CN100590146C - Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material - Google Patents

Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material Download PDF

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CN100590146C
CN100590146C CN200810089637A CN200810089637A CN100590146C CN 100590146 C CN100590146 C CN 100590146C CN 200810089637 A CN200810089637 A CN 200810089637A CN 200810089637 A CN200810089637 A CN 200810089637A CN 100590146 C CN100590146 C CN 100590146C
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nylon
halogen
flame
retardant
hypophosphite
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CN101280105A (en
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卢文生
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Liu Chengzhi
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a preparation method for high-mechanical performance halogen-free flame-retardant nylon 66 composite materials, comprising the following steps: (1) weighing; (2) mixing; (3) blending and extruding. The invention also discloses a composite material prepared with the method; the composite material has the following components: nylon 66, short glass fibers, main antioxidant, auxiliary antioxidant, compound flame retardant and lubricant. The method of the invention has the advantages that the composite material has the fire-retardant performance up to UL 94 V-0 (0.8mm) level, and has more prominent mechanical properties than the existing halogen-free flame retardant system, with equivalent mechanical properties with the halogen-containing flame retardant system; therefore, the composite material of the invention can completely replace the existing halogen-containing flame-retardant products and halogen-free flame-retardant products, with easy preparation method andeasy operation. The high-mechanical performance halogen-free flame-retardant nylon composite material can be widely used in home appliances, electronics parts, auto parts, and so on.

Description

Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and matrix material
Technical field
The present invention relates to a kind of polymer composite, relate in particular to a kind of halogen-free flame-retardant reinforced nylon 66 matrix materials that industries such as electronic electric equipment that environmental protection flame retardant requires, household appliances, auto parts machinery are arranged that can be used for injection moulding.
Background technology
In the prior art, nylon 66 is a kind of even thermoplastic polyesters that formed by hexanodioic acid and hexanediamine polycondensation, have high strength, wear-resisting, anti-solvent, advantage such as self lubricity is good and the use temperature scope is wide, be one of the widest engineering plastics of purposes, be widely used in various electronic electric equipments and household appliances.Because the present used fire retardant nearly 80% of fire-retardant nylon is a halogen containing flame-retardant, be that brominated flame-retardant efficient height, the consumption of representative is few particularly with polybromodiphenyl ether and polybrominated biphenyl material, performance impact to material is little, and it is moderate, its usefulness/price can be equal to than non-other fire retardants, so 70%～80% all uses this based flame retardant in China's electric series products for export.But bromide fire retardant is subjected to the puzzlement of Dioxins problem in recent years, use its (bromine one antimony system) fire-retardant macromolecular material the time can generate a large amount of flue dust and corrosive gases in thermo-cracking and burning simultaneously, European Union and Japan put into effect in succession that it is forbidden by decree to and use this type of fire retardant at present.European Union has risen on July 1st, 2006 and has implemented in full the ROHS instruction, and the electronic and electrical equipment that this decree requires to throw in European Union must not contain polybromodiphenyl ether, Polybrominated biphenyl; Japan has also put into effect corresponding standard JISC0950, and the SONY-SS-00259 standard that Sony Corporation puts into effect is more strict to the requirement of fire retardant; In the U.S., the legislation of indivedual state government is at the use of bromide fire retardant.Above decree and standard have seriously restricted the outlet of China's electronic and electrical equipment, therefore must greatly develop the development trend that bittern-free flame-proof material could adapt to the world market, in order to promote quality product, cooperate the requirement of international standard, " the electronics and IT products pollution control management way " of Chinese version RoHS is also from formal enforcement on March 1 in 2007.Bittern-free flame-proof material has also appearred in the prior art, this fire retardant material has satisfied environmental requirement, comply with the needs of world market development, but the not high problem of not high, the fire-retardant rank of this series products ubiquity mechanical property, therefore it is applied and is subjected to certain restriction, develops high-mechanical property and other bittern-free flame-proof material of high flame retardant level becomes present problem demanding prompt solution.
