasticHDPE
Note:
the abbreviation "SCC" means the block copolymers of the type styrene-ethylene-butylene-styrene;
the abbreviation "TPA" means the polyether block copolymers and polyamide;
the abbreviation "SF" means a thermoplastic polyolefin with seamless elastomeric phase;
the abbreviation "PP" means polypropylene;
the abbreviation "HDPE" means high density polyethylene.

1. Polymeric material containing incorporated or introduced into the polymer matrix halogen-free flame retardant that contains at least the following components a and B:
And: polyphosphate(s) of ammonium in the crystalline modification II and/or its derivatives, representing 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 or crosslinked polystyrene is e particles,
B: oligomeric or polymeric derivative of 1,3,5-triazine or a mixture of several such derivatives of the 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 3 to 50,
the content of chlorine in the component B halogen-free flame retardant is less than 1 wt.% and/or chlorine content throughout the polymeric material is less than 1500 parts by weight of/million
and also contains at least one selected from among the following components b and G connection:
In: phosphates, pyrophosphates, polyphosphates, organic and non-organic phosphonates, organic and inorganic phosphinate, stannate, molybdates or borates of the main group elements II, III, IV or items of auxiliary groups from among Fe, Zn, Ti, Mn, Zr, Mo,
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.% from the total mass to the components And, B, C, and G,
and represents a thermoplastic elastomer.

2. The polymeric material according to claim 1, characterized in that it contains a halogen-free flame retardant in an amount of 5 to 60 wt.%, preferably from 10 to 40 wt.%.

3. The polymeric material according to claim 1 or 2, characterized in that thermoplastic elastomer selected from the group including thermoplastic elastomers based on olefins, crosslinked thermoplastic elastomers based on olefins, urethanes, polyesters, and Capoliveri, copolymers of styrene, polyamides and copolyamids.

4. The polymeric material according to claim 1 or 2, characterized in that thermoplastic elastomer is selected from copolymers of styrene, preferably such as styrene-butadiene-styrene, styrene-etensuren-styrene, styrene-ecoprobe-styrene, styrene-Eten-ecoprobe-styrene and methacrylate-butadiene-styrene.

5. The polymeric material according to claim 1 or 2, characterized in that it contains additives, preferably selected from 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.

6. The polymeric material according to claim 1 or 2, characterized in that the halogen-free flame retardant in the amount of coverage of ammonium polyphosphates and/or derivatives thereof as the component comes the I 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.

7. The polymeric material according to claim 1 or 2, characterized in that the halogen-free flame retardant 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.

8. The polymeric material according to claim 1 or 2, characterized in that the halogen-free flame retardant 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.

9. The polymeric material according to claim 1 or 2, characterized in that the halogen-free flame retardant component selected from dihydroorotate zinc, zinc borate, zinc orthophosphate, zinc pyrophosphate, zinc polyphosphate, hydroxystannate zinc, stannate zinc, boron phosphate, dihydroorotate aluminum, aluminum orthophosphate, metaphosphate aluminum and mixtures thereof.

10. The polymeric material according to claim 1 or 2, characterized in that the halogen-free flame retardant (component D is selected from malema, melon, melam group, cyanurate melamine, melamine borate, melamine orthophosphate, melamine pyrophosphate, timelinedorothea and melamine polyphosphate.

11. The polymeric material according to claim 1 or 2, otlichuy is the, the chlorine content of the component B halogen-free flame retardant is preferably less than 0.8 wt.% and/or chlorine content throughout the polymeric material is preferably less than 900 parts by weight of/million

12. The polymeric material according to claim 1 or 2, characterized in that the halogen-free flame retardant 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 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.

13. The polymeric material according to claim 1 or 2, characterized in that the content of the halogen-free flame retardant free water is less than 0.6 wt.%, preferably less than 0.4 wt.%.



