CN101906117A - Alkyl phosphinate polymer and preparation method and application thereof - Google Patents
Alkyl phosphinate polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an alkyl phosphinate polymer and a preparation method and application thereof. The method comprises the following steps of: filling a mixture of hypophosphorous acid or phosphinate and water or acetic acid into a pressure reactor with a jacket; when the mixture is heated to between 70 and 110 DEG C, adding alkyne into the pressure reactor through a pressure-reducing valve till the mixture in the pressure reactor is saturated; uniformly adding aqueous solution of free radical initiator into the obtained mixture with continuous stirring till reaching the required alkyne quantity, and then switching the alkyne into olefin; adding the olefin into the pressure reactor through the pressure-reducing valve till the mixture in the pressure reactor is saturated, uniformly adding a catalyst into the mixture, reacting the mixture for 8 to 12 hours, reducing the pressure of the pressure reactor, and cooling the mixture to 80 DEG C; and adding a metal compound into the pressure reactor to perform reaction, centrifuging the obtained solid, washing the solid by using water, and drying the solid in vacuum to obtain the alkyl phosphinate polymer. The invention also relates to the application of the alkyl phosphinate polymer serving as a flame retardant, a flame retardant composition and a flame-retardant polymer molding composition.
Description
Technical field
The present invention relates to a kind of alkyl phosphinate polymer and its production and application.
Background technology
The flame retardant properties of polyester or nylon can obtain by mixing various types of additives.Usually, halogenated compound, particularly many bromos aromatic compound has been used as the flame-retardant additive in this base polymer.It has been generally acknowledged that when these products were lighted, this product was suppressed at the free radical gas-phase reaction that takes place in the flame.This makes halogenated flame be used as the additive of the different types of polymers material that comprises polyester and nylon very at large.Yet at nearest about quindecennial, because ecological care, halogenated flame has been subjected to supervisory.At this moment, fire retardant industry will be towards thinking that the direction of more eco-friendly flame-retardant additive changes under pressure.The phosphorated product is the logical substitute of this class halogenated flame.In some applications, the phosphorated additive demonstrates the same high activity with halogenated flame, but the phosphorated additive seldom uses usually.Most of phosphorated fire retardant promotes to provide flame retardant activity with the combination that becomes charcoal by phase reaction with fixed attention, polymkeric substance carbonization.These methods obviously depend on the polymkeric substance that wherein uses this additive.Therefore, concrete phosphorated structure need be designed to the multiple polymers type.At the late 1970s and the beginning of the eighties, prepared the various salt of diaryl phospho acid, alkylaryl Hypophosporous Acid, 50 or dialkyl phosphinic acid, for example aluminium or zinc salt are for example in U.S. Patent No. 4,180,495; 4,208,321; With 4,208, illustrate in 322.These phosphinates are added among the PET or with polyethylene terephthalate copolymer and close.In the level of 10-20wt%, measure by the oxygen index (LOI) of unit, observe flame retardant resistance and improve.But existing fire retardant thermostability deficiency is difficult to satisfy the processing request of portioned product, as glass fiber enhanced nylon or polyester.So fire retardant or the fire-retardant combination of inventing a kind of high thermal stability have its actual value.
Summary of the invention
The object of the present invention is to provide a kind of alkyl phosphinate polymer and its production and application.
The alkyl hypophosphite polymkeric substance that the present invention proposes, the residual moisture content of this polymkeric substance is 0.01-10wt%, and average particle size particle size is 0.1-1000 μ m, and volume density is 80-800g/L, and its structural formula is as follows:
Wherein: R
1And R
2Be in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl or the isohexyl etc. any, M be in Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K or the protonated nitrogen base any, m is 1-4, and n is 1-5.Preferable, M be in aluminium, calcium, titanium, zinc, tin or the zirconium etc. any, the residual moisture content of alkyl phosphinate polymer is 0.01-0.1wt%, average particle size particle size is 50-500 μ m, volume density 200-700g/L, better average particle size particle size is 10-100 μ m.
Among the present invention, described protonated nitrogen base adopts ammonia, melamine, the protonated base of trolamine, especially NH4 '. melamine, urea, biuret, guanidine, Cyprex, wallantoin, the acetate guanamines, benzoguanamine, tolyl-triazole, benzotriazole, 2 one amino one 4 monomethyl pyrimidines, benzylurea, acetylene urea, glycolylurea, Malonamide is narrowed, dimethyl urea, diphenylguanidine, 5,5 one diphenyl hydantoins, N, a N ' diphenyl urea, ethene two (5 one triketone), glycine anhydride, tetramethyl-urea, melamine condensates, as melem, melam or mellon(e), or has a protonated base of this compound of higher condensation degree.
