CN102134393B - Polyphthalamide reinforced material and preparation method thereof - Google Patents

Polyphthalamide reinforced material and preparation method thereof Download PDF

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Publication number
CN102134393B
CN102134393B CN2010106112407A CN201010611240A CN102134393B CN 102134393 B CN102134393 B CN 102134393B CN 2010106112407 A CN2010106112407 A CN 2010106112407A CN 201010611240 A CN201010611240 A CN 201010611240A CN 102134393 B CN102134393 B CN 102134393B
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polyphthalamide
strongthener
red phosphorus
preparation
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CN102134393A (en
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徐东
徐永
马百钧
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Polymer Science Shenzhen New Materials Co Ltd
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Polymer Science Shenzhen New Materials Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/80Component parts, details or accessories; Auxiliary operations
    • B29B7/88Adding charges, i.e. additives
    • B29B7/90Fillers or reinforcements, e.g. fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/201Pre-melted polymers
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/00Use of ingredients characterised by shape
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    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
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    • B29C2948/92504Controlled parameter
    • B29C2948/92514Pressure
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C2948/92561Time, e.g. start, termination, duration or interruption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/10Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids

Abstract

The invention discloses a polyphthalamide reinforced material and a preparation method thereof. The polyphthalamide reinforced material comprises the following formula components in percentage by mass: 48 to 58 percent of polyphthalamide, 6 to 15 percent of modified red phosphorus, 35 to 45 percent of filler intensifier and 1 to 2 percent of additive. The polyphthalamide reinforced material disclosed by the invention tales polyphthalamide as a basic component, and as the polyphthalamide acts with the modified red phosphorus, the filler intensifier, the additive and other components in an extrusion process, the polyphthalamide reinforced material has high flame-retarding performance and mechanical properties such as tensile strength and impact strength. Meanwhile, the production cost of the polyphthalamide reinforced material is low. The preparation method of the polyphthalamide reinforced material comprises: mixing the components according to a formula; and performing segmental feeding and extrusion. The preparation method adopts a simple process, and is low in cost and suitable for industrial production.

Description

A kind of polyphthalamide strongthener and preparation method thereof
Technical field
The invention belongs to chemical technology field, particularly a kind of polyphthalamide strongthener and preparation method thereof.
Background technology
Polyphthalamide (PPA) is a kind of hemicrystalline thermoplasticity aromatic polyamide, is commonly called as fragrant high-temperature nylon.PPA has very excellent heat resisting, and secular working temperature can be up to 180 ℃, and the short-term heatproof can reach 290 ℃; Simultaneously, PPA has high-modulus, high firmness, high performance-price ratio, dimensional stability, low water absorption etc.In view of the further lifting that market requires material environment friendly, increasing application scenario needs bittern-free flame-proof material.At present, the fire-retardant of PPA mainly reaches through halogen, and its halogen-free flameproof exists that cost is high, efficient is lower, to the bigger shortcoming of material property influence, this to a great extent limit the application of PPA.
Red phosphorus is as the comparatively general halogen-free flame retardants of a kind of use, and its cost is relatively low, is applicable to the fire-retardant of most of macromolecular material.Yet it exists flame retarding efficiency not high, and there is big adverse influence in the mechanical property to material simultaneously.
Summary of the invention
The purpose of the embodiment of the invention is to overcome the above-mentioned deficiency of prior art, and a kind of polyphthalamide strongthener with good flame retardancy and mechanical property is provided.
And, the preparation method of above-mentioned polyphthalamide strongthener.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of polyphthalamide strongthener comprises the recipe ingredient of following mass percent:
Figure GDA0000140664730000021
Said modification red phosphorus contains epoxide group and amino red phosphorus for the surface, and it is to obtain through at least a processing in γ-Racemic glycidol oxygen propyl trimethoxy silicane, the γ-An Jibingjisanyiyangjiguiwan with amino that said modification red phosphorus contains epoxide group.
And a kind of polyphthalamide strongthener preparation method comprises the steps:
Prescription according to above-mentioned polyphthalamide strongthener takes by weighing each component;
Said polyphthalamide, modification red phosphorus, additive are mixed, form mixture;
Said mixture is extruded;
In said extrusion, add to fill toughener, continue to extrude, granulation, obtain said polyphthalamide strongthener.
