CN105492520A - Flame retardant prepared from amide derivatives and process for making the same - Google Patents
Flame retardant prepared from amide derivatives and process for making the same Download PDFInfo
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Abstract
A method for manufacturing a melamine derivative mixture, comprising: firstly, reacting at least a nitrogen containing compound and a metallic phosphite or hydrogen phosphite salt in an aqueous solution; and secondly, heating the resultant reaction mixture in solid form, at a temperature comprised between 150-500 DEG C in the presence of an oxidant, to obtain a melamine derivative mixture. The thus obtained melamine derivative mixture is found to be useful as a flame retardant in epoxy polymers and help retain their physical properties.
Description
The cross reference of related application
This application claims the right of priority of the PCT international application no PCT/CN2013/082132 submitted on August 23rd, 2013, the full content of this application is combined in this by reference.
Technical field
The present invention relates to a kind of method for being manufactured melamine derivative mixture by the reaction between at least one amide derivatives and metal phosphinates, and the purposes of fire retardant is produced in described reaction.
Background technology
Fire retardant is the additive for suppressing or resist fire spreading used in plastics and other Industrial products.In recent years, due to the environmental advantage that halogen-free flame retardants is brought by limited levels of halogen, its industrial application has attracted very large research to pay close attention to.Conventional halogen-free flame retardants (HFFR) is a phosphonate HFFR, and as melamine pyrophosphate (MPP), this phosphonate to be widely used in thermoplastics and to have C
3h
6n
6(H
3pO
4)
ngeneral molecular formula.Under case of fire, the nitrogen in MPP and the combination of phosphoric can help to form crosslinked charcoal in applied product, therefore facilitate its flame retardant properties.
But when for thermoplastics, as the phosphonate flame-retardant additive that other are known, MPP has himself constraint and shortcoming.Such as, in conjunction with the thermoplastic system of MPP, find that waste gas and liquid ooze out, and these problems are considered to be caused by the phosphonate in these systems/synergistic agent interaction.
In addition, the many passing had in time finding in known phosphonate HFFR additive are moved and/or to be volatilized or in different thermoplasticity processing temperatures (especially from thermoplastics, extrude processing temperature) under decompose trend, cause this system to suffer the loss gradually of flame-retarding characteristic.In addition, these existing phosphonate HFFR additives because of its moisture-absorption characteristics be also known, these moisture-absorption characteristicss will finally cause the absorption of undesired moisture/moisture.
Therefore the present invention seeks to provide a kind of method of producing the economy of novel phosphonate HFFR additive, this novel phosphonate HFFR additive overcomes the aforesaid drawbacks of conventional phosphonate HFFR additive, and this novel phosphonate HFFR additive provides the good mechanical characteristics that gratifying and stable flame-retarding characteristic remains the polymkeric substance that it is increased to simultaneously.
Summary of the invention
The present invention be directed to a kind of melamine derivative mixture with flame-retarding characteristic, and its manufacture method.
In one aspect of the invention, provide a kind of method manufacturing melamine derivative mixture, the method comprises at least following steps:
I () provides the metal phosphinates of the pH had between 1 and 7 or the aqueous solution [solution (S)] of phosphorous acid hydrogen salt;
(ii) mix at temperature between 5 DEG C with 100 DEG C of this solution (S) and at least one nitrogenous compound [compound (N)], to obtain reaction mixture;
(iii) this reaction mixture that will be obtained in step (ii) by solid-liquid separating method is separated to obtain solid phase; And
(iv) heat at the temperature of this solid phase obtained in the step (iii) between 150 DEG C and 500 DEG C under the existence of oxygenant, to obtain this melamine derivative mixture,
Wherein this compound (N) is the compound with formula (I) or (II)
Wherein: R
1, R
2and R
3hydrogen, hydroxyl, amino or list-or two C independently
1-C
8alkylamino; Or C
1-C
8alkyl, C
5-C
16cycloalkyl ,-alkyl-cycloalkyl, each optionally by hydroxyl or C
1-C
4hydroxyalkyl, C
2-C
8thiazolinyl, C
1-C
8alkoxyl group ,-acyl group ,-acyloxy, C
6-C
12aryl ,-OR
1and-N (R
1) R
2replace; Or N-is alicyclic or N-is aromatic, the wherein alicyclic nitrogenous compound referring to ring-type of N-, as tetramethyleneimine, piperidines, tetrahydroglyoxaline pyridine, piperazine, and N-is aromatic refers to nitrogenous heteroaromatic cyclic cpds, as pyrroles, pyridine, imidazoles and pyrazine; X is phosphoric acid or tetra-sodium, and q is 1,2,3 or 4, and a is 1,2,3 or 4; Condition is R
1, R
2and R
3in at least one there is amino end group;
And wherein this metal phosphinates or phosphorous acid hydrogen salt refer to containing metallic cation and HPO
3 2-or H
2pO
3 -in a kind of salt of negatively charged ion.