The preparation method of the alkyl phosphinate polymer that the present invention proposes, concrete steps are as follows:
(1) mixture of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is packed in the pressure reactor of strap clamp cover,, alkynes is added by reducing valve in pressure reactor, reach capacity when mixture has been heated to 70--110 ℃; Wherein: the weight ratio of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is 1: 4-7;
(2) with the aqueous solution of free-radical initiator under continuously stirring, under temperature 70-110 ℃, evenly join in step (1) the gained mixture, the amount until meeting the requirements of alkynes switches to alkene with alkynes then; Alkene is added until reaching capacity in pressure reactor by reducing valve, under 70-110 ℃ of temperature free-radical initiator is evenly joined in this mixture, reacted 8-12 hour, this pressure reactor that reduces pressure is cooled to after 80 ℃.In 1.5-2.5 hour, the metallic compound that adds Ca, Al, Sn, Ti, Zn or Zr reacts, and the gained solid is centrifugal, washes with water, and vacuum-drying promptly obtains required product.Wherein: the consumption of free-radical initiator is the 0.5-3% of Hypophosporous Acid, 50 or hypophosphite weight.Metallic compound add-on (mole number) is that the mole number of Hypophosporous Acid, 50 or hypophosphite is divided by m.
Among the present invention, alkynes is acetylene described in the step (1).
Among the present invention, free-radical initiator is an azo-compound described in the step (2), and described azo-compound is positively charged ion, azo-compound, non-cationic azo-compound, inorganic peroxide free-radical initiator or organo-peroxide free-radical initiator; Wherein: described cationic azo compound adopts 2,2,---azo two (2 one narrow basic propane) dihydrochloride or 2,2 '----azo, two (N, N,----dimethylene isobutyl is narrowed) in the dihydrochloride any, described non-cationic azo-compound adopts two isobutyronitriles, 4,4---azo two (4 one cyanopentanoic acid) or 2,2 '----azo two (2----methyl fourth eyeball), described inorganic peroxide free-radical initiator adopts hydrogen peroxide, ammonium peroxydisulfate, Sodium persulfate or Potassium Persulfate one to several, the organo-peroxide free-radical initiator adopts the oxidation dibenzoyl, ditertiary butyl peroxide or peracetic acid.
Among the present invention, the metallic compound of Ca, Al, Sn, Ti, Zn or Zr described in the step (2) be in metal oxide, metal hydroxides, metal hydroxides oxide compound, metal sulfate, metal acetate, metal nitrate, metal chloride or the metal alcoholate that contains Ca, Al, Sn, Ti, Zn or Zr any.
Among the present invention, alkene described in the step (2) is one to multiple kind in ethene, positive propylene, different propylene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene or the dissident's alkene.
The alkyl phosphinate polymer that the present invention proposes is as the application of fire retardant, flame retardant composition and flame-retardant polymer moulding compound.
The alkyl phosphinate polymer that the present invention proposes is added on the application of flame-retardant polymer moulding compound as fire retardant.
The alkyl phosphinate polymer that the present invention proposes is as the application of flame retardant composition, concrete grammar is as follows: will add additive in the alkyl phosphinate polymer, obtain flame retardant composition, wherein: the add-on of alkyl phosphinate polymer is 70wt-95wt%, and the add-on of additive is 5wt-30wt%.Average of obtained flame-retardant agent composition is drawn and is of a size of 0.1-3000 μ m, is preferably 0.1-1000 μ m, further is 1-100 μ m.
Among the present invention, described additive be in melamine phosphate, two melamine phosphates, five melamine triphosphates, three melamine diphosphates, four melamine triphosphates, six melamine pentaphosphates, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate salt, melamine polyphosphate, melam polyphosphate, melem polyphosphate or mellon(e) polyphosphate, zn cpds, magnesium compound, calcium cpd, aluminum compound, manganic compound or carbodiimide or (many) isocyanic ester any.Preferable is three (hydroxyethyl) chlorinated isocyanurates and aromatic multi-carboxy acid's oligopolymer vinegar, benzoguanamine, three (hydroxyethyl) chlorinated isocyanurates, wallantoin, glycoluril, melamine, melamine cyanurate, urea cyanuric acid vinegar, Dyhard RU 100 or or guanidine in any.Described zn cpds is zinc oxide, zinc hydroxide, aqua oxidation zinc, zinc carbonate, zinc, zinc hydroxyl stannate, zinc silicate, zinc phosphate, zinc borate or zinc molybdate; Acid amide in described carbodiimide such as carbonyl diurethane are own.Described magnesium compound such as magnesium oxide, magnesium hydroxide, hydrotalcite, two hydrotalcites, magnesiumcarbonate or magnesium calcium carbonate.Described calcium cpd is as calcium hydroxide, calcium oxide, hydrocalumite. as described in zn cpds such as zinc oxide (as active zinc flower), zinc hydroxide, aqua oxidation zinc, zinc carbonate (as alkaline carbonic acid zinc, Carbon Dioxide zinc), zinc, zinc hydroxyl stannate, zinc silicate, alkaline phosphatase zinc, alkaline zinc borate, alkaline zinc molybdate or alkaline zinc sulphide.Described aluminum compound such as aluminum oxide, aluminium hydroxide, hydrargillite or aluminum phosphate.Described manganic compound such as manganese oxide, manganous hydroxide.Described tin compound such as stannic oxide.