Summary of the invention
The technical problem to be solved in the present invention is, the low problem of bittern-free flame-proof material mechanical property at preparation method's production of the prior art, but provide a kind of preparation method of industrialized mass production halogen-free flame-proof nylon 66 having high-mechanical property matrix material, this method is easy, the constant product quality of preparation.
Second technical problem that the present invention will solve is, at the lower problem of bittern-free flame-proof material mechanical property of the prior art, the halogen-free flame-proof nylon 66 having high-mechanical property matrix material that adopts preceding method to produce is provided, this matrix material is the flame retardant properties excellence not only, and environmental protection, safety, electrical insulation capability excellence.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of preparation method of halogen-free flame-proof nylon 66 having high-mechanical property matrix material is characterized in that, may further comprise the steps:
(1) weighing: take by weighing each feed composition respectively according to prescription: nylon 66, short glass fiber, primary antioxidant, auxiliary antioxidant, composite flame-retardant agent, lubricant.
(2) mix: with each component add in proportion variable-ratio by N 2In the stirrer of sealing, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation.
Described step (1) is further comprising the steps of:
(11) preparation composite flame-retardant agent: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, hypophosphite is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N 2Atmosphere in, it is carried out pyroprocessing, repeatedly more than twice or twice, all be cooled to room temperature after finishing pyroprocessing each time, after the cooling hypophosphite is carried out powdered and sub-sieve;
(c) silane coupling agent is slowly watered through on the hypophosphite surface of (b) step process, carry out again high-speed mixing stir it is fully absorbed after, make composite flame-retardant agent.
Described step (1) is further comprising the steps of:
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.
Described step (11) and (12) no sequencing.
Described step (3) is that the raw material behind the thorough mixing is added in the twin screw extruder, carries out melting mixing, extrudes and granulation; The screw diameter of this twin screw extruder is 30～90mm, and the ratio of spiro rod length and diameter is set at 32～44, and extrusion temperature is 240～280.
Step of the present invention (11), owing to having superior especially consistency between the composite flame-retardant agent for preparing through surface treatment step and other components in the matrix material, greatly improved interface between each component in conjunction with dynamics, the lifting of the matrix material machinery performance of preparation is had crucial effects.
Step of the present invention (12) before each component being carried out step (2) mixing, with alkali free glass fibre and silane mixture, stirs, and is prepared into surface treated alkali free glass fibre.Other component compatibilities in surface treated glass fibre and the matrix material are stronger, help further strengthening the mechanical property of whole matrix material.
A kind of nylon 66 composite material that adopts aforesaid halogen-free flame-proof nylon 66 having high-mechanical property composite material and preparation method thereof preparation, it comprises the component of following weight part ratio:
Nylon 66 35～70%;
Short glass fiber 0～40%;
Primary antioxidant 0.2～0.5%;
Auxiliary antioxidant 0.2～0.5%;
Composite flame-retardant agent 15～25%;
Lubricant 0.3～1%.
Described primary antioxidant is an organophosphite, and described organophosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
Described auxiliary antioxidant is N, N-pair-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine.
Described composite flame-retardant agent is the mixture of surface treated hypophosphite and silane.
Described lubricant is a montanin wax, and described montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt.
Described short glass fiber can well merge with the nylon 66 in the component through surface treatment, has improved the mechanical property of material effectively.
Described primary antioxidant is N, N-pair-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine.Described auxiliary antioxidant is an organophosphite, and described organophosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.The adding of oxidation inhibitor makes nylon 66 have good processing stability in the course of processing, avoids color and luster, performance to change.
Described composite flame-retardant agent is the mixture for surface treated hypophosphite and silane.Described fire retardant hypophosphite and silane will carry out surface treatment before compound, the fire retardant mixture of Xing Chenging and other components in the composition (nylon 66 and short glass fiber that especially content is bigger) have better consistency like this, greatly improved interface between each component in conjunction with dynamics, not only effectively raise the flame retardant resistance of whole material, flame retardant rating reaches UL 94 V-0 levels (0.8mm), improve the mechanical property of this material more greatly, effectively solved the low relatively difficult problem of bittern-free flame-proof material mechanical property of the prior art.