The applicant has been surprisingly found that and can produce melamine derivative mixture by aforesaid method, and this mixture provides excellent flame-retarding characteristic and contributes to retaining the good mechanical characteristics of the polymkeric substance that it is increased to.Especially, in flammability test, the melamine derivative mixture produced by above method shows better stability and polymer compatibility compared with business MPP fire retardant, and can be effective as both gas phase and condensed phase fire retardant.In addition, compared with business MPP, also find that the trimeric cyanamide mixture obtained by method of the present invention has lower acidity in aqueous solution, which give better consistency in resinous substrates.
Therefore, in another aspect of the present invention, for be the melamine derivative mixture produced by aforesaid method, or there is the melamine derivative mixture of following feature:
(i) based on the gross weight of this melamine derivative mixture, the metallic element containing scope between 1wt% to 20wt%, between 5wt% and 25wt% scope phosphoric and between 15wt% and 40wt% the nitrogen element of scope; And
(ii) there is the mixture of the phosphorus species containing P (III) of molar percentage between 5% and 100%.
Of the present invention again in another, for be the purposes that fire retardant is produced in reaction in aqueous solution between at least one compound (N) and metal phosphinates or phosphorous acid hydrogen salt, wherein this compound (N) and this metal phosphinates or phosphorous acid hydrogen salt are as defined above.
The group be made up of the following can be selected from: trimeric cyanamide, melamine cyanurate, melamine phosphate compound, two melamine phosphate compound, melamine pyrophosphate compound, melem, melam, melon (melon), cyanurodiamide, cyanuramide and analogue for applicable compound (N) of the present invention.In a preferred embodiment, this compound (N) is trimeric cyanamide.
For the purposes of the present invention, " trimeric cyanamide " compound refers to the compound with formula (III):
According to the present invention, metal phosphinates or phosphorous acid hydrogen salt refer to containing metallic cation and HPO
3 2-or H
2pO
3 -in a kind of salt of negatively charged ion, wherein this metallic cation can derived from the metal be selected from by following every group formed: basic metal, alkaline-earth metal and transition metal.The example of this metal phosphinates or phosphorous acid hydrogen salt comprises: Li
2hPO
3, LiH
2pO
3, Na
2hPO
3, NaH
2pO
3, K
2hPO
3, KH
2pO
3, CaHPO
3, Ca (H
2pO
3)
2, ZnHPO
3, Zn (H
2pO
3)
2, MgHPO
3, Mg (H
2pO
3)
2, Al
2(HPO
3)
3and Al (H
2pO
3)
3, wherein CaHPO
3preferred.
In one embodiment of the invention, this solution (S) is the aqueous solution comprising this metal phosphinates or phosphorous acid hydrogen salt.
Usually, in the step (i) of the inventive method described above, this solution (S) is acid and the pH value had preferably between 1.0 and 6.0, more preferably between 1.5 and 4.5.As run through the application use, term " acidity " refers to the pH value lower than about 7, and this pH value refers to the pH of aqueous phase.Can by acid or alkali be added the pH value wherein regulating this solution (S) carefully.If this solution (S) has the pH value higher than the pH value expected, then by adding suitable acid (such as, HCl, HNO
3, H
3pO
3, H
3pO
2or H
3pO
4) regulate this pH value.On the contrary, if this solution (S) has the pH value lower than the pH value expected, then by adding suitable alkali (such as, NaOH, KOHKOH, Ca (OH)
2or NH
3) regulate this pH value.