The application of the flame-retardant polymer moulding compound that the present invention proposes, concrete grammar is as follows:
Alkyl phosphinate polymer, flame retardant composition, polymkeric substance and additive are mixed in mixing tank, and fusion is even in the compounding associated plant at a certain temperature, and products therefrom is extruded, and cooling promptly gets desired product.
Among the present invention, described polymkeric substance is the polymkeric substance of single or diolefine, or single diolefine is put in poison or with the co-polymer of other vinyl monomer.Or polystyrene (polystyrene 143E (BASF), poly-(p-methylstyrene),, or vinylbenzene and α poly---(α--vinyl toluene)), or vinylbenzene--vinyl toluene and diene or with the multipolymer of acrylic acid derivative, or derived from diamines and dicarboxylic acid, or aminocarboxylic acid, or the polymeric amide of corresponding lactan and copolyamide, or derived from dicarboxylic acid and glycol, and/or hydroxycarboxylic acid, or the polyester of corresponding lactone.
Wherein: the polymer poly propylene of described single or diolefine, polyisobutene, poly-1 one butylene, poly-4 monomethyls, one 1 one amylenes, polyisoprene, or polyhutadiene, or cycloolefin are as the polymkeric substance of cyclopentenes or norbornylene; Or polyethylene (if suitable being crosslinked), as high density polyethylene(HDPE) (HDPE), high-density High molecular weight polyethylene (HDHMWPE), high-density ultrahigh molecular weight polyethylene(UHMWPE) (HDUHMWPE), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (VLDP), or these mixture.
Described single or diolefine mutually or with the multipolymer of other vinyl monomer, as Ethylene propylene copolymer, linear low density polyethylene (LLDPE), or the mixture of itself and new LDPE (film grade) (LDPE), or propylene one 1 one butylene copolymers, propylene one isobutylene copolymers, ethene one 1 one butylene copolymers, ethene one hexene copolymer, ethene monomethyl pentene copolymer, ethene one heptene multipolymer, ethene one octene copolymer, propylene one butadienecopolymer, iso-butylene one isoprene copolymer, ethene one alkyl acrylate copolymer, ethene monomethyl alkyl acrylate copolymer, the intoxicated multipolymer of ethene one vinyl acetate, or the multipolymer of itself and carbon monoxide, or ethene one acrylic copolymer or its salt (from aggressiveness), perhaps ethene and propylene and diene, as hexadiene, Dicyclopentadiene (DCPD), or the ter-polymers of ethylidene norbornene; Or the mutual mixture of these multipolymers, as the polypropylene/ethylene propylene copolymer, the LDPE/ Ethylene vinyl accetate copolymer, LDPE/ ethene one acrylic copolymer, the LLDPE/ Ethylene vinyl accetate copolymer, LLDPE/ ethene one acrylic copolymer, or replace or atactic polyolefin/carbon monoxide multipolymer, or itself and other polymkeric substance, as with the mixture of polymeric amide.α--vinyl toluene and diene or with the multipolymer of acrylic acid derivative, as styrene-butadiene, vinylbenzene one acrylonitrile, vinylbenzene monomethyl alkyl acrylate, styrene-butadiene one alkyl acrylate, with styrene-butadiene monomethyl alkyl acrylate, vinylbenzene one maleic anhydride, vinylbenzene one acrylonitrile one methyl acrylate.
Described by styrol copolymer and another polymkeric substance such as polyacrylic ester, diene polymer, or the high-impact mixture of ethene one propylene diene ter-polymers composition; Perhaps cinnamic segmented copolymer, as styrene-butadiene one vinylbenzene, vinylbenzene one isoprene one vinylbenzene, vinylbenzene one ethylene/butylene one vinylbenzene, or vinylbenzene one ethylene/propene one cinnamic segmented copolymer.
