CN102850552A - 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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- CN102850552A CN102850552A CN201210186839XA CN201210186839A CN102850552A CN 102850552 A CN102850552 A CN 102850552A CN 201210186839X A CN201210186839X A CN 201210186839XA CN 201210186839 A CN201210186839 A CN 201210186839A CN 102850552 A CN102850552 A CN 102850552A
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Abstract
The invention relates to an alkyl phosphinate polymer, and a preparation method and an application thereof. The preparation method comprises the steps that: a mixture of hypophosphorous acid or hypophosphite and water or acetic acid is added into a pressure reactor with a jacket; when the mixture is heated to 70-110 DEG C, alkyne is added into the pressure reactor through a pressure reducing valve, until saturated; under continuous stirring, a water solution of a free radical initiator is uniformly added into the mixture, until the amount of alkyne reaches a requirement; alkyne is shifted into olefin; olefin is added into the pressure reactor through a pressure reducing valve, until saturated; a catalyst is uniformly added into the mixture, and a reaction is carried out for 8-12h; the pressure in the pressure reactor is reduced, and the mixture is cooled to a temperature of 80 DEG C; a metal compound is added for carrying out a reaction; and an obtained solid is subjected to centrifugal separation, water washing, and vacuum drying, such that a required product is obtained. The invention also relates to the application of the alkyl phosphinate polymer as a flame retardant, a flame retardant composition, and a flame retardant polymer molding composition.
Description
Technical field
The present invention relates to organic secondary phosphine acid salt polymkeric substance and its preparation method and application, relate in particular to alkyl phosphinate polymer and its preparation method 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 such flame-retardant additive is suppressed at the free radical gas-phase reaction that occurs in the flame when the series products of polyester or nylon is lighted.This is so that halogenated flame is used as the additive that comprises the different types of polymers materials such as polyester and nylon very at large.Yet at nearest about quindecennial, because ecological relationship, halogenated flame has been subjected to supervisory.Fire retardant industry will be towards the trend development of environmentally friendly flame-retardant additive under this pressure.Phosphorous product is the logical substitute of this class halogenated flame.In some applications, phosphorous additive demonstrates the same high activity with halogenated flame, but phosphorous additive seldom uses usually.Most of phosphorous fire retardant promotes to provide flame retardant activity with the combination that becomes charcoal by solidifying phase reaction, polymkeric substance carbonization.These methods obviously depend on the polymkeric substance that wherein uses this additive.Therefore, concrete phosphorous structure need to be designed to the multiple polymers type.At late 1970s and the beginning of the eighties, prepared the various salt of diaryl phospho acid, alkylaryl phospho acid 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 (L0I) of unit, observe flame retardant resistance and improve.CN 1660875A discloses preparation method and the application of dialkylphosphinic salts.It is applied on glass fiber enhanced nylon or the polyester, adds 20% and can satisfy fire-retardant requirement.
In order to obtain the product of high content of phosphorus, people utilize alkynes and contain the addition reaction of phosphinic compounds generation under free radical causes of P-H, and US5647995A discloses the technology for preparing a series of alkyl phosphinic acid compound.US6727335B2 discloses the polymerization phospho acid of preparation high-polymerization degree, and phosphorus content can be up to 33%.But we find that this polymeric phosphines hydrochlorate is greatly acid, the mechanical property of a lot of materials is had great destruction, and can not be employed.
In any case, these fire retardants or be unfavorable for environmental protection, perhaps its flame retardant effect is limited, therefore, needs in the reality to have developed than high flame retardant efficient, simultaneously environmentally friendly fire retardant again.
Summary of the invention
The object of the invention is to provides fire retardant that a kind of phosphorus content is high, thermotolerance is strong and its production and use by improving the phosphorus content in the fire retardant.Namely the object of the present invention is to provide a kind of alkyl phosphinate polymer and its preparation method and application, and then provide than high flame retardant efficient, the while is environmentally friendly fire retardant again.