Described lubricant is a montanin wax, and described montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt.Described lubricant can promote the fusion of each component, improved the flowability of described matrix material molten mass effectively, has reduced the friction between matrix material solution and processor in the course of processing, has demoulding effect preferably simultaneously, has shortened injection cycle.
Beneficial effect of the present invention is: the preparation method of halogen-free flame-proof nylon 66 having high-mechanical property matrix material provided by the present invention, the technology that it is traditional relatively, need carry out pre-treatment to different compositions, halogen-free flame-proof nylon 66 having high-mechanical property matrix material machinery performance height through this step preparation, flame retardant properties is good, the lifting of composite property is had decisive action, and preparation technology is simple, operation easily, the constant product quality of preparation.Matrix material provided by the invention, with respect to halogen-free flameproof product of the prior art, not only its flame retardant properties reaches UL 94 V-0 (0.8mm) level, and has more outstanding mechanical property than existing halogen-free flame-retardant system, suitable with the mechanical property of Halogen flame-retardant system, therefore can substitute the matrix material of the fire-retardant and halogen-free flameproof of existing Halogen fully.The present invention can be widely used in manufacturing of matrix materials such as household electrical appliances accessory, electronic product accessory or auto parts machinery etc.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1: a kind of preparation method of halogen-free flame-proof nylon 66 having high-mechanical property matrix material, it is characterized in that, and may further comprise the steps:
(1) weighing:, take by weighing each feed composition respectively according to wherein filling a prescription: nylon 66, short glass fiber, primary antioxidant, auxiliary antioxidant, composite flame-retardant agent, lubricant referring to table 1.
(11) preparation composite flame-retardant agent: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, hypophosphite is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N 2Atmosphere in, it is carried out pyroprocessing, all be cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time, after the cooling hypophosphite is carried out powdered and sub-sieve;
(c) silane coupling agent is slowly watered through on the hypophosphite surface of (b) step process, carry out again high-speed mixing stir it is fully absorbed after, make composite flame-retardant agent.
Described step (1) is further comprising the steps of:
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.
Described step (11) and (12) no sequencing.
(2) mix: with each component add in proportion variable-ratio by N 2In the stirrer of sealing, stir and make its thorough mixing;
(3) mixing extruding: be that the raw material behind the thorough mixing is added in the twin screw extruder, carry out twice above melting mixing after, extrude, granulation, the screw diameter of this twin screw extruder is 30～90mm, and the ratio of spiro rod length and diameter is set at 32～44, and extrusion temperature is 240～280.
Referring to table 1, a kind of nylon 66 composite material that adopts aforesaid halogen-free flame-proof nylon 66 having high-mechanical property composite material and preparation method thereof preparation, it comprises the component of following weight part ratio: nylon 6635～70%, short glass fiber 0～40%, primary antioxidant 0.2～0.5%, auxiliary antioxidant 0.2～0.5%, composite flame-retardant agent 15～25%, lubricant 0.3～1%.
Concrete, in the present embodiment, the CAS NO. of described nylon 66 is 32131-17-2, and described short glass fiber (CAS NO. is 65997-17-2) is a toughener, this glass fibre carries out surface treatment with silane, can well merge with the nylon 66 in the component; Described primary antioxidant adopts organophosphite; be specially three (2; the 4-di-tert-butyl-phenyl) phosphorous acid ester (CAS NO. is 31570-04-4); described auxiliary antioxidant is N; N-pair-[3-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine (CAS NO. is 23128-74-7); described fire retardant adopts hypophosphite (CAS NO. is 6303-21-5); described lubricant adopts the illiteracy dawn cured; be specially brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester (CAS NO. is 73138-44-0) and lipid acid-montanin wax calcium salt (CAS NO. is 68308-22-5).