Described polymkeric substance is derived from diamines and dicarboxylic acid, and/or aminocarboxylic acid, or the polymeric amide of corresponding lactan and copolyamide, as polymeric amide---2,12, polymeric amide---4 (poly-one 4 one aminobutyric acids), polymeric amide---4,6 (poly-(tetramethylene adipamides), polymeric amide---6 (polycaprolactams, poly-6 one hexosamines) polymeric amide---6,6 (poly-(N, a N ' hexa-methylene adipamide),), polymeric amide----6,9 (poly-(hexa-methylene nonane two acid amides), polymeric amide---6,10 (poly-(hexa-methylene sebacoyl amine)), polymeric amide---6,12 (poly-(hexa-methylene dodecane diamide)), polymeric amide----6/6,6 (poly-(the hexa-methylene hexanamide has phthalein amine in oneself altogether)), polymeric amide----7 (poly----7---aminoheptylic acid), polymeric amide---7,7 (poly-heptamethylene pimeloyl amine), polymeric amide--8 (poly----8----aminocaprylic acid), polymeric amide---8,8 (poly-eight methylene radical suberamides), polymeric amide--9 (poly----9---amino-nonanoic acid), polymeric amide---9,9 (poly-nine methylene radical pelargonamides), polymeric amide--10 (poly---the amino capric acid of-10---), polymeric amide---10,9 (poly-(decamethylene pelargonamides)), polymeric amide----10,10 (poly-decamethylene certain herbaceous plants with big flowers acid amides), polymeric amide----11 (poly----11----aminoundecanoic acid), polymeric amide---12 (polylauryllactam), derived from---dimethylbenzene, the aromatic poly of diamines and hexanodioic acid; The polymeric amide of making by hexamethylene-diamine and m-phthalic acid and/or terephthalic acid (polyhexamethylene isophthaloyl amine or polyhexamethylene terephthalamide), if it is suitable, make as properties-correcting agent by elastomerics, as poly----2,4,4 one tri-methyl hexamethylene terephthalamides or poly------phenylene isophthaloyl amine; Above-mentioned polymeric amide and polyolefine with olefin copolymer, and from aggressiveness, or connect or the grafted elastomerics with valence bond; Or and polyethers, as with polyoxyethylene glycol, polypropylene glycol, or the segmented copolymer of polytetramethylene glycol; Perhaps by by EPDM or by the copolyamide of ABS modification or polymeric amide; The perhaps polymeric amide of condensation (" RIM polymeric amide system in treating processes ").
Described polymkeric substance is derived from dicarboxylic acid and glycol, and/or hydroxycarboxylic acid, or the polyester of corresponding lactone, and as polyethylene terephthalate, (Celanex 2500, and Celanex 2002, Celanese for polybutylene terephthalate; Ultradur, BASF), poly-(1,4---hydroxymethyl-cyclohexane terephthalate), poly-hydroxybenzoate, and derived from the segmented polyetherester of the polyethers with hydroxyl end groups; And by polycarbonate or by the polyester of MBS modification.
Among the present invention, described compounding associated plant adopts single screw extrusion machine or multi-region screw extrusion press.Effective spiro rod length (L) of the forcing machine (compounding associated plant) of its screw diameter (D) multiple is 4-200D, and that preferable is 10-50D.
Among the present invention, melt temperature is: polystyrene is 170-200 ℃, polypropylene is 200-300 ℃, polyethylene terephthalate (PET) is 250-290 ℃, polybutylene terephthalate (PBT) is 230-270 ℃,-6.6 (PA6,6) are 260-290 ℃ to polymeric amide---6 (PA6) are 260-290 ℃, polymeric amide--.
The production of flame retardant plastics moulding compound and plastic molded articles, processing, and test
Flame retardant compositions is with polymeric aggregate and optionally mix with additive, and adds in twin screw extruders down in temperature 230 to 260 ℃ (GRPBT) or 260 to 280 ℃ (GRPA 66).The polymer-extruded thing of homogenize is drawn, in water-bath, cool off, and granulation subsequently.