In step (ii), the reaction of this compound (N) and solution (S), typically between 5 DEG C and 100 DEG C, preferably between 15 DEG C and 50 DEG C, and is carried out at the temperature of room temperature more preferably between 15 DEG C and 25 DEG C.
Reaction times of the step (ii) of the inventive method from 15 minutes to 3 hours, preferably can change from 30 minutes to 1 hour, and was chosen as time enough for the reaction mixture desired by producing with the productive rate of abundance.Especially, the reaction times of the step (ii) of the inventive method is to a great extent by the impact of other factors in the existence of temperature of reaction, the concentration of reactant and selection, catalyzer and the step (ii) selected by those skilled in the art.
Preferably, for the reaction in described step (ii), the mol ratio of the summation of compound (N) and phosphite and phosphorous acid hydrogen salt is at 1:5 to 5:1 in this solution (S), preferred 1:2 to 2:1, and in the scope of more preferably 1.1:1 to 1:1.1.
In the step (iii) of the inventive method, the reaction mixture coming to obtain in separating step (ii) by suitable solid-liquid separation method is to obtain solid phase, and wherein this solid-liquid separation method can be filtration, spraying dry or similar approach.
In following step (iv), will heat under the existence of oxygenant at the temperature of solid phase between 150 DEG C and 500 DEG C be separated from step (iii).Notably, this step (iv) causes the dry loss on the basis of the weight of the solid phase be separated from step (iii) between 10%wt and 40%wt usually.
In step (iv), the Heating temperature of setting is normally between 150 DEG C and 500 DEG C, preferably between 200 DEG C and 400 DEG C, and more preferably between 300 DEG C and 380 DEG C.
The oxygenant used in step (iv) can be selected from air, oxygen, gaseous oxidizer precursor as nitrogen oxide (N
xo
y) and ozone or this area in conventional other gaseous oxidizers.
Heat-up time in step (iv) is typically selected as 1 to 8 hour, preferably between 2 to 4 hours, and this existence depending on Heating temperature, catalyzer and other conditions used.Typically, the heat-up time in described step (iv) be by those skilled in the art select to obtain based on the dry loss of weight between 10%wt and 40%wt from the solid phase be separated in step (iii).
The invention still further relates to a kind of product obtained easily through the inventive method as described above.
The melamine derivative mixture generated thus is shown to the ultimate analysis of the finished product obtained afterwards in described step (iv) there is following feature:
(i) based on the gross weight of this melamine derivative mixture, the metallic element containing scope between 1wt% to 20wt%, between 5wt% and 25wt% scope phosphoric and between 15wt% and 40wt% the nitrogen element of scope; And
(ii) there is the mixture of the phosphorus species containing P (III) species of molar percentage between 5% and 100%.
Have been found that melamine derivative mixture according to the present invention provides the stability of enhancing.Can start to assess by the decomposition of measuring this mixture by thermogravimetry (TGA) stability of this mixture.The program of this analytical method is well known in the art.In one embodiment, this melamine derivative mixture has at N
2the TGA temperature for 3% weight loss of lower 300 DEG C or higher of atmosphere.In a preferred embodiment, this melamine derivative mixture has at N
2the TGA temperature for 3% weight loss of lower 330 DEG C or higher of atmosphere.Usually, the heating rate of this TGA analytical method is per minute 10 DEG C.
According to another aspect again of the present invention, provide a kind of polymer composition [composition (P)] comprising at least one polymkeric substance and melamine derivative mixture as described above.
Typically, at least one polymkeric substance in said composition (P) is selected from the group be made up of the following: polyphenyl ethers; Polyamide-based, as PA66, PA6, PA610; Or high temperature polyamide class (PPA/PA4.6/PA9T/PA66.6T/PA10T/PA6.6T, and polyamide-based blend, as PA/PET, PA/ABS or PA/PP); Polyester; Polycarbonate-based; Epoxy resin; Resol class; Acronitrile-butadiene-styrene (ABS); Styrene-acrylonitrile (SAN); The mixture (as PPO/HIPS) of high impact polystyrene (HIPS) and polyphenylene oxide; Styrene butadiene ribber and latex (SBR and SB); And halopolymer, as polyvinyl chloride (PVC); And the mixture of these polymkeric substance and blend; Expandable Polystyrene (EPS) (EPS); And polybutylene terephthalate (PBT).