The alkyl hypophosphite polymkeric substance that the present invention proposes, its structural formula are as shown in the formula (I):
Wherein: R
1And R
2Be respectively in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl or the isohexyl any.
U is mean polymerisation degree, and it is by the ratio decision of preparation alkyne monomer and Hypophosporous Acid, 50 or hypophosphite during polymkeric substance.
Re is any 1/m in Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, La, Bi, Sr, Mn, Li, Na, K or the protonated nitrogen base, wherein m is cationic valency, namely the positively charged ion of each m valency simultaneously with m formula (I) structure in the O covalency.
Described Re is preferably one or more mixtures among Al, Ca, Ti, Zn, Sn, Zr, La or the Ce, 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.
Described protonated nitrogen base preferably adopts ammonia, melamine, the protonated base of trolamine, NH4', melamine, urea, biuret, guanidine, Cyprex, wallantoin, the acetic acid guanamines, benzoguanamine, tolyl-triazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, acetylene urea, glycolylurea, Malonamide is narrowed, dimethyl urea, diphenylguanidine, 5, the 5-diphenyl hydantoin, DPU, ethene two (5-triketone), glycine anhydride, tetramethyl-urea, melamine condensates, such as melem, melam or mellon(e), or has a protonated base of this compound of higher condensation degree.
The principle of preparation is as follows:
Wherein
Be mean polymerisation degree, it is by the ratio decision of preparation alkyne monomer and Hypophosporous Acid, 50 or hypophosphite during polymkeric substance.
In the described alkyl phosphinate polymer, the mol ratio of alkynes and Hypophosporous Acid, 50 or hypophosphite is 0.25-0.55.
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 jacketed, when mixture heating up to 70-110 ℃, alkynes is added in the pressure reactor until saturated by reducing valve; Wherein: the mass ratio of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is 1:4-7;
(2) under temperature 70-110 ℃, the aqueous solution continuous uniform of free-radical initiator is joined in step (1) the gained mixture, until after the amount of alkynes reaches requirement, alkynes is switched to alkene; Alkene is added until reach 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 reduces pressure, be cooled to after 80 ℃, in 1.5-2.5 hour, add Ca, A1, Sn, Ti, Zn, Zr, the metallic compound of La or Ce reacts, the gained solid is through centrifugation, water washing, vacuum-drying, namely obtain required product, i.e. alkyl phosphinate polymer, wherein: the consumption of free-radical initiator is the 0.5-3% of Hypophosporous Acid, 50 or hypophosphite quality, metallic compound add-on (mole number) is the 1/m of Hypophosporous Acid, 50 or hypophosphite add-on (mole number), and wherein m is cationic valency.
Alkynes is preferably acetylene described in the step (1).
Free-radical initiator is preferably azo-compound described in the step (2), and described azo-compound is preferably 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 preferably adopts 2,2,-azo two (2-methyl-propyl amidine) dihydrochloride (or claiming V50), described non-cationic azo-compound preferably adopts two isobutyronitriles, 4,4-azo two (4-cyanopentanoic acid) or 2,2 '-azo two (2-methyl fourth eyeball), described inorganic peroxide free-radical initiator adopts one in hydrogen peroxide, ammonium peroxydisulfate, Sodium persulfate or the Potassium Persulfate to several, and the organo-peroxide free-radical initiator adopts oxidation dibenzoyl, ditertiary butyl peroxide or peracetic acid.
The metallic compound of Ca, A1, Sn, Ti, Zn, Zr, La or Ce described in the step (2) be in metal oxide, metal hydroxides, metal acetate, metal nitrate, metal chloride or the metal alcoholate that contains Ca, A1, Sn, Ti, Zn, Zr, La or Ce any.
Alkene described in the step (2) is preferably ethene, positive propylene, isopropyl alkene, n-butene, iso-butylene, positive amylene, isopentene, the one to multiple kind in alkene or the dissident's alkene just.