Preparation method concrete in the present embodiment is: take by weighing each raw material successively in each the ingredients weight parts ratio shown in table 1 the 2nd row; Before mixing, wherein hypophosphite is carried out surface treatment, detailed process is: at first hypophosphite is ground 1～10h, oven dry then places N with the hypophosphite after the oven dry 2Atmosphere in, repeated multiple times (minimum should be more than twice, be generally 3～6 times) carry out pyroprocessing, make its surface state that once chapped, after being cooled to room temperature hypophosphite is carried out powdered and sub-sieve, again silane is watered on the hypophosphite surface, mix to stir that it is fully absorbed, promptly make composite flame-retardant agent; Surface treatment process before alkali free glass fibre mixes is: with alkali free glass fibre and silane mixture, stir, make its abundant, uniform mixing.Above-mentioned two surface treatment step can be carried out respectively simultaneously.
With each component and previously prepared composite flame-retardant agent, short glass fiber, getting material in proportion adds in the agitation vat behind the thorough mixing, add again and carry out repeated multiple times in the twin screw extruder (more than twice, be generally 3～6 times) melting mixing, make each component react fusion fully after, extrude, granulation, the screw diameter of twin screw extruder is 40mm, and the ratio of spiro rod length and diameter is set at 38, and extrusion temperature is 250 ℃.
Embodiment 2: the preparation method and the matrix material of the halogen-free flame-proof nylon 66 having high-mechanical property matrix material that present embodiment provides, it is identical with embodiment 1 basically, its difference is, the screw diameter of twin screw extruder is 70mm, the ratio of spiro rod length and diameter is set at 40, and extrusion temperature is 260 ℃; The raw material that this matrix material is included is table 1 the 3rd listed component of row and part by weight.
Embodiment 3: the preparation method and the matrix material of a kind of halogen-free flame-proof nylon 66 having high-mechanical property matrix material that present embodiment provides, basically identical with embodiment 1, its difference is, the screw diameter of twin screw extruder is 90mm, the ratio of spiro rod length and diameter is set at 44, and extrusion temperature is 280 ℃; The raw material that this matrix material is included is table 1 the 4th listed component of row and part by weight.
Table 1
Material name Embodiment 1 (wt%) Embodiment 2 (wt%) Embodiment 3 (wt%)
Nylon 66 46.5 53.7 78.6
Short glass fiber 35 25 10
Auxiliary antioxidant 0.2 0.4 0.5
Primary antioxidant 0.3 0.2 0.5
Hypophosphite 17 20 25
Montanin wax 1 0.7 0.4
Halogen-free flame-retardant reinforced nylon 66 composite sample test performances with above-mentioned three embodiment preparation, its result and employing standard are as shown in table 2, contrast as can be known with traditional bromo-antimony flame-retardant system test result, the mechanical property of matrix material of the present invention is near the mechanical property of traditional bromo-antimony flame-retardant system, and the flame retardant effect of flame retardant effect and Halogen system is suitable, and the CTI of anti-electric arc value is higher than the Halogen flame-retardant system; Compare with other halogen-free flame-retardant system, not only each parameter of its mechanical property is higher than other halogen-free flame-retardant systems far away, and its flame retardant properties also reaches V-0 (0.8mm) grade, has excellent technique effect.So product performance of the present invention reach the performance requirement to plastic material such as household electrical appliances accessory, electronic product accessory fully, have broad application prospects.