Above-mentioned polyphthalamide strongthener is basic components with the polyphthalamide; And with modification red phosphorus, fill components such as toughener, additive and in extrusion, interact; Make the polyphthalamide strongthener have good flame retardant property, and the mechanical property with good tensile and shock resistance.Simultaneously; The present invention adopts modification red phosphorus as fire retardant; When giving this polyphthalamide strongthener good flame retardant property, thermal property and mechanical property, make that also the raw materials cost of this polyphthalamide strongthener is low, specifically referring to data in the below table 1.This polyphthalamide strongthener preparation method only needs each component to be mixed and the sectional charging is extruded and can be obtained product by prescription, and its preparation method technology is simple, and cost is low, is suitable for suitability for industrialized production.
Description of drawings
To combine accompanying drawing and embodiment that the present invention is described further below, in the accompanying drawing:
Fig. 1 is polyphthalamide strongthener preparing method's of the present invention process flow diagram.
Embodiment
Clearer for technical problem, technical scheme and beneficial effect that the present invention will be solved, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the invention provides a kind of polyphthalamide strongthener with good flame retardancy and mechanical property.This polyphthalamide strongthener comprises the recipe ingredient of following mass percent:
Figure GDA0000140664730000031
Particularly; The quality percentage composition of above-mentioned modification red phosphorus in the recipe ingredient of embodiment of the invention polyphthalamide strongthener is preferably 6%; This preferred modification red phosphorus content; Can effectively reduce modification red phosphorus consumption, reduce production costs, make the polyphthalamide strongthener have good flame retardant property and good mechanical property simultaneously.
The existence of above-mentioned modification red phosphorus component when giving this polyphthalamide strongthener good flame retardant property and mechanical property, makes that also the raw material of this polyphthalamide strongthener is originally low.This modification red phosphorus is preferably the surface and contains epoxide group and amino red phosphorus.Its preparation method is preferably following:
SA1: alcohol or the acetone soln of red phosphorus with γ-Racemic glycidol oxygen propyl trimethoxy silicane and/or γ-An Jibingjisanyiyangjiguiwan mixed, form solidliquid mixture;
SA2: solidliquid mixture is heated to 45~55 ℃, and carries out supersound process;
SA3: the solidliquid mixture after the supersound process is carried out solid-liquid separation, and drying obtains said modification red phosphorus.
Particularly, in the above-mentioned modification red phosphorus preparation method SA1 step, the mass ratio of red phosphorus and γ-Racemic glycidol oxygen propyl trimethoxy silicane and/or γ-An Jibingjisanyiyangjiguiwan is preferably 3: 1.Wherein, The alcohol of γ-Racemic glycidol oxygen propyl trimethoxy silicane and/or γ-An Jibingjisanyiyangjiguiwan or the concentration of acetone soln can be adjusted according to needs of production flexibly, but guarantee that the mass ratio of red phosphorus and γ-Racemic glycidol oxygen propyl trimethoxy silicane and/or γ-An Jibingjisanyiyangjiguiwan is preferably 3: 1.
In the SA1 step, red phosphorus preferably carries out drying treatment under 50~70 ℃ of conditions.
In the above-mentioned modification red phosphorus preparation method SA2 step, the time of supersound process is preferably 1.5 hours.
In the above-mentioned modification red phosphorus preparation method SA3 step, the mode of solid-liquid separation can adopt modes such as centrifugal or filtration to carry out.The exsiccant mode preferably places 30~40 ℃ of vacuum drying oven bakings 4-6 hour with the solid of solid-liquid separation gained.
Above-mentioned filling toughener is preferably alkali free glass fibre.This fills toughener logical other component actings in conjunction in extrusion, can effectively strengthen polyphthalamide strongthener intensity and toughness.
Above-mentioned additive preferably includes at least a in coupling agent, lubricant, the oxidation inhibitor.Wherein, Coupling agent is preferably γ-An Jibingjisanyiyangjiguiwan, and lubricant is preferably one or both in internal lubricant and the external lubricant, and oxidation inhibitor is preferably N; N-hexylidene-1; In 6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide], three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester one or both.Aforementioned internal lubricant is preferably the ester series lubricant agent, and external lubricant is preferably nonpolar lubricant.
Above-mentioned coupling agent, lubricant under the high speed shear effect in the extrusion, reduce the viscosity of mixture in extrusion, strengthened the dispersiveness of each component, make the polyphthalamide strongthener obtain good mechanical property.Oxidation inhibitor makes the polyphthalamide strongthener also have good antioxidant property.