After thorough drying, with moulding compound in injection moulding machine melt temperature 240 to 270 ℃ (GRPBT) or 260 to 290 ℃ (GRPA 66) down processing obtain test sample. measure UL94 (insurance laboratory) burning grade at test sample from the test sample used thickness 1.6mm of every kind of mixture. following burning grade is provided by UL94:
V 1: the time that burns away never was longer than 10 seconds, and the summation of the time that burns away when lighting for 10 times is no more than 50 seconds, does not have drippage on fire, and sample burns down fully, and sample never was longer than 30 seconds in the twilight sunset of lighting after finishing perdurability
V 1: never be longer than 30 seconds in the time that burns away of lighting after finishing, the summation of the time that burns away when lighting for 10 times is no more than 250 seconds, and the twilight sunset of sample after lighting end never was longer than 60 seconds perdurability, and other standard is as V 1
V 1: cotton indicator is dripped by fire. light; Other standard is as V 1
(ncl) can not classify: do not satisfy burning grade V 1.
Flame-retardant polymer moulding compound of the present invention is applicable to producd fibers, and film, or moulded work are particularly useful for the Electrical and Electronic field.The present invention preferably uses flame-retardant polymer moulded work of the present invention as lamp part, as lamp socket and lamp bracket, and plug and insert wiring board, coil stand is used for the shell of electrical condenser or contactor and contactor, relay1 case and reverberator.
Beneficial effect of the present invention is: a kind of high heat-stable compound is provided, is particularly useful for as fiberglass reinforcing polyester the fire retardant of nylon.
Embodiment
Following embodiment further specifies the present invention.
Embodiment 1:
At first prepare the dialkyl phosphinic acid aluminium polymer.For this reason, the mixture of the sodium hypophosphite of 150KG and 750kg deionized water is packed in the pressure reactor of 2000L strap clamp cover.In case reaction mixture has been heated to 100 ℃, acetylene is added until reaching capacity in reactor by the reducing valve that is set to 3 crust.With 2.0KG2,2 ' one azos two (one dimethylene isobutyl is narrowed for N, the N) solution of dihydrochloride in 200KG water evenly is fed in this mixture under temperature 100---105 ℃ under continuously stirring.Consume acetylene 18.5KG altogether.Acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 39.6KG.This reactor and being cooled to after 80 ℃ reduces pressure.In 2 hours, add the Al that contains of 290KG50% concentration
2O
3The Al of 16.53wt%
2(SO
4)
3The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of following vacuum-dryings.Obtain product: phosphorus content: 26.5% (26.9% calculated value) decomposition temperature: 425 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 2:
At first prepare the dialkyl phosphinic acid aluminium polymer.For this reason, the mixture of the sodium hypophosphite of 150KG and 750kg deionized water is packed in the pressure reactor of 2000L strap clamp cover.In case reaction mixture has been heated to 100 ℃, acetylene is added until reaching capacity in reactor by the reducing valve that is set to 3 crust.With 2.0KG2,2 ' one azos two (one dimethylene isobutyl is narrowed for N, the N) solution of dihydrochloride in 200KG water evenly is fed in this mixture under temperature 100---105 ℃ under continuously stirring.Consume acetylene 24.5KG altogether.Acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 26.5KG.This reactor and being cooled to after 80 ℃ reduces pressure.In 2 hours, add the Al that contains of 290KG50% concentration
2O
3The Al of 16.53wt%
2(SO
4)
3The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of following vacuum-dryings.Obtain product: phosphorus content: 28.4% (28.1% calculated value) decomposition temperature: 435 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 3:
At first prepare the dialkyl phosphinic acid aluminium polymer.For this reason, the mixture of the sodium hypophosphite of 150KG and 750kg deionized water is packed in the pressure reactor of 2000L strap clamp cover.In case reaction mixture has been heated to 100 ℃, acetylene is added until reaching capacity in reactor by the reducing valve that is set to 3 crust.The solution of 2.0KG Potassium Persulphate in 200KG water evenly is being fed in this mixture under temperature 100---105 ℃ under the continuously stirring.Consume acetylene 27.6KG altogether.Acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 20.0KG.This reactor and being cooled to after 80 ℃ reduces pressure.In 2 hours, add the Al that contains of 290KG50% concentration
2O
3The Al of 16.53wt%
2(SO
4)
2The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of following vacuum-dryings.Obtain product: phosphorus content: 28.3% (28.8% calculated value) decomposition temperature: 430 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 4:
At first prepare the dialkyl phosphinic acid aluminium polymer.For this reason, the mixture of the sodium hypophosphite of 150KG and 750kg deionized water is packed in the pressure reactor of 2000L strap clamp cover.In case reaction mixture has been heated to 100 ℃, acetylene is added until reaching capacity in reactor by the reducing valve that is set to 3 crust.The solution of 2.0KG Potassium Persulphate in 200KG water evenly is being fed in this mixture under temperature 100---105 ℃ under the continuously stirring.Consume acetylene 29.5KG altogether.Acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 15.5KG.This reactor and being cooled to after 80 ℃ reduces pressure.In 2 hours, add the Al that contains of 290KG50% concentration
2O
3The Al of 16.53wt%
2(SO
4)
3The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of following vacuum-dryings.Obtain product: phosphorus content: 29.0% (29.2% calculated value) decomposition temperature: 427 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 5:
