CN103254424A - Polyamide resin and polyamide composition composed thereof - Google Patents

Abstract

The invention discloses a polyamide resin, which consists of the following components: a component A which includes 40-48mol% of decamethylene diamine and 2-10mol/% of hexane diamine; and a component B which includes 40-48mol% of terephthalic acid and 2-10mol/% of adipic acid. A polyamide composition containing the polyamide resin comprises the following components in percentage by weight: 30-99.9% polyamide resin, 0-60% reinforcing filler, 0-50% of flame retardant, and 0.1 to 10% of other auxiliary agents. The polyamide resin and the polyamide composition composed thereof have the advantages that with relatively high brightness, the resin and the composition can be applied to situations in which the requirement on product luster is relatively high; and with strong heat resistance, the resin and the composition can be applied to situations in which the reflow soldering temperature exceeds 270 DEG C, for example.

Description

A kind of polyamide resin and by its daiamid composition of forming

Technical field

The present invention relates to polymeric material field, particularly a kind of polyamide resin and by its daiamid composition of forming.

Background technology

Polymeric amide is because having good comprehensive performances, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, certain flame retardant resistance is arranged, be easy to processing etc., it extensively is suitable for improves aspects such as performance and broadened application scope with glass fibre and other filler filling enhancing modified.In recent years semiaromatic polyamide composition because its resistance toheat and mechanical property are more excellent by focus development.

A well known fact is, polymeric amide be easy to oxidized or high temperature under produce and decompose, cause the color of resin obfuscation, have a strong impact on its quality.Therefore the improvement of polymeric amide brightness becomes an important research project.

Summary of the invention

For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide the polyamide resin of a kind of high brightness and high heat resistance.

A kind of polyamide resin, by mole per-cent, formed by following component:

The decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%;

The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%.

Described polyamide resin be higher than 270 ^oC is preferably 280 ^oC ~ 320 ^oC; Melting point resin is too low, goods easy deformation under the pyroprocessing of reflow soldering; Melting point resin is too high, causes its processing characteristics to descend; And fusing point is too high near decomposition temperature, and the goods various aspects of performance is all descended.

Obtain the brightness value L of colour table after the injection moulding of described polyamide resin greater than 75.0, be preferably more than 76.0; The resin brightness value is too low, causes its goods obfuscation, and influence is finally used.

A kind of daiamid composition that comprises described polyamide resin by weight percentage, comprises following component:

Polyamide resin 30 ~ 99.9%;

Reinforcing filler 0 ~ 60%;

Fire retardant 0 ~ 50%;

Other auxiliary agents 0 ~ 10%;

The content of described reinforcing filler is preferably 15-40%; Filler content is low excessively, causes the daiamid composition mechanical property relatively poor; Filler content is too high, and the daiamid composition product surface is floating fine serious, influences product appearance.

Being shaped as of described reinforcing filler is fibrous, and its mean length is 0.01 ~ 20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, is preferably 30 ~ 600:1, when fibrous reinforcing filler content is in above-mentioned scope, and the high temperature rigid that daiamid composition will show high heat distortion temperature and increase, above-mentioned size can obtain fiber measurement by milscale.

Described reinforcing filler is inorganic reinforcing filler or organic reinforcing filler;

Described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Use glass fibre not only can improve the mouldability of daiamid composition, and can improve mechanical property for example tensile strength, flexural strength and modulus in flexure, and the heat-drawn wire when improving thermotolerance for example the thermoplastic resin composition carrying out molding.

Described organic reinforcing filler is selected from Kevlar and/or carbon fiber.

Being shaped as of described reinforcing filler is non-fibrous, for example Powdered, particulate state, tabular, needle-like, fabric or felted, its median size is 0.001～10 μ m, is preferably 0.01～5 μ m, will cause the melt processable of polyamide resin difference less than 0.001 μ m when the median size of reinforcing filler; When the median size of reinforcing filler greater than 10 μ m, will cause bad injection moulding product appearance.The median size of above-mentioned reinforcing filler is measured by absorption method, and it can be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.These reinforcing fillers can be hollow; In addition, for swelling property layered silicates such as wilkinite, polynite, lithium montmorillonite, synthetic micas, can use and adopt organic ammonium salt that interlayer ion is carried out organic montmorillonoid after the cationic exchange.