Therefore; Above-mentioned polyphthalamide strongthener is basic components with the polyphthalamide; And with modification red phosphorus, fill components such as toughener, additive and in extrusion, interact; Make the polyphthalamide strongthener have good flame retardant property, and the mechanical property with good thermal property and tensile strength, shock resistance, when containing antioxidant component; The polyphthalamide strongthener also has good antioxidant property, specifically referring to data in the below table 1.Simultaneously, the present invention adopts modification red phosphorus as fire retardant, when giving this polyphthalamide strongthener good flame retardant property and mechanical property, makes that also the raw materials cost of this polyphthalamide strongthener is low.
The present invention also provides above-mentioned polyphthalamide strongthener preparation method, and its technical process is as shown in Figure 1.This method comprises the steps:
S1: the prescription according to above-mentioned polyphthalamide strongthener takes by weighing each component;
S2: said polyphthalamide, modification red phosphorus, additive are mixed, form mixture;
S3: said mixture is extruded;
S4: in said extrusion, add to fill toughener, continue to extrude, granulation, obtain said polyphthalamide strongthener.
Particularly, in the above-mentioned polyphthalamide strongthener preparation method S1 step, the recipe ingredient of the parts by weight that this polyphthalamide strongthener comprises is:
In another preferred embodiment, the recipe ingredient of the parts by weight that this polyphthalamide strongthener comprises is:
Figure GDA0000140664730000052
Wherein, the acquisition methods of modification red phosphorus such as above-mentioned in order to practice thrift length, repeats no more at this, and its concrete acquisition methods sees also the step of SA1~SA3 about modification red phosphorus preparation method.
In the above-mentioned polyphthalamide strongthener preparation method S2 step, before mixing, preferred elder generation carries out drying treatment with polyphthalamide under 100~150 ℃ of temperature.Additive is preferred to carry out drying treatment earlier under 40~60 ℃ of temperature.Preferably be in extrusion, to reduce to greatest extent the participation of moisture, avoid moisture to arrive polyphthalamide strongthener mechanical property through the purpose of drying treatment.
In the above-mentioned polyphthalamide strongthener preparation method S3 step; Each component preferred employing twin screw extruder of extruding of formed mixture after mixing is extruded in the S2 step, is CTE-35 (L-D=48) twin screw extruder etc. like the model of producing through Nanjing Ke Ya company.Extruding; The expressing technique of mixture in this twin screw extruder is preferably: 260~280 ℃ in a district, 280~300 ℃ in two districts, 280~320 ℃ in three districts, 290~320 ℃ in four districts, 290~320 ℃ in five districts, 290~310 ℃ in six districts, 290~310 ℃ in seven districts; This mixture residence time in each district of said twin screw extruder is preferably 3~6min; Preferred 14~the 18MPa of pressure, the rotating speed of said twin screw extruder screw rod are preferably 400~450 rev/mins.
In the above-mentioned polyphthalamide strongthener preparation method S4 step, fill the stage casing that toughener is selected in polyphthalamide strongthener expressing technique, as adding in three districts in the above-mentioned expressing technique, four districts or five districts.Expressing technique in this S4 step is as the expressing technique in the above-mentioned S3 step.
In above-mentioned S1~S4 step, in view of the self attributes of various raw materials and synergistic effect each other, the embodiment of the invention has adopted segmented mode to add raw material.Make that each material is intermolecular and have an effect between mutually when material is heating up rapidly under the high speed shear effect; Thereby form embodiment of the invention polyphthalamide strongthener; And give this polyphthalamide strongthener good flame retardant property, thermal property and good tensile strength, the mechanical property of shock resistance, antioxidant property.This polyphthalamide strongthener preparation method only needs each component to be mixed and the sectional charging is extruded and can be obtained product by prescription, and its preparation method technology is simple, and cost is low, is suitable for suitability for industrialized production.
Existing prescription and preparation method with concrete polyphthalamide strongthener is example, and the present invention is further elaborated.
Embodiment 1
The recipe ingredient of polyphthalamide strongthener mass percent is following:
Polyphthalamide 48%, filling toughener 45%, modification red phosphorus 6%, ester series lubricant agent 0.3%, nonpolar lubricant 0.3%, inhibitor 0.2%, coupling agent 0.2%.