The mixture of the 50% concentration Hypophosporous Acid, 50 aqueous solution of 1.32 kilograms (10 moles) and 3.5 kilograms of acetate is added the 10 power reactors that boost. reaction mixture is being heated to after 80 ℃, acetylene is being added in this reactor to saturated by reducing valve being set in 3 crust.Under constant agitation, evenly add the solution of 60 gram azobisisobutyronitriles in 500 gram acetate.Consume acetylene 235 grams altogether, acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 50 grams.Continue after the reaction 1 hour, with this reactor decompression and be cooled to room temperature, the solution that obtains is removed most solvent acetic acid on rotary evaporator, add 5 premium on currency then.In 1 hour, add 46% concentration Al of 2250 grams (1.75 moles)
2(SO
4)
3.14H
2The O aqueous solution.With the filtration of gained solid matter, washed twice, wash in succession with 2 premium on currency, then then at 130 ℃ of following drying under reduced pressure at every turn.Phosphorus content: 33.0% (30.1% calculated value) decomposition temperature: 440 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 6:
At first prepare dialkyl phosphinic acid calcium polymkeric substance.For this reason, the mixture of the 50% concentration Hypophosporous Acid, 50 of 187KG and 700kg deionized water is packed in the pressure reactor of 2000L strap clamp cover.In case reaction mixture has been heated to 100 ℃, acetylene is added until reaching capacity in reactor by the reducing valve that is set to 3 crust.The solution of 2.0KG Potassium Persulphate in 200KG water evenly is being fed in this mixture under temperature 100---105 ℃ under the continuously stirring.Consume acetylene 18.0KG altogether.Acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 41.0KG.This reactor and being cooled to after 90-95 ℃ reduces pressure.In 2 hours, add 52KG calcium hydroxide, stirred for several hour in batches.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of following vacuum-dryings.Obtain product: phosphorus content: 23.2% (24.5% calculated value) decomposition temperature: 412 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 7:
At first prepare dialkyl phosphinic acid zinc polymkeric substance.For this reason, the mixture of the sodium hypophosphite of 150KG and 750kg deionized water is packed in the pressure reactor of 2000L strap clamp cover.In case reaction mixture has been heated to 100 ℃, acetylene is added until reaching capacity in reactor by the reducing valve that is set to 3 crust.With 2.0KG2,2 ' one azos two (one dimethylene isobutyl is narrowed for N, the N) solution of dihydrochloride in 200KG water evenly is fed in this mixture under temperature 100---105 ℃ under continuously stirring.Consume acetylene 19.1KG altogether.Acetylene is replaced by ethene, ethene is added until reaching capacity in reactor by the reducing valve that is set to 6 crust.Catalyzer evenly is fed in this mixture under temperature 100---105 ℃.Coreaction 10h.Consumption of ethylene 38.0KG.This reactor and being cooled to after 80 ℃ reduces pressure.In 2 hours, add the ZnSO that contains of 407KG50% concentration
4.7H
2The O aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of following vacuum-dryings.Obtain product: phosphorus content: 21.2% (22.3% calculated value) decomposition temperature: 408 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature).
Embodiment 8:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and test " general remark, will by the MPP of the product of the embodiment 1 of 14% weight and 6% weight and mixture that 80% weight polybutylene terephthalate 1 is formed in twin screw extruder 230 to 260 ℃ of following compoundings, obtain the flame-retardant polymer moulding compound.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 9:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, will by the MPP of the product of the embodiment 2 of 14% weight and 6% weight and mixture that 80% weight polybutylene terephthalate 1 is formed in twin screw extruder 230 to 260 ℃ of following compoundings, obtain the flame-retardant polymer moulding compound.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 10:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, the mixture that to be made up of the MPP of the product of the embodiment 3 of 14% weight and 6% weight and 50% weight polybutylene terephthalate 2 and 30% weight glass 230 to 260 ℃ of following compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 11:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, the mixture that to be made up of the MPP of the product of the embodiment 4 of 14% weight and 6% weight and 50% weight polybutylene terephthalate 2 and 30% weight glass 230 to 260 ℃ of following compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 12:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, the mixture that to be made up of the MPP of the product of the embodiment 6 of 14% weight and 6% weight and 50% weight polybutylene terephthalate 2 and 30% weight glass 230 to 260 ℃ of following compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 13:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, will by the product of the embodiment 4 of 20% weight and mixture that 80% weight polybutylene terephthalate 1 is formed in twin screw extruder 230 to 260 ℃ of following compoundings, obtain the flame-retardant polymer moulding compound.After drying, moulding compound obtains the flame-retardant polymer moulded work in 240 to 270 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 14:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, will be by the product of the embodiment 4 of 30% weight, the mixture of forming with 70% weight polystyrene 170 ℃ of following compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work processing down to 250 ℃ of melt temperature 200 in injection moulding machine.Test sample is V 1 according to the classification of UL94.