In order to make daiamid composition obtain more good mechanical property, can adopt coupling agent that inorganic reinforcing filler is carried out functional processing, wherein coupling agent is selected from isocyanic ester based compound, organosilane based compound, organic titanate based compound, organo-borane based compound, epoxy compounds; Be preferably the organosilane based compound;

Wherein, described organosilane based compound be selected from alkoxysilane compound containing trialkylsilyl group in molecular structure, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains urea groups, the alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate group that contain epoxy group(ing), contain amino alkoxysilane compound containing trialkylsilyl group in molecular structure, contain hydroxyl alkoxysilane compound containing trialkylsilyl group in molecular structure, contain the carbon-to-carbon unsaturated group alkoxysilane compound containing trialkylsilyl group in molecular structure, contain one or more of alkoxysilane compound containing trialkylsilyl group in molecular structure of anhydride group.

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains epoxy group(ing) is selected from one or more of γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane;

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains sulfydryl is selected from γ-Qiu Jibingjisanjiayangjiguiwan and/or γ-sulfydryl propyl-triethoxysilicane;

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains urea groups is selected from one or more of γ-urea groups propyl-triethoxysilicane, γ-urea groups propyl trimethoxy silicane, γ-(2-urea groups ethyl) TSL 8330;

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains isocyanate group is selected from one or more of γ-isocyanate group propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group propyl group methyl dimethoxysilane, γ-isocyanate group propyl group methyldiethoxysilane, γ-isocyanate group propyl group ethyl dimethoxy silane, γ-isocyanate group propyl group ethyl diethoxy silane, γ-isocyanate group propyltrichlorosilan;

Describedly contain amino alkoxysilane compound containing trialkylsilyl group in molecular structure and be selected from one or more of γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane;

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains hydroxyl is selected from γ-hydroxypropyl Trimethoxy silane and/or γ-hydroxypropyl triethoxyl silane;

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains the carbon-to-carbon unsaturated group is selected from one or more of γ-methacryloxypropyl trimethoxy silane, vinyltrimethoxy silane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride;

The described alkoxysilane compound containing trialkylsilyl group in molecular structure that contains anhydride group is selected from 3-trimethoxy-silylpropyl succinyl oxide;

Described organosilane based compound is preferably γ-methacryloxypropyl trimethoxy silane, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) TSL 8330, gamma-amino propyl trimethoxy silicane or 3-trimethoxy-silylpropyl succinyl oxide.

Can adopt above-mentioned organosilane based compound that inorganic reinforcing filler is carried out surface treatment according to the method for routine, and then itself and polyamide resin are carried out melting mixing, to prepare described daiamid composition; Also can directly in inorganic reinforcing filler and polyamide resin melting mixing, add the organosilane based compound and carry out in-situ blending;

Wherein, the consumption of described coupling agent is with respect to 0.05 ~ 10wt% of inorganic reinforcing filler weight, is preferably 0.1 ~ 5wt%; When the consumption of coupling agent during less than 0.05wt%, it does not reach the effect of tangible improved mechanical properties; When the consumption of coupling agent during greater than 10wt%, inorganic reinforcing filler condenses easily, and disperses bad risk in polyamide resin, finally causes mechanical property to descend.

Described fire retardant is the composition of fire retardant or fire retardant and fire-retardant assistance agent, and its content is preferably 10 ~ 40wt%; The low excessively flame retardant effect variation that causes of flame retardant agent content, the too high material property that causes of flame retardant agent content descends.

Described fire retardant is halogenated flame retardant or halogen-free flame retardants;

Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecanes or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene;

Described halogen-free flame retardants is selected from one or more of the fire retardant that contains nitrogen combustion inhibitor, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant.

It is that phosphoric acid ester, butylbenzene are one or more of phosphoric acid ester or hypophosphite that described phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene; Be preferably hypophosphite;

Described hypophosphite has the hypophosphite of following structure formula I:

In the formula, R ¹, R ²Identical or different, be expressed as straight chain or contain alkyl and/or aryl or the phenyl of 1 ~ 6 carbon atom of side chain; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or by protonated nitrogenous base; M is 1 ~ 3.

Described other auxiliary agents are selected from one or more of softening agent, thickening material, antistatic agent, releasing agent, toner, staining agent or nucleator.

