CN1079373C - Magnesium hydroxide solid solution, their production and use - Google Patents
Magnesium hydroxide solid solution, their production and use Download PDFInfo
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- CN1079373C CN1079373C CN95107156A CN95107156A CN1079373C CN 1079373 C CN1079373 C CN 1079373C CN 95107156 A CN95107156 A CN 95107156A CN 95107156 A CN95107156 A CN 95107156A CN 1079373 C CN1079373 C CN 1079373C
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Abstract
The present invention provides a magnesium hydroxide sosoloid, a manufacture method thereof and an application method thereof. The magnesium hydroxide sosoloid with a small amount of divalent metals has the same performance as that of magnesium hydroxide sosoloid with the uniform solid solution of divalent metal ions. The magnesium hydroxide sosoloid of the present invention is characterized in that in the magnesium hydroxide sosoloid shown in a formula (1) of Mg<1-x>M<2+>X (OH) 2 (in the formula, M<2+> represents at least one kind of divalent metal ion selected from Mn<2+>, Fe<2+>, Co<2+>, Ni<2+>, Cu<2+> and Zn<2+>, and x represents a value in a range of 0.001<=X<0.05). The present invention also provides a flame retardant with active ingredients of the magnesium hydroxide sosoloid, flame retardant resin and/or rubber compositions matched with the flame retardant, and a manufacture method of the magnesium hydroxide sosoloid.
Description
The present invention relates to new magnesium hydroxide solid solution, its manufacture method, this magnesium hydroxide solid solution is engaged in and forms flame retardant resin and/or rubber combination in resin and/or the rubber-like and contain the fire retardant of this magnesium hydroxide solid solution as effective constituent.
In more detail, the invention relates to by make the divalent transition metal element with high density near the inhomogeneous solid solution of magnesium hydroxide solid solution plane of crystal, can bring into play the new magnesium hydroxide solid solution of the effect of this divalent transition metal with the solid solution capacity of minimum, its manufacture method, the flame retardant resin and/or the rubber combination of the demonstration excellent flame retardancy that cooperates this sosoloid and form, physical strength, acid resistance etc., and about containing the fire retardant of this magnesium hydroxide solid solution as effective constituent.
Requirement to fire-retardantization of resin and rubber strengthens day by day.As fire-retardant method, mainly be to be and ANTIMONY TRIOXIDE SB 203 99.8 PCT simultaneously and with halogen now, but people require not use so-called halogen flame retardant consumingly, but be limited in safe metal hydroxides.But, for the flame retardant resistance of the level of making it, even the minimum magnesium hydroxide of shortcoming in the metal hydroxides also needs to cooperate more than about 70% (weight) with respect to resin and/or rubber.Therefore, just there is the problem of damaging the multiple rerum natura of resin and rubber itself with the degree that can not allow.
Therefore, the people among the inventor had proposed in the past with formula (2)
Mg
1-xM
2+ x(OH)
2(2) (in the formula, M
2+Expression Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+In at least a, x represents the numerical value of 0.001≤x≤0.9 scope) magnesium hydroxide solid solution of solid solution divalent transition metal of expression.When cooperating this magnesium hydroxide solid solution in resin and/or rubber, improve flame retardant resistance significantly, acid resistance etc. consequently, just can reach the flame retardant resistance of target level with the use level that is less than magnesium hydroxide.
But the result who further studies thereafter shows, even also there is the problem that must solve in the magnesium hydroxide solid solution of formula (2) expression.The first, compare M with magnesium raw material
2+Price height, particularly Co and the Ni of raw material are more outstanding.For example, at Mg
1-xNi
x(OH)
2In the magnesium hydroxide sosoloid of system, be the scope of 0.2≤x≤0.6 at x, flame retardant resistance and acid resistance are improved significantly than magnesium hydroxide.But, contain the sosoloid of such minor N i, just than magnesium hydroxide price height.The second, along with the M that is solid-solubilized in the magnesium hydroxide
2+Increase, the crystal growth and the dispersed tendency that worsens of this sosoloid occur.But its degree is because of each M of solid solution
2+Kind and different.
