CN102838098A - Rare earth metal hypophosphite and preparation method and application of rare earth metal hypophosphite - Google Patents
Rare earth metal hypophosphite and preparation method and application of rare earth metal hypophosphite Download PDFInfo
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Abstract
The invention discloses rare earth metal hypophosphite higher in density and high in thermal stability, and a preparation method and an application of the rare earth metal hypophosphite as a flame retardant in a polymer material. The formula of the rare earth metal phosphate is Ln(H 2PO2)3(H2O).The preparation method of the rare earth metal hypophosphite comprises the steps of dissolving hypophosphite in water, adding sodium hydroxide to the solution to allow the pH of the solution to be 3.0-4.0, adding rare earth metal nitrate or an aqueous solution of rare earth metal chloride salt to be solution, stirring for 3-4 hours at 40-60 DEG C, cooling, filtering and washing to a reaction product, and obtaining the rare earth metal hypophosphite after drying. A halogen-free flame retardant polymer composite taking the rare earth metal hypophosphite as the flame retardant comprises the following components by mass percent: 40-90% of polymer and 10-25% of rare earth metal hypophosphite.
Description
Technical field
The invention belongs to halogen-free flameproof and plastics processing and application technology, be specifically related to a kind of rare earth metal hypophosphite and preparation method thereof, reach with it as the application of fire retardant in polymer materials.
Background technology
Polymer materials has become the important materials in fields such as industry, agricultural, national defence and science and technology through the fast development of nearly decades.Polymer materials is omnipresent, extensively permeates in all respects of human being's production life, is bringing into play enormous function.Yet polymer materials is easy to burning, has the potential fire hazard, therefore polymer materials is carried out fire-retardant finish and has seemed very necessary.The domestic halogen containing flame-retardant that generally adopts is handled polymer materials at present.Though halogen containing flame-retardant has advantages such as flame retarding efficiency height, production cost are low, because it can produce a large amount of poison gas in combustion processes, also can produce carcinogenic substance during the halogen containing flame-retardant that has burning, can bring serious harm to environment.Therefore, the research and development of halogen-free flame retardants and application have been the flame retardant area Development Trend.
As a kind of halogen-free flame retardants, hypophosphite receives the very big concern on domestic and international fire-retardant boundary in recent years, and its flame retarding efficiency in materials such as polyester and nylon almost can compare favourably with halogen containing flame-retardant, and in use can not impact environment.Hypophosphite is divided into two kinds of organic hypophosphite and inorganic hypophosphite.As far back as the seventies in 20th century and the eighties, be that organic hypophosphite of representative has been developed out and has been applied in the fire-retardant finish of polyester and nylon with diaryl hypophosphite, alkylaryl hypophosphite and dialkyl hypophosphorous acid salt.Yet this type of hypophosphite in building-up process, exist reactions step loaded down with trivial details, to conversion unit shortcoming such as have relatively high expectations.For example publication number is that the Chinese patent of CN 1280580A has been reported a kind of method that is obtained dialkyl hypophosphorous acid aluminium by raw materials such as element yellow phosphorus, alkylogen, alkene and metallic compounds through three step reaction.This method reactions step is very loaded down with trivial details, prepares at fire retardant to cause cost significantly to improve in the process, thereby has limited the application of fire retardant.
Inorganic hypophosphite preparation method is comparatively simple, and has the flame retardant properties similar with organic hypophosphite.In numerous inorganic hypophosphite, the flame retardant properties of hypo-aluminum orthophosphate in polyester and nylon is very excellent.For example all to have reported with hypo-aluminum orthophosphate be main fire retardant that polyester or nylon are carried out the technology of fire-retardant finish for U.S. Pat 2008/0090950 A1 and Chinese patent CN 1997698A, CN 1926192A, adds a small amount of hypo-aluminum orthophosphate and can make polyester or nylon obtain good flame retardant property.Yet the density of hypo-aluminum orthophosphate is less, and the fire retardant of unit mass has bigger volume, and heavy addition can cause declining to a great extent of polymer materials mechanical property.For this reason, invent a kind of density and its realistic price is arranged than big and the high halogen-free flame retardants of thermostability.