The present invention compared with prior art has following beneficial effect:

1) polyamide resin of the present invention prepares by specific repeating unit, obtains the brightness value L of colour table after the injection moulding greater than 75.0, has higher brightness, can be applied to the occasion that product color is had relatively high expectations;

2) fusing point of polyamide resin of the present invention is higher than 270 ^oC, thermotolerance is strong, can be applied to surpass 270 as the reflow soldering temperature ^oThe occasion of C;

3) daiamid composition for preparing gained by polyamide resin of the present invention also has high brightness and strong thermotolerance, can be applied to the occasion that product color, thermotolerance are had relatively high expectations.

 

Embodiment

Further specify the present invention below by embodiment, following examples are preferred implementation of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.

The testing method of gained polymeric amide relative viscosity: with reference to GB12006.1-89, polymeric amide viscosity number measuring method; Concrete testing method is: 25 ± 0.01 ^OC98% the vitriol oil in to measure concentration be the relative viscosity η r of the polymeric amide of 0.25g/dl;

The testing method of the fusing point of polymeric amide: with reference to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; Concrete testing method is: the fusing point that adopts Perkin Elmer Dimond dsc analysis instrument specimen; Nitrogen atmosphere, flow velocity are 40mL/min; Elder generation is with 10 during test ^oC/min is warming up to 340 ^oC is 340 ^OCKeep 2min, then with 10 ^oC/min is cooled to 50 ^oC is again with 10 ^oC/min is warming up to 340 ^oC is made as fusing point with endotherm peak temperature at this moment T _m

The testing method of gained polymeric amide terminal amino group content: with full-automatic current potential titration apparatus titration sample terminal amino group content; Get the 0.5g polymkeric substance, add phenol 45mL and anhydrous methanol 3mL, reflux after the observation sample dissolves fully, is chilled to room temperature, with the hydrochloric acid standard solution titration terminal amino group content of having demarcated;

The testing method of gained polymeric amide content of carboxyl end group: with full-automatic current potential titration apparatus titration sample content of carboxyl end group; Get the 0.5g polymkeric substance, add ortho-cresol 50mL, the dissolving that refluxes is put cold back and is added 400 μ L formaldehyde solutions rapidly, with the KOH-ethanolic soln titration content of carboxyl end group of having demarcated;

The testing method of gained polyamide resin brightness L value: use the Standard colour board mould, after getting the 3000g polymer particle and carrying out injection moulding, obtain the colour table of one-sided smooth.Place reason to obtain the brightness value L value on the precious Color-Eye7000A computer color measurement instrument this colour table;

Tensile strength: measure according to ISO 527-2, test condition is 23 ^oC and 10mm/min;

Elongation at break: measure according to ISO 527-2, test condition is 23 ^oC and 10mm/min;

Flexural strength and modulus in flexure: measure according to ISO 178, test condition is 23 ^oC and 2mm/min;

The socle girder notched Izod impact strength: measure according to ISO 180/1A, test condition is 23 ^oC, the breach type is the A type.

Embodiment 1 ~ 4 and Comparative Examples 1 ~ 14

In the autoclave pressure of being furnished with magnetic force coupling stirring, prolong, gas phase mouth, charging opening, pressure venting, add reaction raw materials in the ratio in the form; Add phenylformic acid, sodium hypophosphite and deionized water again; The phenylformic acid amount of substance is 2.5% of diamines, diacid, lactan and the total amount of substance of amino acid, and sodium hypophosphite weight is 0.1% of outer other weight that feed intake of deionizing water, and deionized water weight is 30% of the weight that always feeds intake; Vacuumize and charge into high pure nitrogen as protection gas, be warmed up to 220 under agitation 2 hours ^oC, with reaction mixture 220 ^oC stirred 1 hour, under agitation made the temperature of reactant be elevated to 230 then ^oC; Be reflected at 230 ^oProceed 2 hours under the constant temperature of C and the constant voltage of 2.2MPa, by remove formed water keep-up pressure constant, the reaction finish after discharging, prepolymer is in 80 ^oVacuum-drying is 24 hours under the C, obtains prepolymer product, and described prepolymer product is 250 ^oSolid-phase tack producing is 10 hours under C, the 50Pa vacuum condition, obtains polymeric amide.The relative viscosity of polymeric amide, fusing point and brightness L value are listed in the table 1.