The inventor furthers investigate in order to address the above problem.It found that why magnesium hydroxide solid solution demonstrates the flame retardant resistance that is better than magnesium hydroxide, is because the M of solid solution
2+The catalytic effect and the beginning temperature of taking off crystal water lower than the beginning temperature of taking off crystal water of magnesium hydroxide.Find that in addition the effect that catalytic effect improves flame retardant resistance than the difference of the beginning temperature of taking off crystal water is bigger.
Therefore conclude, at least M
2+Catalytic effect, have only the M on the surface of exposing magnesium hydroxide solid solution that contacts with resin and/or rubber or may contact
2+Just contribution to some extent.So, as long as can make M
2+Optionally be solid-solubilized near the magnesium hydroxide crystal surface, and make M
2+Situation about being solid-solubilized in equably in the whole crystal of magnesium hydroxide is compared, just can be with remarkable few M
2+The catalytic effect of solid solution capacity performance and even solid solution phase same level.And at plane of crystal (M in this sosoloid near magnesium hydroxide solid solution
2+In the plane of crystal high density inhomogeneous solid solution in ground near magnesium hydroxide), in the disengaging of the temperature generation crystal water more much lower than magnesium hydroxide, therefore, in the crystallization water yield of low temperature disengaging, though compare M
2+High density the occasion that evenly is solid-solubilized in the whole crystal is few, but this effect also should be able to help flame retardant resistance to a certain degree.
Based on above reasoning, form the magnesium hydroxide solid solution of uniqueness of the present invention.
That is,, provide magnesium hydroxide solid solution, it is characterized in that according to the present invention, in magnesium hydroxide solid solution with formula (1) expression,
Mg
1-xM
2+ x(OH)
2(1) (in the formula, M
2+Expression is from Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+The middle at least a divalent-metal ion of selecting, x represents 0.001≤x＜0.5, better is 0.005≤x≤0.2, is more preferably the numerical value of 0.001≤x≤0.1 scope.) M
2+High density ground is inhomogeneous to be solid-solubilized near each plane of crystal.
In addition, according to the present invention, provide at M near the inhomogeneous solid solution of each plane of crystal
2+Concentration is the M in magnesium hydroxide solid solution
2+At least 2 times of solid solution capacity, at least 5 times above-mentioned magnesium hydroxide solid solution preferably.
In addition, also provide and contained the fire retardant of above-mentioned magnesium hydroxide solid solution as effective constituent.In addition, also provide flame retardant resin and/or the rubber combination that cooperates the above-mentioned fire retardant of 20-250 parts by weight with respect to the resin of 100 parts by weight and/or rubber.
In addition, according to the present invention, provide the manufacture method of above-mentioned magnesium hydroxide solid solution.
The magnesium hydroxide solid solution of formula (1), preferably to use crystal grain diameter be 0.2-4 μ m, be more preferably the scope of 0.4-2 μ m, and almost do not have secondary aggegation or this sosoloid of secondary agglutinative seldom.In more detail, to it is desirable to the offspring diameter be 0.2-4 μ m, be more preferably the 0.4-2 mu m range, and the BET specific surface area is 1-20m
2/ g, be more preferably 3-10m
2This sosoloid of/g.The above-mentioned scope of magnesium hydroxide solid solution is that the characteristics such as intermiscibility, dispersiveness, shaping or processibility, molding outward appearance, physical strength and flame retardant resistance in order will to cooperate in resin and/or rubber the time remain on the preferred range in the OK range.
In the magnesium hydroxide solid solution of formula (1), M
2+Be from Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+The middle at least a divalent-metal ion of selecting, M
2+When being a few metal ion species, x represents their summation.In above-mentioned divalent-metal ion, preferably Ni, Co, Mn it is desirable to Ni and Mn especially.Ni demonstrates significant effect aspect the acid resistance improving, and simultaneously, also makes flame retardant resistance, and heat-resistant aging etc. are good.Mn makes flame retardant resistance good especially, and simultaneously, it is a white, can be painted arbitrarily.
Magnesium hydroxide solid solution of the present invention is with M
2+The magnesium hydroxide solid solution difference of solid solution equably, the M of the close plane of crystal of measuring with XPS (the sub-spectrography of x ray photoelectric) or Auge
2+The M that concentration ratio is measured with chemical analysis
2+Solid solution capacity x is high significantly.In addition, for many M
2+, for example for Ni, the acid-respons speed at the initial stage that usefulness PHSTAT (statistics) method is measured is significant slower than homogenous solid solution.