Summary of the invention
Less for overcoming the hypo-aluminum orthophosphate density that exists in the prior art; The shortcoming that heavy addition can cause the polymer materials mechanical property to decline to a great extent; The present invention proposes a kind of rare earth metal Hypophosporous Acid, 50 Salt And Preparation Method, with and as the application of fire retardant in polymer materials.
Reach above-mentioned technique effect for solving the problems of the technologies described above, the present invention has adopted following technical scheme:
A kind of rare earth metal hypophosphite, the molecular formula of said rare earth metal hypophosphite are Ln (H
2PO
2)
3(H
2O)
n, wherein Ln is any one among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb or the Dy; N is 0 or 1.
A kind of preparation method of rare earth metal hypophosphite may further comprise the steps:
Step 1) is dissolved in the water Hypophosporous Acid, 50;
Step 2) in above-mentioned solution, adds sodium hydroxide, make that the pH value of this solution is 3.0～4.0;
Step 3) adds the aqueous solution of rare-earth metal nitrate or rare earth metal chlorate in above-mentioned solution, stirred 3-4 hour down at 40-60 ℃, and cooling, filtration washing reaction product after the drying, promptly get the rare earth metal hypophosphite.
Further, said rare-earth metal nitrate is any one in Lanthanum trinitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Terbium trinitrate or the Dysprosium trinitrate
Further, said rare earth metal chlorate is any one in Lanthanum trichloride, Cerium II Chloride, praseodymium chloride, Neodymium trichloride, samarium trichloride, Europium trichloride, Gadolinium trichloride, terbium chloride or the Dysprosium trichloride.
A kind of with the Halogenless fire retarded polymer matrix material of rare earth metal hypophosphite as fire retardant, comprise that mass percent is 30～90% polymkeric substance, 10～20% rare earth metal hypophosphite, 0～30% toughener, 0～8% char-forming agent, 0～5% fire retarding synergist, 0～1% nucleator, 0～0.5% lubricant, 0～0.5% oxidation inhibitor and 0～5% toughner.
Further, said polymkeric substance is vibrin or nylon resin; Said polyester is selected from one or more in polyethylene terephthalate, polybutylene terephthalate, the PTT; Said nylon resin is selected from one or more in nylon 6, nylon 66, the nylon 12.
Further, said toughener is an alkali free glass fibre; Said char-forming agent is selected from one or more in epoxy resin, polycarbonate, polymethylmethacrylate, polymeric amide or the urethane; Said fire retarding synergist is selected from one or more in melamine polyphosphate, melamine cyanurate, melem, melamine pyrophosphate, silicate, borate, oxyhydroxide, double-hydroxide, the MOX; Said nucleator is selected from one or more in silicon-dioxide, talcum, mica, the lime carbonate; Said lubricant is the tetramethylolmethane stearate; Said oxidation inhibitor is four (3,5-di-t-butyl-4-phenylor) propionic acid; Said toughner is selected from one or more in MBS, Injecatable EVA Copolymer, the acrylonitrile-styrene-butadienecopolymer.
A kind of preparation method of Halogenless fire retarded polymer matrix material may further comprise the steps:
With being that 30～90% polymkeric substance and 10～20% rare earth metal hypophosphite mix by mass percentage; Get mixing raw material; In said mixing raw material, add mass percent and be 0～30% toughener, 0～8% char-forming agent, 0～5% fire retarding synergist, 0～1% nucleator, 0～0.5% lubricant, 0～0.5% oxidation inhibitor and 0～5% toughner; Be heated to 230～275 ℃ then; Through melt blending, again through extrude, tie rod, cooling, pelletizing, promptly get said Halogenless fire retarded polymer matrix material.
Because the utilization of such scheme, the present invention compared with prior art has advantage and effect:
Rare earth metal hypophosphite density of the present invention is big and thermostability is high, unit mass rare earth metal hypophosphite have a smaller volume, thereby less to the influence of polymer materials mechanical property.In addition, the flame retarding efficiency of rare earth metal hypophosphite in polyester or nylon material is similar with hypo-aluminum orthophosphate, and thermostability is higher.