Table 2
Test event Testing standard Embodiment 1 (containing 35% glass) Embodiment 2 (containing 25% glass) Embodiment 3 (containing 10% glass) Bromo-antimony flame-retardant system (containing 35 % glasses) Halogen-free flameproof product (containing 25% glass)
Density (g/cm 3) ISO1183 1.48 1.39 1.34 1.67
Vertical forming shrinking percentage (%) LIXIN-EP 0.4 0.6 1.2 0.6
Parallel molding shrinkage (%) LIXIN-EP 0.3 0.4 0.7 0.3
Tensile strength (Mpa) ISO527 160 135 95 160 95.6
Elongation at break (%) ISO527 1.7 3 5 3
Flexural strength (Mpa) ISO178 230 200 140 240 137.9
Modulus in flexure (Mpa) ISO178 10800 9100 6000 11000 6806.4
Notched Izod impact strength (KJ/m 2) ISO180 13.5 10 5 12 7.9
Unnotched impact strength (KJ/m 2) ISO180 55 35 15 60
Fusing point (℃) ISO3146-C 260-265 260-265 260-265 260-265
Heat-drawn wire (66psi) ISO75-1 255 250 245 260
Heat-drawn wire (264psi) ISO75-2 250 245 210 250
0.8mm flame retardant rating ISO1210/UL94 V-0 V-0 V-0 V-0
1.6mm flame retardant rating ISO1210/UL94 V-0 V-0 V-0 V-0
3.2mm flame retardant rating ISO1210/UL94 V-0 V-0 V-0 V-0 V-0
Glowing filament (℃) IEC 695-2-1 960 960 960 960
The CTI of anti-electric arc (Volt) UL-746A 600 550 500 300

Claims (5)

1. the preparation method of a halogen-free flame-proof nylon 66 having high-mechanical property matrix material is characterized in that, it may further comprise the steps:
(1) weighing: take by weighing each feed composition respectively according to prescription: nylon 66, short glass fiber, primary antioxidant, auxiliary antioxidant, composite flame-retardant agent, lubricant;
Described prescription according to the ingredients weight parts ratio is:
Nylon 66 35～70%;
Short glass fiber 10～40%;
Primary antioxidant 0.2～0.5%;
Auxiliary antioxidant 0.2～0.5%;
Composite flame-retardant agent 15～25%;
Lubricant 0.3～1%;
(2) mix: each component is added in the stirrer by the N2 sealing of variable-ratio by described formula rate, stir and make its thorough mixing;
(3) mixing extruding: the raw material behind the thorough mixing is added in the forcing machine, carry out twice above melting mixing after, extrude granulation;
Described step (1) is further comprising the steps of:
(11) preparation composite flame-retardant agent: after taking by weighing hypophosphite and silane coupling agent, the two is carried out surface treatment, the concrete operations step is:
(a) take by weighing hypophosphite according to prescription, hypophosphite is ground 1～10h, then oven dry;
(b) hypophosphite after will drying places N 2Atmosphere in, it is carried out pyroprocessing, all be cooled to room temperature repeatedly more than twice or twice, and after finishing pyroprocessing each time, after the cooling hypophosphite is carried out powdered and sub-sieve;
(c) silane coupling agent is slowly watered through on the hypophosphite surface of (b) step process, carry out again high-speed mixing stir it is fully absorbed after, make composite flame-retardant agent.
(12) prepare surface treated alkali free glass fibre: after taking by weighing alkali free glass fibre and silane respectively,, stir then with the two mixing.
Described step (11) and (12) no sequencing;
Described lubricant is a montanin wax, and described montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt.
2. according to the preparation method of the described halogen-free flame-proof nylon 66 having high-mechanical property matrix material of claim 1, it is characterized in that described step (3) is that the raw material behind the thorough mixing is added in the twin screw extruder, carries out melting mixing, extrudes and granulation; The screw diameter of this twin screw extruder is 30～90mm, and the ratio of spiro rod length and diameter is set at 32～44, and extrusion temperature is 240～280.
3. nylon 66 composite material that adopts the described halogen-free flame-proof nylon 66 having high-mechanical property composite material and preparation method thereof of claim 1 to make is characterized in that it is the component of following weight part ratio:
Nylon 66 35～70%;
Short glass fiber 10～40%;
Primary antioxidant 0.2～0.5%;
Auxiliary antioxidant 0.2～0.5%;
Composite flame-retardant agent 15～25%;
Lubricant 0.3～1%;
Described composite flame-retardant agent is the mixture of surface treated hypophosphite and silane;
Described lubricant is a montanin wax, and described montanin wax is brown coal cerinic acid-1-methyl isophthalic acid, the blend of 3-glyceryl ester and lipid acid-montanin wax calcium salt;
Described short glass fiber is through surface treatment.
4. nylon 66 composite material according to claim 3 is characterized in that: described primary antioxidant is an organophosphite, and described organophosphite is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
5. nylon 66 composite material according to claim 3 is characterized in that: described auxiliary antioxidant is N, N-pair-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine.
CN200810089637A 2008-04-11 2008-04-11 Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material Expired - Fee Related CN100590146C (en)

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