In addition, said composition (P) can comprise one or more extra flame-retardant additives further, and these additives can strengthen its flame-retarding characteristic, as endothermic degradation, thermoshield, gas phase dilution, combustible portion dilution and free radical quencher.
Extra flame-retardant additive in said composition (P) is notably described in US6344158, US6365071, US6211402 and US6255371.
Preferably, the extra flame-retardant additive used in said composition (P) is selected from the group comprising the following:
A) phosphor-containing flame-proof additive, as:
-phosphine oxide, such as, as triphenylphosphine oxide, three-(3-hydroxypropyl) phosphine oxide and three-(3-hydroxy-2-methyl propyl group) phosphine oxides;
-phosphonic acids and salt thereof and phospho acid and salt thereof, such as the phospho acid of zinc, magnesium, calcium, aluminium or manganese, are notably the aluminium salt of the aluminium salt of diethyl phosphonic acids, dimethyl phosphonic acids, or the zinc salt of dimethyl phosphonic acids;
-cyclic phosphonate ester, as bisphosphate cyclic ester, this bisphosphate cyclic ester is such as Antiblaze1045;
-organophosphate, as triphenylphosphate;
-inorganic phosphate salt, as ammonium polyphosphate and sodium polyphosphate; And
-red phosphorus, under this red phosphorus can be found in various shape, as stabilization, coated, as powder,
B) nitrogenous flame-retardant additive, as: triazine, cyanuric acid and/or isocyanuric acid, trimeric cyanamide or derivatives thereof as cyanurate, oxalate, phthalate, borate, vitriol, phosphoric acid salt, polyphosphate and/or pyrophosphate salt, the condensation product of trimeric cyanamide as melem, melam, melon, three (hydroxyethyl) chlorinated isocyanurates, benzoguanamine, guanidine, wallantoin and glycoluril
C) Halogen flame-retardant additive, as:
-brominated flame-retardant additive, as the Saytex8010 of many bromines diphenyl oxide (PBDPO), brominated Polystyrene (BrPS), poly-(pentabromobenzyl acrylate), bromination titanium dioxide indenes, ten tetrabromo two phenoxy groups benzene (Saytex120), 1,2-two (penta-bromophenyl) ethane or Albemarle Corporation (Albemarle), tetrabromo-bisphenol and brominated epoxy oligomer.Notably can use following compound: the PDBS-80 from Chemtura Corporation (Chemtura), the SaytexHP3010 from Albemarle Corporation or the FR-803P from Dead Sea bromine group (DeaSeaBromineGroup), the FR-1210 from Dead Sea bromine group, octabromodiphenyl ether (OBPE), from the FR-245 of Dead Sea bromine group, from the FR-1025 of Dead Sea bromine group and F-2300 or F2400 from Dead Sea bromine group; And
-chloride flame-retardant additive, Tathagata is from the Dechlorane of Occidental Chemical Corp (OxyChem)
(CAS13560-89-9); And
D) inorganic fire-retarded additive, as ANTIMONY TRIOXIDE SB 203 99.8 PCT, aluminium hydroxide, magnesium hydroxide, cerium oxide, boron-containing compound is as lime borate.
These above flame-retardant additive compounds enumerated can be used alone or in combination in said composition (P).If necessary, carbonized agent and charing catalyst can also be added.
In addition, said composition (P) can comprise filler and strongthener and/or other additives further, as lubricant (such as, stearic acid or stearate, as calcium stearate), glass fibre or dripping inhibitor, as poly-(tetrafluoroethylene), such as, PTFESN3306.
Additionally, said composition (P) can also comprise the additive being usually used in manufacturing polymer composition, if softening agent, nucleator, catalyzer, light and/or thermo-stabilizer, antioxidant, static inhibitor, tinting material, pigment, matting agent, conductive agent are as carbon black, molded additive or analogue.