The following describes manufacture method about magnesium hydroxide solid solution of the present invention.Under fully stirring, in the water medium system of homodisperse magnesium hydroxide or in this water medium system, add in the aqueous solution system of calcium chloride, sodium-chlor, magnesium chloride etc., add M
2+The aqueous solution, make it to react and make above-mentioned sosoloid.Temperature of reaction is about 20-200 ℃, and preferably about 70-150 ℃, the reaction times is different with temperature of reaction, is about 0.1-5 hour, preferably about 0.2-2 hour.In addition, M
2+Concentration lower be advisable.
Manufacture method according to the magnesium hydroxide solid solution of the invention described above can make M
2+To the crystal grain diameter of raw material-magnesium hydroxide and dispersed no any baneful influence ground only in the near surface solid solution of magnesium hydroxide.
The magnesium hydroxide that the present invention uses can in all sorts of ways and make.For example, under agitation, about below 40 ℃, preferably below 30 ℃, to add in the aqueous solution that contains magnesium ion of magnesium chloride etc. with respect to alkali such as the normal calcium hydroxides of the about 0.5-0.95 of magnesium, react, carry out a few hours hydrothermal treatment consists together with mother liquor at about 100-200 ℃ then, manufacture magnesium hydroxide.Again for example, also can make magnesium oxide, under the coexistence of monobasic acids such as acetate, carry out the method for hydration and make in about 1200-1600 ℃ following high-temperature calcination.
Magnesium hydroxide solid solution of the present invention, can directly use, also can utilize at least a the carrying out of the surface treatment agent of from the ester class of for example higher fatty acid, anion surfactant, phosphoric acid ester, coupler (silane system, titanic acid ester system, aluminium system) and polyvalent alcohol and lipid acid, selecting to use after the surface treatment as fire retardant.
The ideal example of surface treatment agent can be enumerated as follows: the higher fatty acid classes of carbonatoms more than 10 such as stearic acid, oleic acid, erucic acid, palmitinic acid, lauric acid, docosoic; An alkali metal salt of above-mentioned higher fatty acid; The sulfuric acid of higher alcohols such as Stearyl alcohol, oleyl alcohol; The sulfuric acid of polyglycol ether, acid amides conjugated sulfatases salt, ester conjugated sulfatases salt, ester in conjunction with sulfonate, acid amides in conjunction with sulfonate, ether in conjunction with sulfonate, ether in conjunction with alkylaryl sulphonate, ester in conjunction with alkylaryl sulphonate, acid amides in conjunction with anion surfactant classes such as alkylaryl sulphonates; The monoesters of ortho-phosphoric acid and oleyl alcohol, Stearyl alcohol etc. or diester or both mixtures, the phosphoric acid ester of their acid type or an alkali metal salt or amine salt etc.; Organosilane coupler classes such as vinyl Ethoxysilane, vinyl-three (2-methoxyl group-oxyethyl group) silane, γ-methacryloxypropyl trimethoxy silane, gamma-amino propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan; Titanic acid ester such as sec.-propyl three isostearoyl titanic acid ester, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, sec.-propyl three (N-amino-ethyl-amino-ethyl) titanic acid ester, sec.-propyl tridecyl benzenesulfonyl titanic acid ester are coupler; Aluminium such as acetyl alkoxyl group diisopropyl acid aluminium are the coupler class; The ester class of polyvalent alcohol such as Zerol, glyceryl monooleate and lipid acid.
The lining that can utilize known wet type or dry method to implement the magnesium hydroxide solid solution surface of the formula (1) that produced by surface treatment agent is handled.For example, as damp process, can slip with the aqueous adding magnesium hydroxide solid solution of aqueous or milkiness of this surface treatment agent in, mechanically carry out thorough mixing in about temperature below 100 ℃.As drying process, surface treatment agent can be added in the magnesium hydroxide pressed powder with aqueous, turbid liquid, solid state, utilize mixing machine such as Chinese house (ヘ Application シ ェ Le) mixing machine fully to stir, carry out thorough mixing in heating or under not heating.Can suitably select the addition of surface treatment agent, be benchmark with the weight of this magnesium hydroxide solid solution, and its addition preferably about 0.1 is to about 10% (weight).After carrying out surface treatment, as required, suitably select for example to wash, dehydration, granulation, drying, pulverizing, classification etc., make the end article shape.