Described alkyl phosphinate polymer 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 as the application of flame retardant composition, concrete grammar is as follows: add additive in 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%.The average particle size particle size of obtained flame-retardant agent composition is 0.1-3000 μ m, is preferably 0.1-1000 μ m, more preferably 1-100 μ m.
Described additive is any 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.Be preferably in three (hydroxyethyl) chlorinated isocyanurates and aromatic multi-carboxy acid's oligopolymer ester, benzoguanamine, three (hydroxyethyl) chlorinated isocyanurates, wallantoin, glycoluril, melamine, melamine cyanurate, urea cyanurate, Dyhard RU 100 or the guanidine 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 such as calcium hydroxide, calcium oxide, hydrocalumite.Described zn cpds such as zinc oxide (such as active zinc flower), zinc hydroxide, aqua oxidation zinc, zinc carbonate (such 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.
Described alkyl phosphinate polymer is in the application of flame-retardant polymer moulding compound, and concrete grammar is as follows:
Alkyl phosphinate polymer, flame retardant composition, polymkeric substance and additive are mixed in mixing tank, and melting is even in the compounding associated plant at a certain temperature, and products therefrom is extruded, and cooling namely gets desired product, i.e. the flame-retardant polymer moulding compound.
Polymkeric substance of the present invention is derived from diamines and dicarboxylic acid, and/or aminocarboxylic acid, or the polymeric amide of corresponding lactan and copolyamide, such as polymeric amide-2,12, polymeric amide-4(gathers-4-Aminobutanoicacid), polymeric amide-4,6(gathers (tetramethylene adipamide), polymeric amide-6(polycaprolactam, poly-6-aminocaprolc acid) polymeric amide---6,6(gathers (N, N '-hexa-methylene adipamide)), polymeric amide-6,9(gathers (hexa-methylene nonane two acid amides), polymeric amide-6,10(gathers (hexa-methylene decanediamide)), polymeric amide-6,12(gathers (hexa-methylene dodecane diamide)), polymeric amide-6/6,6(poly-(hexa-methylene hexanamide-be total to-phthalein amine in oneself)), polymeric amide-7(gathers-the 7-aminoheptylic acid), polymeric amide-7,7(gathers heptamethylene pimeloyl amine), polymeric amide-8(poly-8-amino eaprylic acid), polymeric amide-8,8(gathers eight methylene radical suberamides), polymeric amide-9(gathers-9 aminononanoic acid), polymeric amide-9,9(gathers nine methylene radical pelargonamides), polymeric amide-10(poly-10-amino capric acid), polymeric amide-10,9(gathers (decamethylene pelargonamide)), polymeric amide-10,10(gathers decamethylene certain herbaceous plants with big flowers acid amides), polyamide-11 (poly-11-amino undecanoic acid), polymeric amide-12(polylauryllactam), derived from meta-dimethylbenzene, the aromatic polyamide of diamines and hexanodioic acid; The polymeric amide (polyhexamethylene isophthaloyl amine or polyhexamethylene terephthalamide) of being made by hexamethylene-diamine and m-phthalic acid and/or terephthalic acid, if suitable, made as properties-correcting agent by elastomerics, such as poly--2,4,4-tri-methyl hexamethylene terephthalamide or poly--meta-phenylene isophthaloyl amine; Above-mentioned polymeric amide and polyolefine with olefin copolymer, and from aggressiveness, or connect with valence bond or the elastomerics of grafting; 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 preferably derived from dicarboxylic acid and glycol, and/or hydroxycarboxylic acid, or the polyester of corresponding lactone, and such as polyethylene terephthalate, (Celanex 2500, and Celanex 2002, Celanese for polybutylene terephthalate; Ultradur, BASF), poly-(Isosorbide-5-Nitrae-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.
Described compounding associated plant preferably adopts single screw extrusion machine or multi-region screw extrusion press.The length-to-diameter ratio of its screw rod (L/D) is 4-200D, and that better is 10-50D.L is effective spiro rod length, and D is screw diameter.