In order to prepare said composition (P), can any conventional means be passed through, such as, add these fillers and additive in the course of the polymerization process or as molten mixture.Preferably, in melting process, these additives add in this polymkeric substance by (as melt extruded in step process).Alternately, can solid processing in, in mechanical mixer, these additives are added to produce solid mixture in this polymkeric substance, this solid mixture is melted subsequently, such as, pass through extrusion.
Said composition (P) can be used as raw material at field of plastics processing, as the preparation of the goods formed by the following: injection molding, injection moulding/blown-moulding, extrude or extrude/blown-moulding.According to a common embodiment, said composition (P) is extruded with the form of rod, such as, in twin-screw extrusion equipment, then described rod is cut into particle.Then by melting the particle of above production and the composition of this melting is fed in injection moulding equipment prepares molded assembly.
As the goods be made up of said composition (P), example comprises vehicle part, as pipe fitting, groove, and vehicle body component, or the assembly under engine shield, and for the goods that Electrical and Electronic is applied, as junctor.
Be combined in this patent, patent application and the disclosure content of publication and the afoul degree of the description of the application by reference if any to term may be caused unclear, then this explanation should be preferential.
The present invention is further illustrated with reference to following instance.
The explanation of embodiment
Material
PA66: the fatty polyamide obtained from the advanced Polymer Company (SolvayAdvancedPolymers) of Su Wei;
PBT1200: the polybutylene terephthalate resin obtained from Changchun, Taiwan company limited (TaiwanChangchunLtd);
ExolitOP1230: from the phosphonous acid aluminium of Clariant Corporation (ClariantGmbH);
MPP (Melapur-200): from BASF AG (BASF)
Example 1
Under agitation by the H of 78g
3pO
3add the Ca (OH) of 70.86g
2with the H of 400g
2in the mixture of O.Subsequently, the mixture of generation is stirred 2.5h at 40 DEG C, then filter to obtain the solid mixture comprising Arizona bacilli.Dry 3h by this solid mixture deionized water wash and at 105 DEG C.
The Arizona bacilli mixture obtained as mentioned above of water and the 30.46g loading 120g in the 250mL reactor of mechanical stirrer will be equipped with.Under agitation, at room temperature the 85% orthophosphoric acid salt acid solution of 53.3g is added in the mixture of this generation.After interpolation, by this mixture stir half an hour and then filter remove insolubility solid to obtain settled solution.Then the trimeric cyanamide of 58g is under agitation slowly added in this filtrate the reaction being used for another 1 hour.After this, this mixture is evaporated to remove all water to obtain white solid.This white solid is heated at 330 DEG C 3 hours (wherein weight loss is 22%) to change into calcium trimeric cyanamide microcosmic salt.By using the ultimate analysis of gas chromatography system, thus obtained calcium trimeric cyanamide microcosmic salt contain by weight 27.68% N, C, the H of 2.40% of 12.24%, the Ca of the P of 19.68% and 7.09%.By calculating, in this calcium trimeric cyanamide microcosmic salt, the per-cent of remaining oxygen element is by weight 30.91%.Therefore, balance based on overall valence state, the valence state of the phosphoric in this calcium trimeric cyanamide microcosmic salt can be calculated by following formula (a):
Be 4.66.According to this valence state value, the molar percentage that can calculate P (III) in the phosphorus species in this calcium trimeric cyanamide microcosmic salt is 17%.
The further 10wt% water paste analyzing this calcium trimeric cyanamide microcosmic salt of display has the pH of 5.4, and the 10wt% aqueous solution of MPP has the pH being measured as 5.0.Therefore, compared with MPP, the calcium microcosmic salt obtained in this example has lower acidity and therefore gives better resinous substrates consistency.In addition, instruction is analyzed at N to the TGA of the product salt of this example
2at 383 DEG C, the weight loss of 3% is there is under atmosphere.