Embodiment 15:
According to " production of flame retardant plastics moulding compound and plastic molded articles; processing; and the test " general remark, will be by the product of the embodiment 4 of 12% weight, 5% weight melamine polyphosphate, 1% weight zinc oxide, 52% weight polyamide PA66, the mixture of forming with 30% weight glass fiber 260 to 280 ℃ of following compoundings, obtains the flame-retardant polymer moulding compound in twin screw extruder.After drying, moulding compound obtains the flame-retardant polymer moulded work in 260 to 300 ℃ of following processing of melt temperature in injection moulding machine.Test sample is V 1 according to the classification of UL94.
The embodiment application result sees Table two
The used chemical of table one
| Melamine pyrophosphate MPP | Ciba?M200 |
| Polybutylene terephthalate PBT1 | Celanex2300GV1/30 (containing 30% glass) |
| Polybutylene terephthalate PBT2 | GE307 |
| Glass | HP37863.2MM Taiwan BiCheng Co., Ltd |
| Polystyrene PS | BASF143 |
| Nylon 66PA66 | BASFA3 |
| Zinc borate ZB | Lucky blue or green chemical industry |
Table two embodiment application result
| Embodiment | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
| Embodiment 1 product | 14 | |||||||
| Embodiment 2 products | 14 | |||||||
| Embodiment 3 products | 14 | |||||||
| Embodiment 4 products | 14 | 20 | 30 | 12 | ||||
| Embodiment 6 products | 14 | |||||||
| ?ZB | 1 | |||||||
| ?MPP | 6 | 6 | 6 | 6 | 6 | 5 | ||
| ?PBT1 | 80 | 80 | 80 | |||||
| ?PBT2 | 50 | 50 | 50 | |||||
| Glass 1 | 30 | 30 | 30 | 30 | ||||
| PS | 70 | |||||||
| PA6，6 | 52 | |||||||
| The UL94 classification | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 |
Claims (15)
1. alkyl hypophosphite polymkeric substance, the residual moisture content that it is characterized in that this polymkeric substance is 0.01-10wt%, and average particle size particle size is 0.1-1000 μ m, and volume density is 80-800g/L, and its structural formula is as follows:
Wherein: R
1And R
2Be in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl or the isohexyl any, M be in Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K or the protonated nitrogen base any, m is 1-4, and n is 1-5.
2. alkyl phosphinate polymer according to claim 1, it is characterized in that described M is any or its mixture in aluminium, calcium, titanium, zinc, tin or the zirconium, the residual moisture content of described alkyl phosphinate polymer is 0.01-0.1wt%, average particle size particle size is 50-500 μ m, volume density 200-700g/L.
3. alkyl phosphinate polymer according to claim 1 and 2, it is characterized in that described protonated nitrogen base NH4 '. melamine, urea, biuret, guanidine, Cyprex, wallantoin, acetate guanamines, benzoguanamine, tolyl-triazole, benzotriazole, 2 one amino one 4 monomethyl pyrimidines, benzylurea, acetylene urea, glycolylurea, Malonamide are narrowed, dimethyl urea, diphenylguanidine, 5,5 one diphenyl hydantoins, N, in a N ' diphenyl urea, ethene two (5 one triketone), glycine anhydride, tetramethyl-urea or the melamine condensates any.
4. the preparation method of an alkyl phosphinate polymer as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) mixture of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is packed in the pressure reactor of strap clamp cover,, alkynes is added by reducing valve in pressure reactor, reach capacity when mixture has been heated to 70--110 ℃; Wherein: the weight ratio of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is 1: 4-7;
(2) with the aqueous solution of free-radical initiator under continuously stirring, under temperature 70-110 ℃, evenly join in step (1) the gained mixture, the amount until meeting the requirements of alkynes switches to alkene with alkynes then; Alkene is added until reaching capacity in pressure reactor by reducing valve, under 70-110 ℃ of temperature catalyzer is evenly joined in this mixture, reacted 8-12 hour, this pressure reactor that reduces pressure is cooled to after 80 ℃.In 1.5-2.5 hour, the metallic compound that adds Ca, Al, Sn, Ti, Zn or Zr reacts, and the gained solid is centrifugal, washes with water, and vacuum-drying promptly obtains required product; Wherein: the consumption of free-radical initiator is the 0.5-3% of Hypophosporous Acid, 50 or hypophosphite weight, and metallic compound add-on (mole number) is that the mole number of Hypophosporous Acid, 50 or hypophosphite is divided by m.