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.1% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan; Modification red phosphorus acquisition methods is following:
SA1: the ethanolic soln of red phosphorus with γ-Racemic glycidol oxygen propyl trimethoxy silicane mixed, form solidliquid mixture, wherein, the mass ratio of red phosphorus and γ-Racemic glycidol oxygen propyl trimethoxy silicane is 3: 1;
SA2: solidliquid mixture is heated to 55 ℃, and carried out supersound process 1.5 hours;
SA3: the solidliquid mixture after the supersound process is carried out spinning, and baking was carried out drying in 6 hours in 30 ℃ of vacuum drying ovens, obtained said modification red phosphorus.
The preparation method is following for the polyphthalamide strongthener:
S11: polyphthalamide is for use 150 ℃ of following forced air dryings 6 hours;
S12: utilize impeller with pentaerythritol stearate, siloxanes, N; N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] and three (2; The 4-di-tert-butyl-phenyl) after phosphorous acid ester carries out mixed at high speed, for use 60 ℃ of dryings 2 hours;
S13: the raw material of handling well in step S11, the S12 step is put in the high-speed mixer, added the γ-An Jibingjisanyiyangjiguiwan uniform mixing again 3 minutes;
S14: mixed raw material among the step c is mixed through twin screw extruder, and the stage casing adds alkali free glass fibre, through melt extruding granulation.The complete processing of twin screw extruder is: 280 ℃ in a district, 300 ℃ in two districts, 320 ℃ in three districts, 320 ℃ in four districts, 290 ℃ in five districts, 290 ℃ in six districts, 300 ℃ in seven districts, residence time 6min, pressure 14MPa.
Embodiment 2:
The recipe ingredient of polyphthalamide strongthener mass percent is following:
Polyphthalamide 51%, filling toughener 40%, modification red phosphorus 7%, ester series lubricant agent 0.5%, nonpolar lubricant 0.5%, inhibitor 0.4%, coupling agent 0.6%;
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.2% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan; Modification red phosphorus acquisition methods is following:
SA1: red phosphorus is mixed with the acetone soln of γ-An Jibingjisanyiyangjiguiwan, form solidliquid mixture, wherein, the mass ratio of red phosphorus and γ-An Jibingjisanyiyangjiguiwan is 3: 1;
SA2: solidliquid mixture is heated to 45 ℃, and carried out supersound process 2 hours;
SA3: the solidliquid mixture after the supersound process is filtered, and baking is 4 hours in 40 ℃ of vacuum drying ovens, obtains said modification red phosphorus.
The preparation method is following for the polyphthalamide strongthener:
S21: polyphthalamide is for use 100 ℃ of following forced air dryings 6 hours;
S22: utilize impeller with pentaerythritol stearate, siloxanes, N; N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] and three (2; The 4-di-tert-butyl-phenyl) after phosphorous acid ester carries out mixed at high speed, for use 40 ℃ of dryings 2 hours;
S23: the raw material of handling well in step S11, the S12 step is put in the high-speed mixer, added the γ-An Jibingjisanyiyangjiguiwan uniform mixing again 3 minutes;
S24: mixed raw material among the step c is mixed through twin screw extruder, and the stage casing adds alkali free glass fibre, through melt extruding granulation.The complete processing of twin screw extruder is: 260 ℃ in a district, 280 ℃ in two districts, 280 ℃ in three districts, 290 ℃ in four districts, 300 ℃ in five districts, 300 ℃ in six districts, 310 ℃ in seven districts, residence time 3min, pressure 18MPa.
Embodiment 3:
The recipe ingredient of polyphthalamide strongthener mass percent is following:
Polyphthalamide 55%, filling toughener 37.5%, modification red phosphorus 6%, ester series lubricant agent 0.4%, nonpolar lubricant 0.4%, inhibitor 0.4%, coupling agent 0.3%.
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.2% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.2%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan.
The preparation method is following for the polyphthalamide strongthener:
S31: polyphthalamide is for use 100~150 ℃ of following forced air dryings 6 hours;
S32: utilize impeller with pentaerythritol stearate, siloxanes, N; N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] and three (2; The 4-di-tert-butyl-phenyl) after phosphorous acid ester carries out mixed at high speed, for use 40~60 ℃ of dryings 2 hours;
S33: the raw material of handling well in step S11, the S12 step is put in the high-speed mixer, added the γ-An Jibingjisanyiyangjiguiwan uniform mixing again 3 minutes;
S34: mixed raw material among the step c is mixed through twin screw extruder, and the stage casing adds alkali free glass fibre, through melt extruding granulation.The complete processing of twin screw extruder is: 270 ℃ in a district, 290 ℃ in two districts, 290 ℃ in three districts, 300 ℃ in four districts, 295 ℃ in five districts, 295 ℃ in six districts, 305 ℃ in seven districts, residence time 4min, pressure 16MPa.