Example 2
The water of 400g and the Arizona bacilli mixture of 60g is loaded by being equipped with in the 500mL reactor of mechanical stirrer.Under agitation, at room temperature 38% hydrochloric acid soln of 91.34g is added in the mixture of this generation.After interpolation, by this mixture stir half an hour and then filter remove insolubility solid to obtain settled solution.Then the trimeric cyanamide of 144g is under agitation slowly added in this filtrate the reaction being used for another 1 hour.After this, this reaction mixture is filtered to remove aqueous solution and to obtain white solid.Then this white solid is heated at 330 DEG C 3 hours (wherein weight loss is 23%) to change into calcium trimeric cyanamide microcosmic salt.By ultimate analysis, thus obtained calcium trimeric cyanamide microcosmic salt contains the Ca of the N of 41.55%, the P of 7.27% and 7.98%.By calculating, in this calcium trimeric cyanamide microcosmic salt, the per-cent of remaining oxygen element is by weight 23.67%.Therefore, based on above formula (a), this product salt has the phosphorus valence state of 4.41, and the per-cent corresponding to the P (III) in its phosphorus species is 29.5%.
The further 10wt% water paste analyzing the calcium trimeric cyanamide microcosmic salt obtained in this example of display has the pH of 5.2, notably compare the acidity that the 10wt% aqueous solution of MPP is lower, and because herein is provided relatively better consistency in resinous substrates.In addition, instruction is analyzed at N to the TGA of this product salt
2at 369 DEG C, the weight loss of 3% is there is under atmosphere.
Example 3
The water of 400g and the Arizona bacilli mixture of 65.5g is loaded by being equipped with in the 500mL reactor of mechanical stirrer.Under agitation, at room temperature 38% hydrochloric acid soln of 91.34g is added in the mixture of this generation.After interpolation, by this mixture stir half an hour and then filter remove insolubility solid to obtain settled solution.Then the trimeric cyanamide of 144g is under agitation slowly added the reaction being used for another hour in this filtrate.After this, this mixture is filtered to remove aqueous solution to obtain white solid.This white solid is heated at 330 DEG C 3 hours to produce calcium trimeric cyanamide microcosmic salt, in heat-processed, wherein there is the weight loss of 23%.By ultimate analysis, thus obtained calcium trimeric cyanamide microcosmic salt contain 31.5% N, C, the H of 2.60% of 16.0%, the Ca of the P of 14.2% and 7.98%.By calculating, in this calcium trimeric cyanamide microcosmic salt, the per-cent of remaining oxygen element is by weight 27.72%.Therefore, based on above formula (a), this product salt has the phosphorus valence state of 4.11, and the per-cent corresponding to the P (III) in its phosphorus species is 44.5%.
The 10wt% water paste that further analysis is presented at the calcium trimeric cyanamide microcosmic salt obtained in above program also has the pH being greater than 5, notably compare the acidity that the 10wt% aqueous solution of MPP is lower, and because herein is provided relatively better consistency in resinous substrates.In addition, instruction is analyzed at N to the TGA of this product salt
2at 335 DEG C, the weight loss of 3% is there is under atmosphere.
Example 4
The water of 400g and the Arizona bacilli mixture of 65.5g is loaded by being equipped with in the 500mL reactor of mechanical stirrer.Under agitation, at room temperature 67% salpeter solution of 66g is added in the mixture of this generation.After interpolation, by this mixture stir half an hour and then filter remove insolubility solid to obtain settled solution.Then the trimeric cyanamide of 106g is under agitation slowly added the reaction being used for another hour in this filtrate.After this, this mixture is filtered to remove all aqueous solutions to obtain white solid.This white solid is heated at 330 DEG C 3 hours to produce calcium trimeric cyanamide microcosmic salt, in heat-processed, wherein there is the weight loss of 21%.By ultimate analysis, thus obtained calcium trimeric cyanamide microcosmic salt contain 27.68% N, C, the H of 2.39% of 13.21%, the Ca of the P of 18.55% and 7.89%.By calculating, in this calcium trimeric cyanamide microcosmic salt, the per-cent of remaining oxygen element is by weight 30.28%.Therefore, based on above formula (a), this product salt has the phosphorus valence state of 4.23, and the per-cent corresponding to the P (III) in its phosphorus species is 38.5%.