5. preparation method according to claim 4 is characterized in that alkynes is acetylene described in the step (1).
6. preparation method according to claim 4, it is characterized in that free-radical initiator is an azo-compound described in the step (2), described azo-compound is positively charged ion, azo-compound, non-cationic azo-compound, inorganic peroxide free-radical initiator or organo-peroxide free-radical initiator.
7. preparation method according to claim 4, the metallic compound that it is characterized in that Ca, Al, Sn, Ti, Zn or Zr described in the step (2) be in metal oxide, metal hydroxides, metal hydroxides oxide compound, metal sulfate, metal acetate, metal nitrate, metal chloride or the metal alcoholate that contains Ca, Al, Sn, Ti, Zn or Zr any.
8. preparation method according to claim 4 is characterized in that alkene described in the step (2) is one to multiple kind in ethene, positive propylene, different propylene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene or the dissident's alkene.
9. an alkyl phosphinate polymer as claimed in claim 1 is as the application of fire retardant, flame retardant composition and flame-retardant polymer moulding compound.
10. application according to claim 9, it is characterized in that when alkyl phosphinate polymer is used for flame retardant composition, concrete grammar is as follows: will add additive in the alkyl phosphinate polymer, obtain flame retardant composition, wherein: the add-on of alkyl phosphinate polymer is 70wt～95wt%, and the add-on of additive is 5wt～30wt%.Average of obtained flame-retardant agent composition is drawn and is of a size of 0.1-3000 μ m.
11. application according to claim 10 is characterized in that described additive is any one or more mixture in melamine phosphate, two melamine phosphates, five melamine triphosphates, three melamine diphosphates, four melamine triphosphates, six melamine pentaphosphates, melamine diphosphate, melamine tetraphosphate, melamine pyrophosphate salt, melamine polyphosphate, melam polyphosphate, melem polyphosphate or mellon(e) polyphosphate, zn cpds, magnesium compound, calcium cpd, aluminum compound, manganic compound or carbodiimide or (many) isocyanic ester.
12. application according to claim 9, it is characterized in that when alkyl phosphinate polymer is used for the flame-retardant polymer moulding compound, concrete grammar is as follows: alkyl phosphinate polymer, flame retardant composition, polymkeric substance and additive are mixed in mixing tank, fusion is even in the compounding associated plant at a certain temperature, products therefrom is extruded, cooling promptly gets desired product.
13. application according to claim 12, it is characterized in that described polymkeric substance is the polymkeric substance of single or diolefine, single or diolefine is put in poison or with the co-polymer of other vinyl monomer, or polystyrene, or vinylbenzene, or vinylbenzene and α--vinyl toluene and diene or with the multipolymer of acrylic acid derivative, or derived from diamines and dicarboxylic acid, or aminocarboxylic acid, or the polymeric amide of corresponding lactan and copolyamide, or derived from dicarboxylic acid and glycol, and/or hydroxycarboxylic acid, or the polyester of corresponding lactone; Described additive is a melamine phosphate, two melamine phosphates, five melamine triphosphates, three melamine diphosphates, four melamine triphosphates, six melamine pentaphosphates, the melamine diphosphate, the melamine tetraphosphate, the melamine pyrophosphate salt, the melamine polyphosphate, the melam polyphosphate, melem polyphosphate or mellon(e) polyphosphate, zn cpds, magnesium compound, calcium cpd, aluminum compound, any one or more mixture in manganic compound or carbodiimide or (many) isocyanic ester.
14. according to right 12 described application, it is characterized in that described compounding associated plant adopts single screw extrusion machine or multi-region screw extrusion press, effective spiro rod length (L) of the compounding associated plant of its screw diameter (D) multiple is 4-200D.
15. application according to claim 12, it is characterized in that the uniform treatment temp of described fusion, for polystyrene is 170-200 ℃, for polypropylene is 200-300 ℃, for polyethylene terephthalate is 250-290 ℃, for polybutylene terephthalate is 230-270 ℃, for polymeric amide～6th, and 260-290 ℃, for polymeric amide～6.6th, 260-290 ℃.
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