Described melt temperature is preferably: polyethylene terephthalate (PET) is 250-290 ℃, polybutylene terephthalate (PBT) is 230-270 ℃, polymeric amide-6 (PA6) is 260-290 ℃, and polymeric amide-6.6 (PA6,6) is 260-290 ℃.
General remark: 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 extruder in that temperature 230-260 ℃ (GRPBT) or 260-280 ℃ (GRPA 66) is lower.The polymer-extruded thing of homogenize is drawn, in water-bath, cool off, and subsequently granulation.
After abundant drying, moulding compound is obtained test sample in melt temperature 240-270 ℃ (GRPBT) or 260-290 ℃ (GRPA 66) lower processing in injection moulding machine. measure UL94(insurance laboratory for the test sample from the test sample used thickness 1.6mm of every kind of mixture) the burning grade. following burning grade is provided by UL94:
V-0: 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-0
V-2: cotton indicator is dripped by fire. lights; Other standard is as V-1
Unclassified (n.r.): do not satisfy burning grade V-2.
The breach resistance to impact shock is utilized the test of ISO 180 testing method
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, such as lamp socket and lamp bracket, and plug and insertion wiring board, coil stand, 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-resisting fire retardant 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 dialkyl phosphinic acid Al 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 jacketed.In case reaction mixture has been heated to 100 ℃, acetylene is added in the reactor until saturated by the reducing valve that is set to 0.3MPa.With 2,2 of 2.0kg ,-azo two (2-methyl-propyl amidine) dihydrochloride (or claim V50) is dissolved in the 200kg water, and with this solution in continuously stirring, under temperature 100-105 ℃, evenly be fed in this mixture.Consume altogether acetylene 18.5kg.Acetylene is replaced by ethene, ethene is added in the reactor until saturated by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h.Consumption of ethylene 39.6kg.This reactor that reduces pressure, and be cooled to after 80 ℃.In 2 hours, adding 290kg concentration is the Al that contains of 50wt%
2O
3The A1 of 16.53wt%
2(SO
4)
3The aqueous solution.With by centrifugation, deionized water wash twice is then 130 ℃ of lower vacuum-dryings with the gained solid.Obtain product: phosphorus content: the 26.5%(26.9% calculated value), decomposition temperature: 425 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature)
Embodiment 2:
At first prepare dialkyl phosphinic acid Al 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 jacketed.In case reaction mixture has been heated to 100 ℃, acetylene is added until reach capacity in reactor by the reducing valve that is set to 0.3MPa.With 2,2 of 2.0kg, the solution of-azo two (2-methyl-propyl amidine) dihydrochloride (or claiming V50) in 200kg water evenly is fed in this mixture under temperature 100-105 ℃ under continuously stirring.Consume altogether acetylene 9.2kg.Acetylene is replaced by ethene, ethene is added until reach capacity in reactor by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h.Consumption of ethylene 59.7kg.This reactor that reduces pressure, and be cooled to after 80 ℃.In 2 hours, add 290kg 50wt% concentration contain Al
2O
3The A1 of 16.53wt%
2(SO
4)
3The aqueous solution.With the subsequently centrifugation of gained solid, deionized water wash twice is then 130 ℃ of lower vacuum-dryings.Obtain product: phosphorus content: the 25.1%(25.3% calculated value), decomposition temperature: 435 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature)
Embodiment 3:
At first prepare dialkyl phosphinic acid Al 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 jacketed.In case reaction mixture has been heated to 100 ℃, acetylene is added until reach capacity in reactor by the reducing valve that is set to 0.3MPa.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 altogether acetylene 12.9kg.Acetylene is replaced by ethene, ethene is added until reach capacity in reactor by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h.Consumption of ethylene 51.8kg.This reactor that reduces pressure, and be cooled to after 80 ℃.In 2 hours, add 290kg 50wt% concentration contain Al
2O
3The A1 of 16.53wt%
2(SO
4)
3The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of lower vacuum-dryings.Obtain product: phosphorus content: the 25.7%(25.9% calculated value) decomposition temperature: 430 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature)