The 10wt% water paste that further analysis is presented at the calcium trimeric cyanamide microcosmic salt obtained in above program also has the pH being greater than 5, notably compare the acidity that the 10wt% aqueous solution of MPP is lower, and because herein is provided relatively better consistency in resinous substrates.In addition, instruction is analyzed at N to the TGA of this product salt
2at 400 DEG C, the weight loss of 3% is there is under atmosphere.
Test case 1: the mensuration of the fire retardancy of example 1-4
The calcium trimeric cyanamide microcosmic salt obtained from example 1-4 is tested as the fire retardant for epoxy resin separately.Definitely, by the monomer (see table 1) of these calcium trimeric cyanamide microcosmic salts from glass fibre and selection is mixed to prepare different resin sample in injection-molding machine, be cured subsequently and then extrude in granular form.In order to compare, prepare two extra resin sample in an identical manner, just not add according to calcium trimeric cyanamide microcosmic salt (CE1 and CE2 see in table 1) of the present invention.According to UL94 vertical combustion test procedure, the thickness of sample of 1.6mm and 0.8mm is used to test the flame retardant properties of these resin sample.
Table 1
As seen from Table 1, resin sample in conjunction with the calcium trimeric cyanamide microcosmic salt of example 1-4 reaches the V0 grade in UL94 vertical combustion test procedure separately, show gratifying fire prevention level and as compared to the resin not having salt to add (that is, CE1 with CE2) flame retardant resistance improving many.
Test case 2: comparing of the fire retardancy of example 1 and MPP
In order to compare, test contains the flame retardant resistance of the resin sample of the MPP of specified rate or the calcium trimeric cyanamide microcosmic salt of example 1.Definitely, by the product salt of MPP (melapur-200) or example 1 being mixed into glass fibre, the monomer (see following) of selection and Zn
3(BO
3)
2combination in (with the weight percent that often kind of composition is equal) prepare two resin sample, extrude in granular form with after fixing.Test the flame retardant properties of these two resin sample and physical property and result instruction in following table 2.
Table 2
As seen from Table 2, this resin sample in conjunction with the calcium trimeric cyanamide microcosmic salt of example 1 reaches the same good flame retardant resistance of the sample adding MPP with this, and compares the physical property that the latter notably improves.
Claims (16)
1., for the manufacture of a method for melamine derivative mixture, the method comprises at least following steps:
I () provides the metal phosphinates of the pH had between 1 and 7 or the aqueous solution [solution (S)] of phosphorous acid hydrogen salt;
(ii) mix at temperature between 5 DEG C with 100 DEG C of this solution (S) and at least one nitrogenous compound [compound (N)], to obtain reaction mixture;
(iii) this reaction mixture that will be obtained in step (ii) by solid-liquid separating method is separated to obtain solid phase; And
(iv) heat at the temperature of this solid phase obtained in the step (iii) between 150 DEG C and 500 DEG C under the existence of oxygenant, to obtain this melamine derivative mixture,
Wherein this compound (N) is the compound with formula (I) or (II)
Wherein: R
1, R
2and R
3hydrogen, hydroxyl, amino or list-or two C independently
1-C
8alkylamino; Or C
1-C
8alkyl, C
5-C
16cycloalkyl ,-alkyl-cycloalkyl, each optionally by hydroxyl or C
1-C
4hydroxyalkyl, C
2-C
8thiazolinyl, C
1-C
8alkoxyl group ,-acyl group ,-acyloxy, C
6-C
12aryl ,-OR
1and-N (R
1) R
2replace; Or N-is alicyclic or N-is aromatic, the wherein alicyclic nitrogenous compound referring to ring-type of N-, as tetramethyleneimine, piperidines, tetrahydroglyoxaline pyridine, piperazine, and N-is aromatic refers to nitrogenous heteroaromatic cyclic cpds, as pyrroles, pyridine, imidazoles and pyrazine; X is phosphoric acid or tetra-sodium, and q is 1,2,3 or 4, and a is 1,2,3 or 4; Condition is R
1, R
2and R
3in at least one there is amino end group;
And wherein this metal phosphinates or phosphorous acid hydrogen salt refer to containing metallic cation and HPO
3 2-or H
2pO
3 -in a kind of salt of negatively charged ion.