Above-mentioned explanation only is the general introduction of technical scheme of the present invention, to understand technique means of the present invention in order can more knowing, and can to implement according to the content of specification sheets, below in conjunction with specific embodiment the present invention is described in further detail.
Embodiment
Embodiment 1:
The Hypophosporous Acid, 50 of 4.0g is dissolved in the 50ml water, and the pH value that adds sodium hydroxide to this solution is 3.0, and the 50ml aqueous solution that will contain the 7.0g Lanthanum trichloride more dropwise adds in the above-mentioned solution; Stirred 3 hours down at 40 ℃; Cooling, filtration washing reaction product after the drying, promptly get the Hypophosporous Acid, 50 lanthanum.
Embodiment 2:
The Hypophosporous Acid, 50 of 4.5g is dissolved in the 55ml water, and the pH value that adds sodium hydroxide to this solution is 3.5, and the 55ml aqueous solution that will contain the 7.5g Cerium II Chloride more dropwise adds in the above-mentioned solution; Stirred 3.5 hours down at 50 ℃; Cooling, filtration washing reaction product after the drying, promptly get cerous hypophosphite.
Embodiment 3:
The Hypophosporous Acid, 50 of 5.0g is dissolved in the 60ml water, and the pH value that adds sodium hydroxide to this solution is 4, and the 60ml aqueous solution that will contain the 8.0g samaric nitrate more dropwise adds in the above-mentioned solution; Stirred 4 hours down at 55 ℃; Cooling, filtration washing reaction product after the drying, promptly get the Hypophosporous Acid, 50 samarium.
Embodiment 4:
The Hypophosporous Acid, 50 of 5.5g is dissolved in the 55ml water, and the pH value that adds sodium hydroxide to this solution is 3.5, and the 60ml aqueous solution that will contain the 8.5g Gadolinium trinitrate more dropwise adds in the above-mentioned solution; Stirred 4 hours down at 60 ℃; Cooling, filtration washing reaction product after the drying, promptly get the Hypophosporous Acid, 50 gadolinium.
In addition; In these four embodiment, under the constant situation of other conditions, also can obtain corresponding rare earth metal hypophosphite with Lanthanum trinitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, europium nitrate, Terbium trinitrate, Dysprosium trinitrate, praseodymium chloride, Neodymium trichloride, samarium trichloride, Europium trichloride, Gadolinium trichloride, terbium chloride or Dysprosium trichloride replacement Lanthanum trichloride, Cerium II Chloride, samaric nitrate or Gadolinium trinitrate.
Application implementation example 1:
The prescription of according to the form below is got the raw materials ready, the polybutylene terephthalate that drying is good (calling PBT in the following text) master batch, cerous hypophosphite
,Melamine cyanurate mixes, and in twin screw extruder, is heated to 230～275 ℃, through melt blending, again through extrude, tie rod, cooling, pelletizing and oven dry, promptly obtain Halogenless fire retarded polymer matrix material of the present invention.Inject through injection moulding machine then and be used for oxygen index test and vertical combustion test bars, carry out combustionproperty and test.The oxygen index test is carried out according to international standard ASTM D2863, and the vertical combustion test is carried out according to international standard ASTM D3801.
In addition; Under should using the constant situation of other conditions among the embodiment; With one or more equivalent substitution cerous hypophosphites in Hypophosporous Acid, 50 praseodymium, Hypophosporous Acid, 50 neodymium, Hypophosporous Acid, 50 europium, Hypophosporous Acid, 50 terbium, Hypophosporous Acid, 50 dysprosium, Hypophosporous Acid, 50 lanthanum, Hypophosporous Acid, 50 samarium, the Hypophosporous Acid, 50 gadolinium, also can make the Halogenless fire retarded polymer matrix material reach the flame retardant properties similar with using embodiment with one or more equivalent substitution polybutylene terephthalates in polyethylene terephthalate, the PTT.