Embodiment 4:
At first prepare dialkyl phosphinic acid Al 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 jacketed.In case reaction mixture has been heated to 100 ℃, acetylene is added in the reactor until saturated by the reducing valve that is set to 0.3MPa.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 altogether acetylene 16.6kg.Acetylene is replaced by ethene, ethene is added in the reactor until saturated by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h.Consumption of ethylene 43.9kg.This reactor that reduces pressure, and be cooled to after 80 ℃.In 2 hours, add 290kg 50wt% concentration contain Al
2O
3The A1 of 16.53wt%
2(SO
4)
3The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of lower vacuum-dryings.Obtain product: phosphorus content: the 26.7%(26.6% calculated value) decomposition temperature: 427 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature)
Embodiment 5:
At first prepare dialkyl phosphinic acid Al polymkeric substance.For this reason, with the 1.32kg(10 mole) concentration be that the mixture of the 50wt% Hypophosporous Acid, 50 aqueous solution and 3.5kg acetic acid adds the 10L pressure reactor. reaction mixture is being heated to after 80 ℃, by reducing valve being set in 0.3MPa acetylene is being added in this reactor to saturated.Under constant agitation, evenly add the solution of 60g azobisisobutyronitrile in 500g acetic acid.Consume altogether acetylene 145g, acetylene is replaced by ethene, ethene is added in the reactor until saturated by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h.Consumption of ethylene 260g.Continue after the reaction 1h, with this reactor decompression and be cooled to room temperature, the solution that obtains is removed most solvent acetic acid at rotary evaporator, then adds 5L water.In 1h, add 2250g(1.75mol) 46% concentration A1
2(SO
4)
3.14H
20 aqueous solution.Then with the filtration of gained solid matter, washed twice, in succession wash with 2 premium on currency, then at 130 ℃ of lower drying under reduced pressure at every turn.Phosphorus content: the 26.7%(27.0% calculated value), decomposition temperature: 440 ℃ of (TGA test, N
2Be carrier gas, decompose 5% temperature)
Embodiment 6:
At first prepare dialkyl phosphinic acid La 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 jacketed.In case reaction mixture has been heated to 100 ℃, acetylene is added in the reactor until saturated by the reducing valve that is set to 0.3MPa.With 2.0kg2,2, the solution of-azo two (2-methyl-propyl amidine) dihydrochloride (or claiming V50) in 200KG water evenly is fed in this mixture under temperature 100-105 ℃ under continuously stirring.Consume altogether acetylene 16.8KG.Acetylene is replaced by ethene, ethene is added in the reactor until saturated by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h, consumption of ethylene 43.8kg.This reactor that reduces pressure, and be cooled to after 80 ℃.In 2 hours, add 332kg 50wt% contain LaCl
3.6H
20 aqueous solution.With the subsequently centrifugation of gained solid, deionized water wash twice is then 130 ℃ of lower vacuum-dryings.Obtain product: phosphorus content: the 21.2%(22.3% calculated value) decomposition temperature: 408 ℃ (TGA test, N2 is carrier gas, decomposes 5% temperature)
Embodiment 7:
At first prepare dialkyl phosphinic acid Al 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 jacketed.In case reaction mixture has been heated to 100 ℃, acetylene is added until saturated in reactor by the reducing valve that is set to 0.3MPa.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 altogether acetylene 29.5kg.Acetylene is replaced by ethene, ethene is added until reach capacity in reactor by the reducing valve that is set to 0.6MPa.Catalyzer evenly is fed in this mixture under temperature 100-105 ℃.Coreaction 10h.Consumption of ethylene 15.5kg.This reactor that reduces pressure, and be cooled to after 80 ℃.In 2 hours, add the Al that contains of 290kg50% concentration
2O
3The A1 of 16.53wt%
2(S04)
3The aqueous solution.The gained solid is centrifugal subsequently, wash twice with water, then 130 ℃ of lower vacuum-dryings.Obtain product: phosphorus content: the 29.0%(29.2% calculated value) decomposition temperature: 427 ℃ (TGA test, N2 is carrier gas, decomposes 5% temperature).