2. the method for claim 1, wherein this metal phosphinates or phosphorous acid hydrogen salt are selected from the group be made up of the following: Li
2hPO
3, LiH
2pO
3, Na
2hPO
3, NaH
2pO
3, K
2hPO
3, KH
2pO
3, CaHPO
3, Ca (H
2pO
3)
2, ZnHPO
3, Zn (H
2pO
3)
2, MgHPO
3, Mg (H
2pO
3)
2, Al
2(HPO
3)
3and Al (H
2pO
3)
3.
3. method as claimed in claim 2, wherein this metal phosphinates is CaHPO
3.
4. method according to any one of the preceding claims, wherein this compound (N) is selected from the group be made up of the following: trimeric cyanamide, melamine cyanurate, melamine phosphate compound, two melamine phosphate compound, melamine pyrophosphate compound, melem, melam, melon, cyanurodiamide and cyanuramide.
5. method as claimed in claim 4, wherein this compound (N) is trimeric cyanamide.
6. method according to any one of the preceding claims, wherein in step (i), this solution (S) is acid and has between 1.0 to 6.0, the pH value preferably between 1.5 and 4.5.
7. method according to any one of the preceding claims, wherein in step (ii), in this solution (S), compound (N) is at 1:5 to 5:1 with the mol ratio of this phosphite and/or phosphorous acid hydrogen salt, preferred 1:2 to 2:1, and in the scope of more preferably 1.1:1 to 1:1.1.
8. method according to any one of the preceding claims, wherein in step (iv), this Heating temperature is between 200 DEG C and 400 DEG C, and preferably between 300 DEG C and 380 DEG C.
9. method according to any one of the preceding claims, wherein in step (iv), the oxygenant used is selected from air, oxygen, nitrogen (N
xo
y) and ozone.
10. method according to any one of the preceding claims, wherein in step (iv), this heat-up time is from 1 to 8 hour, preferably between 2 to 4 hours, to obtain the dry loss of weight between 10%wt and 40%wt based on the solid phase be separated from step (iii).
11. 1 kinds of products obtained easily through method according to any one of the preceding claims.
The purposes of fire retardant is produced in 12. reactions in aqueous solution between at least one compound (N) and metal phosphinates or phosphorous acid hydrogen salt, and wherein this compound (N) and metal phosphinates or phosphorous acid hydrogen salt are as defined in claim 1.
13. 1 kinds of melamine derivative mixtures, is characterized in that:
(i) based on the gross weight of this melamine derivative mixture, the metallic element containing scope between 1wt% to 20wt%, between 5wt% and 25wt% scope phosphoric and between 15wt% and 40wt% the nitrogen element of scope; And
(ii) there is the mixture of the phosphorus species containing P (III) species of molar percentage between 5% and 100%.
14. melamine derivative mixtures according to claim 13, wherein this melamine derivative mixture has at N
2the TGA temperature for 3% weight loss of lower 300 DEG C or higher of atmosphere.
15. 1 kinds of polymer compositions [composition (P)], comprise at least one polymkeric substance and the melamine derivative mixture by obtaining any one of claim 1 to 10.
16. 1 kinds of polymer compositions [composition (P)], comprise at least one polymkeric substance and the melamine derivative mixture as described in claim 13 or 14.
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| CN107760023A (en) * | 2017-11-22 | 2018-03-06 | 江苏利思德新材料有限公司 | A kind of glass fiber enhanced nylon halogen-free flameproof compound system and its application |
| CN107936297A (en) * | 2017-11-22 | 2018-04-20 | 江苏利思德新材料有限公司 | Glass fiber enhanced nylon halogen-free flameproof compound system and its application in halogen-free flame-retardant glass fiber strengthens nylon material |
| CN108102361A (en) * | 2017-11-22 | 2018-06-01 | 浙江大学 | The halogen-free flameproof compound system of organic phosphorous acid aluminium collaboration and its application in fiberglass reinforced engineering plastics |
| WO2019100592A1 (en) | 2017-11-22 | 2019-05-31 | 江苏利思德新材料有限公司 | Halogen-free flame retardant compound system for glass fiber reinforced nylon and application thereof in halogen-free flame retardant glass fiber reinforced nylon material |
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