Embodiment 4:
The recipe ingredient of polyphthalamide strongthener mass percent is following:
Polyphthalamide 58%, filling toughener 35%, modification red phosphorus 6%, ester series lubricant agent 0.2%, nonpolar lubricant 0.3%, inhibitor 0.2%, coupling agent 0.3%.
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.1% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan.
The preparation method is identical with embodiment 1 for present embodiment polyphthalamide strongthener.
Comparison example 5:
The recipe ingredient of polyphthalamide strongthener mass percent that contains undressed red phosphorus combustion inhibitor component is following:
Polyphthalamide 58%, filling toughener 35%, red phosphorus 6%, ester series lubricant agent 0.2%, nonpolar lubricant 0.3%, inhibitor 0.2%, coupling agent 0.3%.
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.1% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan.
The polyphthalamide strongthener preparation method that this comparison example contains undressed red phosphorus combustion inhibitor component is identical with embodiment 1.
Comparison example 6:
The recipe ingredient of polyphthalamide strongthener mass percent that contains undressed red phosphorus combustion inhibitor component is following:
Polyphthalamide 53%, filling toughener 35%, red phosphorus 11%, ester series lubricant agent 0.2%, nonpolar lubricant 0.3%, inhibitor 0.2%, coupling agent 0.3%.
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.1% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan.
The polyphthalamide strongthener preparation method that this comparison example contains undressed red phosphorus combustion inhibitor component is identical with embodiment 1.
Comparison example 7:
The recipe ingredient of polyphthalamide strongthener mass percent that does not contain flame retardant compositions is following:
Polyphthalamide 64%, filling toughener 35%, ester series lubricant agent 0.2%, nonpolar lubricant 0.3%, inhibitor 0.2%, coupling agent 0.3%.
Wherein, above-mentioned nonpolar lubricant is a siloxanes; The ester series lubricant agent is a pentaerythritol stearate; The filling toughener is an alkali free glass fibre; Inhibitor is N, N-hexylidene-1,6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] 0.1% and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester 0.1%; Coupling agent is a γ-An Jibingjisanyiyangjiguiwan.
The polyphthalamide strongthener preparation method that this comparison example does not contain flame retardant compositions is identical with embodiment 1.
During the foregoing description 1 to embodiment 4 is filled a prescription about the polyphthalamide strongthener with comparison example 5 to comparison example 7; Fill the alkali free glass fibre that toughener is produced for megalith group; Coupling agent is the γ-An Jibingjisanyiyangjiguiwan that Chengdu Long March chemical reagents corporation produces; Internal lubricant is that the pentaerythritol stearate that Suzhou Xingtai state photochemistry auxiliary agent ltd produces is PETS, and nonpolar lubricant is the siloxanes that Chengdu Long March chemical reagents corporation produces, and oxidation inhibitor is the N that Chengdu Long March chemical reagents corporation produces; N-hexylidene-1; 6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide] and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester are composite.
The performance test experiment:
The polyphthalamide strongthener that makes in the foregoing description 1 to embodiment 4 and comparison example 5 to the comparison example 7 is carried out performance test according to criterion:
Tensile strength: detect by ASTM D-638 standard.Specimen types is the I type, batten size (millimeter): 150 (length) * (20 ± 0.2) (end size) * (4 ± 0.2) (thickness), draw speed is 50 mm/min.
Flexural strength and modulus in flexure: detect by ASTM D-790 standard.Specimen types is specimen size (millimeter): (80 ± 2) * (20 ± 0.2) * (4 ± 0.2), rate of bending are 20 mm/min.
Socle girder notched Izod impact strength: detect by ASTM D-256 standard.Specimen types is the I type, batten size (millimeter): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2); The breach type is a category-A, and notch depth is 1/3 of a thickness.
Heat-drawn wire: detect by ISO 75-2 standard.Specimen types is the I type, batten size (millimeter): 127 (length) * (13 ± 0.1) * (6.35 ± 0.1); Temperature rise rate is 120 ℃/h, pressure position 1.82MPa, and setting deformation quantity is 0.21 millimeter.
Flame retardant properties: press the UL-94 standard testing, batten thickness is approximately 1.6 millimeters.