Embodiment 8:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with the product among the embodiment 1 and MPP and polybutylene terephthalate (PBT1) and 17:1:82 in mass ratio in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Embodiment 9:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with the product among the embodiment 2 and MPP and polybutylene terephthalate (PBT1) in mass ratio 18:1:81 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Embodiment 10:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with product, MPP and the polybutylene terephthalate (PBT2) of embodiment 3 and glass fibre in mass ratio 18:1:51:30 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Embodiment 11:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with product, MPP and the polybutylene terephthalate (PBT2) of embodiment 4 and glass fibre in mass ratio 17:1:52:30 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Embodiment 12:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with product, MPP and the polybutylene terephthalate (PBT2) of embodiment 6 and glass fibre in mass ratio 14:6:50:30 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-1 according to the classification of UL94.
Embodiment 13:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with the product of embodiment 4 and polybutylene terephthalate (PBT1) in mass ratio 18:82 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Embodiment 14:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", be that 12:5:1:52:30 is in twin screw extruder in mass ratio with product, melamine polyphosphate, zinc borate and polymeric amide PA66 and the glass fibre of embodiment 4, temperature is 260-280 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 260-300 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Comparative example 1:
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with OP1230, MPP and 50% weight polybutylene terephthalate (PBT2) and glass fibre in mass ratio 14:6:50:30 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
Comparative example 2
General remark according to " production of flame retardant plastics moulding compound and plastic molded articles, processing and test ", with product, MPP and the 50% weight polybutylene terephthalate (PBT2) of embodiment 7 and glass fibre in mass ratio 14:6:50:30 in twin screw extruder, temperature is 230-260 ℃ of lower compounding, obtains the flame-retardant polymer moulding compound.After the drying, moulding compound is in injection moulding machine, and melt temperature is that 240-270 ℃ of lower processing obtains the flame-retardant polymer moulded work.Test sample is V-0 according to the classification of UL94.
The embodiment application result sees Table two
The used chemical of table one
Table two embodiment application result
The phosphorus content of fire retardant OP1230 is 23.8%, satisfies the fire-retardant needs that require and adds 20%.Embodiment 6 product phosphorus contents are 21.2%, add 20%(14% embodiment 6 products, 6%MPP) fire-retardantly can only reach the V1 rank.Other embodiment product phosphorus contents are all greater than 25%.Be less than 20% addition and just can reach fire-retardant requirement.Obviously the increase of phosphorus content is conducive to improve flame retardant properties.Comparative example 2 shows that the shock resistance of material sharply descends when the mol ratio of alkynes and time sodium is 0.8.
Claims (16)
1. alkyl phosphinate polymer is characterized in that structural formula is as follows:
Wherein: R
1And R
2Be respectively in ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl or the isohexyl any,
Re is any 1/m in Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, La, Bi, Sr, Mn, Li, Na, K or the protonated nitrogen base, and wherein m is cationic valency.
U is mean polymerisation degree, and it is by the ratio decision of preparation alkyne monomer and Hypophosporous Acid, 50 or hypophosphite during polymkeric substance.
2. alkyl phosphinate polymer according to claim 1, the molar ratio that it is characterized in that described alkynes and Hypophosporous Acid, 50 or hypophosphite is 0.25-0.55.
3. alkyl phosphinate polymer according to claim 1, it is characterized in that described Re in its structure is one or more the mixture among Al, Ca, Ti, Zn, Sn, Zr or the La, the residual moisture content of described alkyl phosphinate polymer is 0.01-0.1wt%, average particle size particle size is 50-500 μ m, and volume density is 200-700g/L.