Application implementation example 2:
The prescription of according to the form below is got the raw materials ready; The polyethylene terephthalate that drying is good (calling PET in the following text) master batch, spun glass, Hypophosporous Acid, 50 lanthanum, melamine polyphosphate are heated to 265～275 ℃ in twin screw extruder; Through melt blending; Again through extrude, tie rod, cooling, pelletizing and oven dry, promptly obtain Halogenless fire retarded polymer matrix material of the present invention.Inject through injection moulding machine then and be used for oxygen index test and vertical combustion test bars, carry out combustionproperty and test.The oxygen index test is carried out according to international standard ASTM D2863, and the vertical combustion test is carried out according to international standard ASTM D3801.
In addition; Under should using the constant situation of other conditions among the embodiment, adopt one or more equivalent substitution melamine polyphosphates in melamine cyanurate, melem, melamine pyrophosphate, silicate, borate, oxyhydroxide, double-hydroxide, the MOX also can make halogen-free flame-retardant composite material reach the flame retardant properties similar with using embodiment.
Application implementation example 3:
The prescription of according to the form below is got the raw materials ready; Nylon 6 master batches, spun glass, cerous hypophosphite, melamine polyphosphate that drying is good are heated to 230～270 ℃ in twin screw extruder; Through melt blending; Again through extrude, tie rod, cooling, pelletizing and oven dry, promptly obtain Halogenless fire retarded polymer matrix material of the present invention.Inject through injection moulding machine then and be used for oxygen index test and vertical combustion test bars, carry out combustionproperty and test.The oxygen index test is carried out according to international standard ASTM D2863, and the vertical combustion test is carried out according to international standard ASTM D3801.
In addition, under should using the constant situation of other conditions among the embodiment, adopt one or more equivalent substitution nylon 6 in nylon 66, the nylon 12 also can make halogen-free flame-retardant composite material reach the flame retardant properties similar with using embodiment.
Application implementation example 4:
The prescription of according to the form below is got the raw materials ready; The PBT master batch that drying is good, spun glass, Hypophosporous Acid, 50 praseodymium, melamine cyanurate, polycarbonate, lime carbonate, tetramethylolmethane stearate, four (3; 5-di-t-butyl-4-phenylor) propionic acid, Injecatable EVA Copolymer mix, and in twin screw extruder, are heated to 230～240 ℃, through melt blending; Again through extrude, tie rod, cooling, pelletizing and oven dry, promptly obtain Halogenless fire retarded polymer matrix material of the present invention.Inject through injection moulding machine then and be used for oxygen index test, vertical combustion test and tensile strength test bars, carry out combustionproperty and Mechanics Performance Testing.The oxygen index test is carried out according to international standard ASTM D2863, and the vertical combustion test is carried out according to international standard ASTM D3801, and the tensile strength test is carried out according to international standard ASTM D638.
In addition; Under should using the constant situation of other conditions among the embodiment; With the lime carbonate that uses in one or more equivalent substitution present embodiments in silicon-dioxide, talcum, the mica; With the polycarbonate that uses in one or more equivalent substitution present embodiments in epoxy resin, polymethylmethacrylate, polymeric amide or the urethane; And should use the Injecatable EVA Copolymer that uses among the embodiment with one or more equivalent substitutions in MBS, the acrylonitrile-styrene-butadienecopolymer, also can make the Halogenless fire retarded polymer matrix material reach the fire-retardant and mechanical property similar with using embodiment.
Above-mentioned each embodiment just is to let the one of ordinary skilled in the art can understand content of the present invention and enforcement according to this in order technical conceive of the present invention and characteristics to be described, to be its objective is, can not limit protection scope of the present invention with this.The variation or the modification of every equivalence that the essence of content has been done according to the present invention all should be encompassed in protection scope of the present invention.
Claims (8)
1. rare earth metal hypophosphite, it is characterized in that: the molecular formula of said rare earth metal hypophosphite is Ln (H
2PO
2)
3(H
2O)
n, wherein Ln is any one among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb or the Dy; N is 0 or 1.