The example of resin of Shi Yonging and rubber in the present invention, can enumerate: polyethylene, the multipolymer of ethene and other alpha-olefins, ethene and vinyl-acetic ester, the multipolymer of ethyl propenoate or methyl acrylate, polypropylene, the multipolymer of propylene and other alpha-olefins, polyvinyl chloride, polybutene-1, polystyrene, the multipolymer of vinylbenzene and vinyl cyanide, the multipolymer of ethene and propylene diene rubber or divinyl, vinyl acetate, polyacrylic ester, polymethacrylate, urethane, polyester, polyethers, thermoplastic resins such as polymeric amide, resol, melmac, Resins, epoxy, unsaturated polyester resin, thermosetting resins such as Synolac, EPDM, SBR, NBR, isobutylene-isoprene copolymer, polyisoprene rubber, chlorosulfonated polyethylene etc., but be not limited to these.
In the present invention, with respect to resin and/or rubber, the amount of allocating into of the magnesium hydroxide solid solution of formula (1) can suitably be selected according to the kind of the magnesium hydroxide solid solution of the kind of resin and/or rubber and formula (1), in general, resin and/or rubber with respect to 100 parts by weight, can allocate about 20-250 parts by weight into, preferably about 30-200 parts by weight are through surface treatment or do not carry out surface-treated formula (1) magnesium hydroxide solid solution.If the amount of allocating into of the magnesium hydroxide solid solution of formula (1) is more very few than above-mentioned scope, flame retardant resistance deficiency then, otherwise if too much, then reduction such as tensile strength, cantilever-type impact strength, therefore perhaps adverse influences such as acid resistance deterioration of Chan Shenging can suitably be selected and cooperate in above-mentioned use level scope.
For mixing of the magnesium hydroxide solid solution of resin and/or rubber and formula (1), compounding process does not have special restriction, can adopt to make both mixed uniformly any mixing devices.For example single shaft or biaxial extruder, cylinder, Ban Baili mixing roll etc.Manufacturing process is not had particular restriction yet, can adopt any known manufacturing process according to the kind of resin and/or rubber and the kind of needed molding etc.For example, injection molded, extrusion molding, blow molding, compression molding forming, spinning-shaping, calendaring molding, sheet material shaping, transfer mould shaping, lamination shaping, vacuum forming etc.
Resistance of the present invention burning property resin and/or rubber combination, as required, also can add the various additives except that the magnesium hydroxide solid solution of formula (1), for example at least a in carbon dust, ferrocene, anthracene, polyacetylene, red phosphorus, acrylic fibre, nickel oxide, the fibrous magnesium hydroxide.The amount of allocating into of these flame retardants with respect to the resin and/or the rubber of 100 parts by weight, preferably adopts about 0.01-10 parts by weight.
In addition, as other additive, as required, also can add lubricants such as docosoic zinc, docosoic magnesium, Zinic stearas, calcium stearate, Magnesium Stearate, lead stearate, aluminum stearate water-fast, acidproof (anti-albefaction) modifying agent of holding concurrently.The amount of allocating into of these lubricants with respect to the resin and/or the rubber of 100 parts by weight, preferably adopts about 0.1-10 parts by weight.
Flame retardant resin composition of the present invention can also be allocated other the habitual additives except that mentioned component into.Such additive for example can be enumerated: antioxidant, ultraviolet ray prevent agent, antistatic agent, pigment, whipping agent, softening agent, weighting agent, toughener, organic halogen fire retardant, linking agent etc.
Illustrate in greater detail the present invention according to embodiment below.In each following embodiment, unless otherwise noted, umber and % represent parts by weight and % (weight) separately.