Table 1

?	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Comparative Examples 1	Comparative Examples 2	Comparative Examples 3	Comparative Examples 4	Comparative Examples 5	Comparative Examples 6
											Terephthalic acid/mol	18	19	16	24	9	11	14	10	24.5	25
Hexanodioic acid/mol	2	1	4	1	11	9	6	10	0.5	0
											1/mol	18	19	16	24	0	0	14	10	24.5	25
Hexanediamine/mol	2	1	4	1	20	20	6	10	0.5	0
											End amino/mol/t	38	44	40	45	40	38	41	48	39	45
End carboxyl/mol/t	92	89	78	96	82	71	95	101	98	88
											Relative viscosity	2.220	2.231	2.244	2.250	2.233	2.228	2.238	2.201	2.232	2.271
Fusing point/ oC	292	304	276	309	292	311	251	240	311	316
											Resin brightness (L)	78.1	79.3	78.6	78.9	70.2	71.1	69.3	68.2	66.7	68.2

Continuous table 1

?	Comparative Examples 7	Comparative Examples 8	Comparative Examples 9	Comparative Examples 10	Comparative Examples 11	Comparative Examples 12	Comparative Examples 13	Comparative Examples 14
									Terephthalic acid/mol	18	19	24.5	25	18	19	11	9
Hexanodioic acid/mol	7	6	0.5	0	2	1	9	11
									1/mol	24.5	25	18	19	14	10	16	19
Hexanediamine/mol	0.5	0	7	6	6	10	4	1
									End amino/mol/t	40	32	38	47	42	37	34	46
End carboxyl/mol/t	101	95	97	87	91	85	96	89
									Relative viscosity	2.223	2.263	2.259	2.245	2.260	2.280	2.246	2.215
Fusing point/ oC	275	277	301	296	289	304	269	255
									Resin brightness (L)	67.5	66.9	67.9	69.9	70.3	68.5	67.6	69.0

From embodiment 1 ~ 4 and Comparative Examples 1 ~ 14 more as can be seen, the brightness L value of embodiment gained 10T resin of the present invention is all more than 78, and the resinoid brightness L of Comparative Examples 6T value is all about 70, its brightness L value is far below the embodiment resin.And among the Comparative Examples 10T/66,66 content are when 30mol% is above, and the fusing point of polyamide resin is reduced to 250 ^oBelow the C, this just means its stable on heating decline, can't be used for heat-resisting place of having relatively high expectations, and surpasses 270 as the reflow soldering temperature ^oThe occasion of C.

Embodiment 5 ~ 8 and Comparative Examples 15 ~ 21

The prescription of pressing table 2 with polyamide resin, fire retardant, other auxiliary agents high-speed mixer and mixing evenly after, add in the twin screw extruder by main spout, reinforcing filler is fed by side feeding scale side, extrudes, cross water cooling, obtain described daiamid composition after granulation and the drying.Wherein, extrusion temperature is 330 ^oC.

 

Prescription is weight part in table 2 following table

?	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Comparative Examples 15	Comparative Examples 16	Comparative Examples 17	Comparative Examples 18	Comparative Examples 19	Comparative Examples 20	Comparative Examples 21
												Polyamide resin	Embodiment 1	Embodiment 1	Embodiment 4	Embodiment 4	Comparative Examples 1	Comparative Examples 3	Comparative Examples 5	Comparative Examples 7	Comparative Examples 9	Comparative Examples 11	Comparative Examples 13
Resin content	70	50	30	99.9	70	50	70	50	99.9	70	30
												Glass fibre	29	30	60	0	29	30	29	30	0	29	60
Hypophosphite fire retardant	0	15	5	0	0	15	0	15	0	0	5
												Polybutene	0	2	2	0	0	2	0	2	0	0	2
Dipentaerythritol	0	1	1	0	0	1	0	1	0	0	1
												Zinc borate	0	1	1	0	0	1	0	1	0	0	1
Phenolic antioxidant	0.5	0.5	0.5	0.05	0.5	0.5	0.5	0.5	0.05	0.5	0.5
												Polyethylene wax	0.5	0.5	0.5	0.05	0.5	0.5	0.5	0.5	0.05	0.5	0.5
Resin brightness (L)	79.4	77.6	80.3	79.8	80.3	76.3	68.3	71.6	66.1	67.2	63.2
												Tensile strength/MPa	181	232	185	179	138	162	190	183	176	172	218
Elongation at break/%	3.2	2.2	3.3	3.1	2.8	2.6	3.1	3.1	3.0	3.3	2.1
												Flexural strength/MPa	267	336	261	258	197	224	273	265	251	247	330
Modulus in flexure/MPa	8343	14312	8167	8437	9324	10386	8612	8572	8629	8273	14721
												Socle girder notched Izod impact strength/kJ/m 2	11.7	14.7	12.3	11.4	8.9	9.1	11.0	10.4	11.8	12.3	13.6