4. alkyl phosphinate polymer according to claim 1 and 2, it is characterized in that described protonated nitrogen base is that NH4 ', melamine, urea, biuret, guanidine, Cyprex, wallantoin, acetic acid guanamines, benzoguanamine, tolyl-triazole, benzotriazole, 2-amino-4-methylpyrimidine, benzylurea, acetylene urea, glycolylurea, Malonamide narrow, dimethyl urea, diphenylguanidine, 5, in 5-diphenyl hydantoin, DPU, ethene two (5-triketone), glycine anhydride, tetramethyl-urea or the melamine condensates any.
5. the preparation method of an alkyl phosphinate polymer as claimed in claim 1 is characterized in that comprising the steps:
(1) mixture of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is packed in the pressure reactor of jacketed, when mixture has been heated to 70-110 ℃, alkynes is added in the pressure reactor until saturated by reducing valve; Wherein: the mass ratio of Hypophosporous Acid, 50 or hypophosphite and water or acetic acid is 1: 4-7;
(2) under temperature 70-110 ℃, the aqueous solution of free-radical initiator is evenly joined in step (1) the gained mixture, and add continuously alkynes, until after reaching the amount of alkynes and requiring, alkynes is switched to alkene; Alkene is added in the pressure reactor until saturated by reducing valve, under 70-110 ℃ of temperature, 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, A1, Sn, Ti, Zn, Zr or La reacts, with the gained solid through centrifugation, water washing, vacuum-drying namely obtains required alkyl phosphinate polymer; Wherein: the consumption of free-radical initiator is the 0.5-3% of Hypophosporous Acid, 50 or hypophosphite quality, and the mol ratio of the add-on of metallic compound and Hypophosporous Acid, 50 or hypophosphite is 1: m, wherein m is the valency of metallic cation in this metallic compound.
6. preparation method according to claim 5 is characterized in that alkynes is acetylene described in the step (1).
7. preparation method according to claim 5, it is characterized in that free-radical initiator is azo-compound described in the step (2), described azo-compound is cationic azo compound, non-cationic azo-compound, inorganic peroxide free-radical initiator or organo-peroxide free-radical initiator.
8. preparation method according to claim 5, the metallic compound that it is characterized in that Ca, A1, Sn, Ti, Zn, Zr or La described in the step (2) is any in metal oxide, metal hydroxides, metal acetate, metal nitrate, metal chloride or the metal alcoholate that contains Ca, A1, Sn, Ti, Zn, Zr or La.
9. preparation method according to claim 5 is characterized in that alkene described in the step (2) is one or more in ethene, positive propylene, isopropyl alkene, n-butene, iso-butylene, positive amylene, isopentene, n-hexylene or the dissident's alkene.
One kind such as each described alkyl phosphinate polymer among the claim 1-5 as the application of fire retardant, flame retardant composition and flame-retardant polymer moulding compound.
11. application according to claim 10, 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%, the add-on of additive is 5wt-30wt%, and the average particle size particle size of obtained flame-retardant agent composition is 0.1-3000 μ m.
12. application according to claim 11 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.
13. application according to claim 10, it is characterized in that when alkyl phosphinate polymer is used for the flame-retardant polymer moulding compound, concrete grammar is as follows: described alkyl phosphinate polymer, flame retardant composition, polymkeric substance and additive are mixed in mixing tank, melting is even in the compounding associated plant again, products therefrom is extruded, cooling namely gets required flame-retardant polymer moulding compound.
14. application according to claim 13 is characterized in that described polymkeric substance is 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 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.
15. according to right 13 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 of compounding associated plant is 4-200D, D is screw diameter.
16. application according to claim 13, it is characterized in that the uniform treatment temp of described melting, it is 250-290 ℃ for polyethylene terephthalate, it is 230-270 ℃ for polybutylene terephthalate, for polymeric amide-the 6th, 260-290 ℃, for polymeric amide-the 6.6th, 260-290 ℃.
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