Embodiment 1
In the calcium chloride of 2mol/L, add the normal sodium hydroxide of 2mol/L, form calcium hydroxide, with respect to the magnesium component in the ionic bittern that contains 2.0mol/L magnesium chloride and 0.8mol/L calcium chloride, add 0.9 normal above-mentioned calcium hydroxide down at 25 ℃, stir.The resultant of reaction of gained is directly injected autoclave without washing, and 170 ℃ of insulations 2 hours, hydrothermal treatment consists was carried out in pressurization.The average offspring diameter of the magnesium hydroxide of gained is 0.81 μ m, and the BET specific surface area is 7.0m
2/ g reaches good crystallization and dispersion.
From autoclave, take out magnesium hydroxide,, under agitation, the nickel chloride aqueous solution of 0.2mol/L is added in the above-mentioned magnesium hydroxide, make mol ratio Ni/Mg=0.02, under 70 ℃, carry out reaction in 1 hour after the temperature regulation to 70 ℃.Filter then, wash, a part is dewatered, drying.Residual most of redispersion is in 80 ℃ hot water, then under agitation, add 80 ℃ of hot water being dissolved with 3% the sodium stearate that is equivalent to magnesium hydroxide solid solution weight, keep carrying out surface treatment in about 30 minutes, filter then, wash, dehydration, granulation and drying.
Measure chemical constitution with chelatometry, measure the composition of plane of crystal with XPS.With determination of nitrogen adsorption BET specific surface area, with ultrasonic dispersing handle the test portion powder is dispersed in 0.2% sodium hexametaphosphate solution after, measure average offspring diameter with little track method.200mg test portion powder is added pH value is adjusted in 4 100 milliliters the deionized water, keep pH4 on one side, on one side at 30 ℃ down with 10.3 milliliters of (suitable 15mol%) needed time (T of N/10 hydrochloric acid of pH statistical technique mensuration consumption
15).
Do not measure the chemical constitution of chemical constitution, plane of crystal, acid resistance, BET specific surface area and average offspring diameter to carrying out the surface-treated test portion.It the results are shown in table 1:
Embodiment 2
After hydrothermal treatment consists finishes in embodiment 1, be cooled to 110 ℃.Then be pressed in the autoclave, under agitation kept 1 hour at 110 ℃ with the nickel chloride aqueous solution (mol ratio that is equivalent to Ni/Mg is 0.02) of ram pump with 0.2mol/L.After this carry out 1 identical operations, carry out surface treatment, filtration, washing, dehydration, granulation, drying afterwards with embodiment.The evaluation result of product is shown in table 1.
Embodiment 3
In embodiment 1, from autoclave, take out magnesium hydroxide, after filtering, washing, redispersion is in water.Then, under agitation,, continue to stir after 30 minutes, move in the autoclave, 140 ℃ of hydrothermal treatment consists of carrying out 1 hour at about 25 ℃ of nickel chloride aqueous solutions (mol ratio that is equivalent to Ni/Mg is 0.02) that add 0.4mol/L down.After this, carry out 1 identical operations, carry out surface treatment, filtration, washing, dehydration, granulation and drying then with embodiment.The evaluation result of product is shown in table 1.
Embodiment 4,5
In embodiment 2, (be equivalent to the Ni/Mg mol ratio is 0.01 (embodiment 4) to the filling rate of change nickel chloride aqueous solution, and 0.05 (embodiment 5) are in addition with embodiment 2 identical operations.The evaluation result of product is shown in table 1.
Comparative example 1
In embodiment 1, will filter with the part that autoclave carries out the magnesium hydroxide that hydrothermal treatment consists crosses, carry out drying after the washing.With remainder filter, washing back redispersion in water, under agitation, dissolved the aqueous solution of 3% the sodium stearate that is equivalent to magnesium hydroxide weight in 80 ℃ of addings, carry out surface treatment.After this filter, wash, dewater, drying.The evaluation result of product is shown in table 1.
Comparative example 2,3
Under agitation, the calcium hydroxide (20 ℃) with the 2mol/L of 18L adds the magnesium chloride of 40L and the mixed aqueous solution (Mg of nickelous chloride
2+=0.8mol/L, Ni
2+=0.3mol/L, comparative example 2) (Mg
2+=1.1mol/L, Ni
2+=0.01mol/L, comparative example 3) in (20 ℃).Reactant and mother liquor are moved in the autoclave together, carry out 4 hours hydrothermal treatment consists at 175 ℃.After this its part filtered, wash, drying, simultaneously, with remainder filter, washing back redispersion in water, carry out 1 identical operations with embodiment, carry out surface treatment with sodium stearate then.After this filter, wash, dehydration, granulation and drying.