2. the preparation method of a rare earth metal hypophosphite according to claim 1 is characterized in that, may further comprise the steps:
Step 1) is dissolved in the water Hypophosporous Acid, 50;
Step 2) in above-mentioned solution, adds sodium hydroxide, make that the pH value of this solution is 3.0～4.0;
Step 3) adds the aqueous solution of rare-earth metal nitrate or rare earth metal chlorate in above-mentioned solution, stirred 3-4 hour down at 40-60 ℃, and cooling, filtration washing reaction product after the drying, promptly get the rare earth metal hypophosphite.
3. the preparation method of rare earth metal hypophosphite according to claim 2 is characterized in that: said rare-earth metal nitrate is any one in Lanthanum trinitrate, cerous nitrate, praseodymium nitrate, neodymium nitrate, samaric nitrate, europium nitrate, Gadolinium trinitrate, Terbium trinitrate or the Dysprosium trinitrate.
4. the preparation method of rare earth metal hypophosphite according to claim 2 is characterized in that: said rare earth metal chlorate is any one in Lanthanum trichloride, Cerium II Chloride, praseodymium chloride, Neodymium trichloride, samarium trichloride, Europium trichloride, Gadolinium trichloride, terbium chloride or the Dysprosium trichloride.
5. one kind with the Halogenless fire retarded polymer matrix material of the described rare earth metal hypophosphite of claim 1 as fire retardant, it is characterized in that: comprise that mass percent is 30～90% polymkeric substance, 10～20% rare earth metal hypophosphite, 0～30% toughener, 0～8% char-forming agent, 0～5% fire retarding synergist, 0～1% nucleator, 0～0.5% lubricant, 0～0.5% oxidation inhibitor and 0～5% toughner.
6. Halogenless fire retarded polymer matrix material according to claim 4 is characterized in that: said polymkeric substance is vibrin or nylon resin; Said polyester is selected from one or more in polyethylene terephthalate, polybutylene terephthalate, the PTT; Said nylon resin is selected from one or more in nylon 6, nylon 66, the nylon 12.
7. Halogenless fire retarded polymer matrix material according to claim 4 is characterized in that: said toughener is an alkali free glass fibre; Said char-forming agent is selected from one or more in epoxy resin, polycarbonate, polymethylmethacrylate, polymeric amide or the urethane; Said fire retarding synergist is selected from one or more in melamine polyphosphate, melamine cyanurate, melem, melamine pyrophosphate, silicate, borate, oxyhydroxide, double-hydroxide, the MOX; Said nucleator is selected from one or more in silicon-dioxide, talcum, mica, the lime carbonate; Said lubricant is the tetramethylolmethane stearate; Said oxidation inhibitor is four (3,5-di-t-butyl-4-phenylor) propionic acid; Said toughner is selected from one or more in MBS, Injecatable EVA Copolymer, the acrylonitrile-styrene-butadienecopolymer.
8. the preparation method of Halogenless fire retarded polymer matrix material according to claim 4 is characterized in that, may further comprise the steps:
With being that 30～90% polymkeric substance and 10～20% rare earth metal hypophosphite mix by mass percentage; Get mixing raw material; In said mixing raw material, add mass percent and be 0～30% toughener, 0～8% char-forming agent, 0～5% fire retarding synergist, 0～1% nucleator, 0～0.5% lubricant, 0～0.5% oxidation inhibitor and 0～5% toughner; Be heated to 230～275 ℃ then; Through melt blending, again through extrude, tie rod, cooling, pelletizing, promptly get said Halogenless fire retarded polymer matrix material.
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| CN103772748A (en) * | 2014-01-20 | 2014-05-07 | 合肥安聚达新材料科技有限公司 | Silica compound microencapsulation rare-earth metal hypophosphite and preparation method thereof |
| CN104448803A (en) * | 2014-12-01 | 2015-03-25 | 贵州凯科特材料有限公司 | Halogen-free flame-retardant long-fiber-reinforced nylon 6 composite material and preparation method thereof |
| CN104910591A (en) * | 2015-05-20 | 2015-09-16 | 合肥安聚达新材料科技有限公司 | Polymer material containing microencapsulated rare earth metal hypophosphite, and preparation method thereof |
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Application publication date: 20121226 |