According to above-mentioned testing standard, the The performance test results such as the following table 1 of the polyphthalamide strongthener that makes in the foregoing description 1 to embodiment 4 and comparison example 5 to the comparison example 7:
Table 1
Figure GDA0000140664730000111
Can find out from last table 1; As PPA, to fill toughener be that the content of alkali free glass fibre is when being respectively 48~58%, 35~45%; Tensile strength, flexural strength and modulus that the modification red phosphorus flame-retardant strengthens the PPA matrix material all remain on a higher level, and its heat-drawn wire can reach 280 ℃.Simultaneously, Flame Retardancy can also reach V 0Level.And through with the performance of comparison example 5,6 relatively, it is untreated that the flame retarding efficiency that can obviously find modification red phosphorus will be higher than, when the content of modification red phosphorus was 6%, Flame Retardancy can reach V 0, be HB and adopt the red phosphorus flame-retardant performance of non-modified, when non-modified red phosphorus add-on was 11%, the flame retardant properties of material just reached V 1Simultaneously, the mechanical property of comparative material and thermal property can find out that the surface-treated to red phosphorus helps the lifting of material property, the reduction by a relatively large margin of the red phosphorus of non-modified the mechanical property of material.Can find out with comparison example 7 by embodiment 4, the adding of modification red phosphorus, descending does not appear in the thermal property of PPA strongthener and mechanical property; On the contrary; Under the condition that other performances maintain an equal level, the impact property of material obviously rises, and this shows that the adding of modification red phosphorus has improved the toughness of material.This also further specifies, and the present invention is effective to the surface modification treatment of red phosphorus.Polyphthalamide strongthener mechanical property, flame retardant properties and the thermal property excellence that contains the modification red phosphorus flame-retardant provided by the invention is applicable to fields such as electronics, electrical equipment, aerospace.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. polyphthalamide strongthener comprises the recipe ingredient of following mass percent:
Figure FDA0000140664720000011
Said modification red phosphorus contains epoxide group and amino red phosphorus for the surface, and it is to obtain through at least a processing in γ-Racemic glycidol oxygen propyl trimethoxy silicane, the γ-An Jibingjisanyiyangjiguiwan with amino that said modification red phosphorus contains epoxide group.
2. polyphthalamide strongthener according to claim 1 is characterized in that: in the said polyphthalamide strongthener recipe ingredient, the quality percentage composition of modification red phosphorus is 6%.
3. polyphthalamide strongthener according to claim 1 is characterized in that: said filling toughener is an alkali free glass fibre; Said additive comprises at least a in coupling agent, lubricant, the oxidation inhibitor.
4. polyphthalamide strongthener according to claim 3 is characterized in that: said coupling agent is a γ-An Jibingjisanyiyangjiguiwan;
Said lubricant is one or both in internal lubricant, the external lubricant;
Said oxidation inhibitor is N, N-hexylidene-1, one or both in 6-two [3-(3,5-di-t-butyl-4-phenylor) propionic acid amide], three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
5. a polyphthalamide strongthener preparation method comprises the steps:
Prescription according to the arbitrary said polyphthalamide strongthener of claim 1~4 takes by weighing each component;
Said polyphthalamide, modification red phosphorus, additive are mixed, form mixture;
Said mixture is extruded;
In said extrusion, add to fill toughener, continue to extrude, granulation, obtain said polyphthalamide strongthener.
6. polyphthalamide strongthener preparation method according to claim 5; It is characterized in that: said extruding is to adopt twin screw extruder to extrude; Said expressing technique is: 260~280 ℃ in a district, 280~300 ℃ in two districts, 280~320 ℃ in three districts, 290~320 ℃ in four districts, 290~320 ℃ in five districts, 290~310 ℃ in six districts, 290~310 ℃ in seven districts; Said mixture residence time in each district of said twin screw extruder is 3~6min, pressure 14~18MPa.
7. polyphthalamide strongthener preparation method according to claim 5 is characterized in that: said modification red phosphorus acquisition methods is following:
Alcohol or the acetone soln of red phosphorus with γ-Racemic glycidol oxygen propyl trimethoxy silicane and/or γ-An Jibingjisanyiyangjiguiwan mixed, form solidliquid mixture;
Solidliquid mixture is heated to 45~55 ℃, and carries out supersound process;
Solidliquid mixture after the supersound process is carried out solid-liquid separation, and drying obtains said modification red phosphorus.
8. polyphthalamide strongthener preparation method according to claim 7 is characterized in that: the mass ratio of said red phosphorus and γ-Racemic glycidol oxygen propyl trimethoxy silicane and/or γ-An Jibingjisanyiyangjiguiwan is 3: 1.
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