Table 1
The equalization average secondary acid resistance of BET of coming to the surface
Learn to form and learn constituent particle diameter (T
15)
Ni/Mg mol ratio Ni/Mg mol ratio (m
2/ g) (μ m) (branch) embodiment 1 0.02 0.32 7.7 0.78 86 embodiment 2 0.02 0.27 7.1 0.80 71 embodiment 3 0.02 0.24 7.5 0.71 62 embodiment 4 0.01 0.13 7.0 0.80 20 embodiment 5 0.05 0.62 7.1 0.81 112 comparative examples 100 7.0 0.81 1.5 comparative examples 2 0.30 0.30 8.2 0.70 80 comparative examples 3 0.01 0.01 7.6 0.76 3.0
Embodiment 6
In embodiment 1, after carrying out hydrothermal treatment consists with autoclave, be cooled to 110 ℃, behind the nitrogen replacement autoclave, be pressed into the cobalt chloride solution that the mol ratio of Co/Mg the magnesium hydroxide in autoclave is equivalent to 0.02 0.1mol/L with ram pump, kept 1 hour at 110 ℃.After this, surface treatment, filtration, washing, dehydration, granulation and drying are carried out in operation then similarly to Example 1.The evaluation result of product is shown in table 2.
Embodiment 7
In embodiment 6, use with respect to the magnesium hydroxide mol ratio of Mn/Mg to be equivalent to 0.01 manganous nitrate and replace cobalt chloride, in addition, operation similarly to Example 6.The evaluation result of product is shown in table 2.
Embodiment 8
In embodiment 6, replace outside the cobalt chloride with iron protochloride, in addition, operation similarly to Example 6.The evaluation result of product is shown in table 2.
Embodiment 9,10
In embodiment 3, replace nickelous chloride, add the cupric nitrate (embodiment 9) of 0.1mol/L respectively, perhaps mixed aqueous solution (the Zn of zinc nitrate and nickelous chloride
2+=0.1mol/L, Ni
2+=0.1mol/L, embodiment 10), make the mol ratio that forms Cu/Mg=0.01, (Zn+Ni)/Mg=0.01 with respect to magnesium hydroxide, under agitation be warmed to 100 ℃, under this temperature, kept 1 hour.After this a part filter, wash, drying, remainder is operated similarly to Example 1, carries out surface treatment again.The evaluation result of product is shown in Table 2.
Table 2
The equalization average secondary of BET that comes to the surface
Learn to form and learn the constituent particle diameter
M
2+/ Mg mol ratio M
2+/ Mg mol ratio (m
2/ g) (μ m) embodiment 6 0.02 0.28 7.2 0.80 embodiment 7 0.01 0.15 7.5 0.81 embodiment 8 0.02 0.25 6.9 0.82 embodiment 9 0.01 0.16 7.0 0.83 embodiment 10 0.01 0.14 7.1 0.80
Embodiment 11-15, comparative example 4-6
With obtain among embodiment 1-10 and the comparative example 1-3, surface treated magnesium hydroxide solid solution or magnesium hydroxide, with respect to segmented copolymer polypropylene 100 parts by weight of ethene, mix with the proportioning shown in the table 3.Then, carry out mixingly at about 230 ℃ with forcing machine, after the small pieces vacuum-drying with gained, carry out injection molded, make sample at about 230 ℃.Sample is measured its incendivity and physical strength.Measurement result is shown in table 4.In addition, incendivity is that thick 1/16 inch sample is carried out UL 94VE test.
Table 3
Fire retardant use level M
2+X embodiment 11 embodiment 1 145 Ni 0.02 embodiment 12 embodiment 2 150 Ni 0.02 embodiment 13 embodiment 3 150 Ni 0.02 embodiment 14 embodiment 4 170 Ni 0.01 embodiment 15 embodiment 5 130 Ni 0.05 comparative example 4 comparative examples 1 205-0 comparative example 5 comparative examples 2 145 Ni 0.3 comparative example 6 comparative examples 3 195 Ni 0.01 notes of formula (1): each embodiment, comparative example cooperate the antioxidant Irganox (ィ Le ガ ノ ッ Network ス) 1010 (チ バ ガ ィ キ-(strain) manufacturing) of 0.2 parts by weight and Weston (ゥ ェ ス ト Application) 626 (manufacturings of GE company) of 0.1 parts by weight jointly.