 

Same patents:

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

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: invention relates to a fire retardant resin composition which can be used for a component of an image output apparatus. The fire retardant composition contains a thermoplastic resin and a fire retardant. The thermoplastic resin used is an aliphatic polyester. The aliphatic polyester contains at least one compound selected from polylactic acid, polybutylene succinate, polycaprolactone, polytrimethylene terephthalate, and microbiologically produced polyhydroxyalkanoate. The fire retardant is obtained from phosphorated polysaccharide which is obtained by attaching thiophosphoric acid ester or phosphoric acid ester to a side chain of natural polysaccharide. The natural polysaccharide is selected from cellulose, chitin, chitosan, starch and derivatives thereof.

EFFECT: articles made from the fire retardant composition have improved fire resistance, mouldability and impact viscosity.

12 cl, 6 tbl, 1 dwg, 6 ex

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 for fire-proof treatment of synthetic fibres contains the following in pts. wt: methylphosphite borate 25.00-30.00, water 70.00-75.00, and additionally - ammonia, copper sulphate in the following ratio of components in pts. wt: methylphosphite borate-, water-, ammonia - 25.00-30.00, copper sulphate 0.75-3.00.

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: composition contains the following in pts. wt: methylphosphite borate 15, water 85, triethanolamine 0.25 and copper sulphate 0.38-1.50.

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

2 tbl, 4 ex

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 relates to preparation of fire-retardant solutions for treating wood and wood-based materials. The method is realised through condensation of carbamide and aldehyde in the presence of an amine with subsequent addition of orthophosphoric acid. Condensation is carried out in two steps. At the fist step the amine used is monoethanol amine and an ammonium salt of nitrile trimethylene phosphonic acid and condensation is carried out by successively mixing carbamide, 37% aqueous solution of formaldehyde, monoethanol amine and ammonium salt of nitrile trimethylene phosphonic acid in molar ratio equal to 1.0:1.3-2.5:0.1-0.2:0.005-0.08 respectively. At the second step acid condensation is carried out by adding orthophosphoric acid based on molar ratio of initial carbamide to orthophosphoric acid equal to 1.0:0.45-1.5.

EFFECT: method stabilises the technological process, improves fire-retardant properties of the end product, preserves outer appearance of the treated surface and reduces consumption during coating.

2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyphosphate derivatives of 1,3,5-triazine compound, preferably melamine polyphosphate, which have high heat resistance during processing and are used as antipyrene. The compounds have average degree of condensation n (number average) of over 20, pH value of a 10% suspension of the corresponding polyphosphate derivative in water at 25°C is equal to or greater than 5, molar ratio of 1,3,5-triazine compound to phosphorus (M/F) less than 1.1 and decomposition temperature above 320°C. The polyphosphate derivatives are obtained through thermal treatment of orthophosphate or condensed phosphate with average degree of condensation n (number average) less than 20 in an ammonium atmosphere at temperature ranging from 300 to 400°C until attaining average degree of condensation greater than 20 and molar ratio of 1,3,5-triazine compound to phosphate (M/F) less than 1.1.

EFFECT: increased heat resistance with low water-solubility and low conductivity of obtained compounds.

18 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing polymer material, enriched with phosphorus, which is used as a fireproof additive. A method is described for producing fireproof polymer material in two stages by reacting initial reagents in a reactor. The first stage involves reacting anhydrous phosphorous pentoxide with a second reagent, chosen from a group consisting of (a) diol, which is 1,3-propanediol and 1,4-butanediol, and (b) a mixture of cyclic ether and alcohol, obtaining polymer precursor material. The second stage involves reacting polymer precursor material with cyclic ether, for example ethylene oxide, propylene oxide and/or glycidol, obtaining the final product. Described also is a fireproof composition, which contains polymer material in form of a salt, obtained by reacting phosphoric ester with an amine, chosen from melamine and polyethylenimine.

EFFECT: obtaining water-insoluble intumescent polymer material which promotes reduction of flammability.

47 cl, 3 dwg, 5 tbl, 13 ex

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

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

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

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