From the embodiment 5 ~ 8 of table 2 and Comparative Examples 15 ~ 21 more as can be seen, the composition that the composition that the embodiment of the present application prepares prepares than Comparative Examples has more outstanding brightness L value, its brightness value is better than Comparative Examples, can be applied to the occasion that product color is had relatively high expectations.

Claims (9)

1. a polyamide resin is characterized in that, by mole per-cent, is made up of following component:

The decamethylene diamine of component A:40-48mol% and the hexanediamine of 2-10mol%;

The terephthalic acid of B component: 40-48mol% and the hexanodioic acid of 2-10mol%.

2. polyamide resin according to claim 1 is characterized in that, described polyamide resin be higher than 270 ^oC is preferably 280 ~ 330 ^oC.

3. polyamide resin according to claim 1 is characterized in that, obtains the brightness value L of colour table after the injection moulding of described polyamide resin greater than 75.0, is preferably more than 76.0.

4. daiamid composition that comprises each described polyamide resin of claim 1 ~ 3, percentage ratio meter by weight comprises following component:

Polyamide resin 30 ~ 99.9%;

Reinforcing filler 0 ~ 60%;

Fire retardant 0 ~ 50%;

Other auxiliary agents 0.1 ~ 10%.

5. daiamid composition according to claim 4 is characterized in that, being shaped as of described reinforcing filler is fibrous, and its mean length is 0.01-20mm, is preferably 0.1 ~ 6mm; Its length-to-diameter ratio is 5 ~ 2000:1, is preferably 30 ~ 600:1; The content of described reinforcing filler is 10 ~ 50wt%.

6. daiamid composition according to claim 5, it is characterized in that, described reinforcing filler is inorganic reinforcing filler or organic reinforcing filler, described inorganic reinforcing filler is selected from one or more of glass fibre, potassium titanate fiber, metalclad glass fibre, ceramic fiber, wollastonite fibre, metallic carbide fibres, metal-cured fiber, fibrous magnesium silicate, sapphire whisker, silicon carbide fiber, gypsum fiber or boron fibre, is preferably glass fibre; Described organic reinforcing filler is selected from Kevlar and/or carbon fiber.

7. daiamid composition according to claim 4, it is characterized in that, being shaped as of described reinforcing filler is non-fibrous, its median size is 0.001～10 μ m, be preferably 0.01～5 μ m, be selected from potassium titanate crystal whisker, ZnOw, aluminium borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, agalmatolite, wilkinite, polynite, lithium montmorillonite, synthetic mica, asbestos, silico-aluminate, aluminum oxide, silicon oxide, magnesium oxide, zirconium white, titanium oxide, ferric oxide, calcium carbonate, magnesiumcarbonate, rhombspar, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, granulated glass sphere, ceramic bead, boron nitride, one or more of silicon carbide or silicon-dioxide.

8. daiamid composition according to claim 4, it is characterized in that, described fire retardant is halogenated flame retardant or halogen-free flame retardants, described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecanes or brominated aromatic cross-linked polymer, is preferably preferred brominated Polystyrene; Described halogen-free flame retardants is selected from one or more of the fire retardant that contains nitrogen combustion inhibitor, phosphonium flame retardant or nitrogenous and phosphorus; Be preferably phosphonium flame retardant; The content of described fire retardant is 10 ~ 40wt%.

9. daiamid composition according to claim 8, it is characterized in that it is that phosphoric acid ester, butylbenzene are one or more of phosphoric acid ester, hypophosphite that described phosphonium flame retardant is selected from monophosphate aryl phosphate ester, bis phosphoric acid aryl phosphate ester, alkyl phosphonic acid dimethyl ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene; Be preferably the hypophosphite with following structure formula I:

In the formula, R ¹, R ²Identical or different, be expressed as straight chain or contain alkyl and/or aryl or the phenyl of 1 ~ 6 carbon atom of side chain; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or by protonated nitrogenous base; M is 1 ~ 3.