Table 4
Incendivity tensile strength unit elongation cantilever-type impact strength
(kg.f/mm
2), (%), (kg.cm/cm) embodiment 11 V-O 1.75 30 15 embodiment 12 V-O 1.73 26 12 embodiment 13 V-O 1.72 25 11 embodiment 14 V-O 1.68 18 10 embodiment 15 V-O 1.86 42 20 comparative examples 4 V-O 1.60 56 comparative examples 5 V-O 1.71 24 13 comparative examples 6 V-O 1.64 87 notes: cantilever-type impact strength is tested with notched thick 1/16 inch sample.
Shown in the result of table 3 and table 4, in flame retardant test, thick UL94VE, 1/16 inch, the minimum use level that is used for qualified V-O is the magnesium hydroxide of 205 parts by weight.Under the situation of inhomogeneous sosoloid of the present invention, only use the nickel of 2mol%, be qualified with the use level of about 150 parts by weight in V-O.This is comparable to the roughly situation of the sosoloid of 30mol% nickel of even solid solution.
Embodiment 16-20, comparative example 7
Surface treated magnesium hydroxide solid solution or magnesium hydroxide with embodiment 6-10 and comparative example 1 obtain with respect to the nylon 6 of 100 parts by weight, mix with the proportioning shown in the table 5.Then, carry out mixingly with forcing machine at about 230 ℃, after the small pieces vacuum-drying with gained, carry out injection molded, make sample at about 230 ℃.Each sample is measured flame retardant resistance and physical strength.Measurement result is shown in table 6.
Table 5
Fire retardant use level M
2+X embodiment 16 embodiment 6 45 Co 0.02 embodiment 17 embodiment 7 45 Mn 0.01 embodiment 18 embodiment 8 45 Fe 0.02 embodiment 19 embodiment 9 45 Cu 0.01 embodiment 20 embodiment 10 45 Zn of formula (1), Ni 0.01 comparative example 7 comparative examples 1 70-0
Annotate: the common antioxidant Irganox 1010 that cooperates 0.2 parts by weight of each embodiment and comparative example.
Table 6
Incendivity tensile strength cantilever-type impact strength
(kg.f/mm
2) (kg.cm/cm) embodiment 16 V-O 8.50 3.1 embodiment 17 V-O 8.45 3.2 embodiment 18 V-O 8.30 3.2 embodiment 19 V-O 8.20 3.0 embodiment 20 V-O 8.52 3.2 comparative examples 7 V-O 7.50 2.4
Annotate: flammability test is carried out according to UL 94 VE with thick 1/8 inch sample.
Cantilever beam impact strength test (band breach) is tested with thick 1/8 inch sample.
Shown in the result of table 5 and table 6, in flammability test, with 1/8 inch thick, according to UL94VE test, be used for qualified minimum and join the magnesium hydroxide that content is 70 parts by weight in V-O.By contrast,, only use the Co of 1-2mol% etc. in the situation of inhomogeneous sosoloid of the present invention, can be qualified with the minimum use level of 45 parts by weight in V-O.
The effect of invention
According to the present invention, provide near each crystal surface partially solid solution Mn, Fe, Co, The magnesium hydroxide solid solution of the bivalent metal ions such as Ni contains this solid solution as effectively becoming The fire retardant that divides, the flame retardant resin that this fire retardant is engaged in resin and/or the rubber makes up Thing, and the manufacture method of this magnesium hydroxide solid solution. This kind magnesium hydroxide solid solution, Only use a small amount of bivalent metal ion, with the hydroxide that makes the even solid solution of bivalent metal ion Magnesium is the solid solution phase ratio, has the good fire retardant characteristic that is better than the latter.
Claims (7)
1. magnesium hydroxide solid solution is characterized in that, in magnesium hydroxide solid solution with formula (1) expression:
Mg
1－xM
2+ x(OH)
2 (1)
M
2+High density ground is inhomogeneous to be solid-solubilized near each plane of crystal place wherein said M
2+High density be at least average M
2+The twice of concentration, in formula (1), M
2+Expression is selected from Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+In at least a divalent-metal ion, x represents the numerical value of 0.001≤x＜0.5 scope.
2. the described magnesium hydroxide solid solution of claim 1, wherein, at M near the inhomogeneous solid solution of each plane of crystal
2+Concentration is average M
2+At least 5 times of concentration.
3. the preparation method of the described magnesium hydroxide solid solution of claim 1 comprises the following steps:
Under fully stirring, with M
2+The aqueous solution of salt adds homodisperse to be had in the aqueous solution of magnesium hydroxide, perhaps is added in the aqueous solution of magnesium hydroxide to be dissolved with in the aqueous solution of at least a salt of selecting from magnesium chloride, calcium chloride and sodium-chlor, makes it to react wherein said M
2+Salt is muriate or nitrate.
4. the purposes of the described magnesium hydroxide solid solution of claim 1 in preparation flame retardant resin and/or rubber combination, it is characterized in that described composition is made up of the resin of 100 parts by weight and/or the described magnesium hydroxide solid solution of claim 1 of rubber and 20-250 parts by weight.
5. the purposes of claim 4 is characterized in that, the M of the described magnesium hydroxide solid solution of claim 1
2+Be Ni
2+And/or Mn
2+
6. the purposes of claim 4, it is characterized in that the described magnesium hydroxide solid solution of claim 1 is that coupler, titanic acid ester are that coupler, aluminium are that at least a surface treatment agent in coupler and the polyhydric alcohol fatty acid ester is handled with being selected from higher fatty acid or its an alkali metal salt, anion surfactant, phosphoric acid ester, silane.
7. the described magnesium hydroxide solid solution of claim 1 is characterized in that in the purposes of preparation in the fire retardant, and described fire retardant contains with the magnesium hydroxide solid solution of formula (1) expression as effective constituent:
Mg
1－xM
2+ x(OH)
2 (1)
In the following formula, M
2+Expression is selected from Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+And Zn
2+In at least a divalent-metal ion, x represents the numerical value of 0.001≤x＜0.5 scope; In the magnesium hydroxide solid solution of formula (1) expression, near the uneven solid solution M in high density ground each plane of crystal
2+, wherein said M
2+High density be at least average M
2+The twice of concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107156A CN1079373C (en) | 1995-05-31 | 1995-05-31 | Magnesium hydroxide solid solution, their production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107156A CN1079373C (en) | 1995-05-31 | 1995-05-31 | Magnesium hydroxide solid solution, their production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1137024A CN1137024A (en) | 1996-12-04 |
| CN1079373C true CN1079373C (en) | 2002-02-20 |
Family
ID=5076200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95107156A Expired - Fee Related CN1079373C (en) | 1995-05-31 | 1995-05-31 | Magnesium hydroxide solid solution, their production and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1079373C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0498566A1 (en) * | 1991-02-06 | 1992-08-12 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Composite metal hydroxide and its use |
| EP0544502A1 (en) * | 1991-11-27 | 1993-06-02 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Anti-microorganism agent and anti-microorganism resin or rubber composition |
| JPH0761812A (en) * | 1993-08-19 | 1995-03-07 | Tateho Chem Ind Co Ltd | Production of magnesium hydroxide containing additive added thereto and production of magnesium oxide, containing additive therein and utilizing the same |
-
1995
- 1995-05-31 CN CN95107156A patent/CN1079373C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0498566A1 (en) * | 1991-02-06 | 1992-08-12 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Composite metal hydroxide and its use |
| EP0544502A1 (en) * | 1991-11-27 | 1993-06-02 | Kabushiki Kaisha Kaisui Kagaku Kenkyujo | Anti-microorganism agent and anti-microorganism resin or rubber composition |
| JPH0761812A (en) * | 1993-08-19 | 1995-03-07 | Tateho Chem Ind Co Ltd | Production of magnesium hydroxide containing additive added thereto and production of magnesium oxide, containing additive therein and utilizing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1137024A (en) | 1996-12-04 |
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