CN104072981A - Halogen-free flame retardant polyamide material and preparation method thereof - Google Patents

Halogen-free flame retardant polyamide material and preparation method thereof Download PDF

Info

Publication number
CN104072981A
CN104072981A CN201410331829.XA CN201410331829A CN104072981A CN 104072981 A CN104072981 A CN 104072981A CN 201410331829 A CN201410331829 A CN 201410331829A CN 104072981 A CN104072981 A CN 104072981A
Authority
CN
China
Prior art keywords
halogen
nylon
free flame
poly
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410331829.XA
Other languages
Chinese (zh)
Inventor
储卫国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SUZHOU CHUANGJIA PLASTIC Co Ltd
Original Assignee
SUZHOU CHUANGJIA PLASTIC Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SUZHOU CHUANGJIA PLASTIC Co Ltd filed Critical SUZHOU CHUANGJIA PLASTIC Co Ltd
Priority to CN201410331829.XA priority Critical patent/CN104072981A/en
Publication of CN104072981A publication Critical patent/CN104072981A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B9/14Making granules characterised by structure or composition fibre-reinforced
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04Ingredients characterised by their shape and organic or inorganic ingredients
    • 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
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • 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
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means 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
    • B29C48/40Means 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
    • 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • B29B7/30Mixing; 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
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • 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
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • 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
    • B29C2948/92009Measured parameter
    • B29C2948/92266Mechanical properties
    • 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition

Abstract

The invention discloses a halogen-free flame retardant polyamide material which is mainly prepared from the following components in parts by weight: 40-72 parts of polyamide, 8-15 parts of a halogen-free flame retardant, 3-9 parts of a flame retardant synergist, 0.5-2 parts of a processing aid and 0-40 parts of a reinforcing modifier, wherein the halogen-free flame retardant is hypophosphite and the flame retardant synergist is silicon stannate with the silicon content being 30-60%. By adding the flame retardant synergist silicon stannate to reduce the use level of the halogen-free flame retardant hypophosphite, the flame retardant performance and the mechanical property are more excellent than those of a flame retardant material without adding silicon stannate, so that the cost is lowered. For the flame retardant material without adding silicon stannate, in spite of high content of the halogen-free flame retardant hypophosphite, the GWIT (Glow Wire Ignition Temperature) still cannot reach 960 DEG C. By adding silicon stannate, the GWIT of the material is greatly enhanced and substantially reaches 960 DEG C.

Description

Halogen-free flame-retardant polyamide material and preparation method thereof
Technical field
The present invention relates to halogen-free flame-retardant polyamide material and preparation method thereof.
Background technology
The excellent characteristics such as that polyamide resin has is wear-resisting, oil resistant, shock-resistant, antifatigue, corrosion-resistant, self-lubricating property is good, frictional coefficient is little, apply very extensive.Flame Retardant Modified because of its mechanical property outstanding, flame retardant properties excellence, is widely used in the fields such as electronics, electric, communications and transportation, power tool and component of machine.The flame-retardant modified technology of bromo-antimony because of fire retardant addition few, flame retarding efficiency height is the common technology of flame Retardant Modified all the time, but bromo-antimony type fire retardant exists the shortcoming that toxicity is large.Along with the day by day raising of people to environmental requirement, market is more and more large to the non-halogen demand of fire retardant material in recent years, and in foreseeable future, halogen-free flameproof modified polyamide will become the mainstream technology of flame Retardant Modified.Although halogen-free flameproof modified polyamide is little compared to bromo-its toxicity of antimony flame-retardant system, environmental friendliness, but its shortcoming is very obvious, as large in halogen-free flame retardants addition, mechanical property is reduced obviously, make cost can not be in any more simultaneously, also have the low shortcoming of glow-wire ignition temperature (GWIT), limited it and at low-voltage electrical etc., GWIT is required the application in high field.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flame-retardant polyamide material and preparation method thereof, this halogen-free flame-retardant polyamide material has reduced the usage quantity of halogen-free flame retardants, has kept the mechanical property of materials, has reduced material cost, and has improved glow-wire ignition temperature.
For achieving the above object, the invention provides a kind of halogen-free flame-retardant polyamide material, its main component comprises by weight:
40~72 parts of polymeric amide,
8~15 parts of halogen-free flame retardantss,
3~9 parts of fire retarding synergists,
0.5~2 part of processing aid,
0~40 part of reinforced modifier;
Wherein,
Described halogen-free flame retardants is hypophosphite;
Described fire retarding synergist is that silicone content is the stannic acid silicon of 30%-60%.
Preferably, described polymeric amide is a kind of in following polymeric amide or several mixture arbitrarily wherein: polycaprolactam (nylon 6), poly hexamethylene adipamide Aden diamines (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (NYLON610), poly-dodecane two acyl hexa-methylene amine (nylon 612), poly hexamethylene adipamide 11 methylene diamine (nylon 11 6), poly-11 lactan (nylon 11), nylon 12 (nylon 12), PPTA, poly(isophthaloyl metaphenylene diamine), poly-paraphenylene terephthalamide's trimethylhexamethylenediamine, poly-isophthaloyl hexamethylene-diamine (nylon 6I), poly-paraphenylene terephthalamide's nine methylene diamine (nylon 9 T), poly-paraphenylene terephthalamide's hexamethylenediamine (nylon 6T), nylon 10T, nylon 12T, nylon 10T/1012, nylon 6/6T, nylon 46/10T, two (4-aminocyclohexyl) methane (nylon PACM12) of poly-dodecane two acyls.
Preferably, described processing aid is lubricant and oxidation inhibitor.
Preferably, described reinforced modifier is alkali free glass fibre.
Preferably, described polymeric amide is polycaprolactam (nylon 6) and/or polyhexamethylene adipamide (nylon 66).
The present invention also provides the preparation method of above-mentioned halogen-free flame-retardant polyamide material, comprises the steps:
1) get the raw materials ready according to weight part;
2) first polymeric amide, processing aid are mixed, then add halogen-free flame retardants, fire retarding synergist to mix, obtain mixture;
3) mixture is added from the main spout of twin screw extruder, then reinforced modifier is added from the side spout of forcing machine, through melt extruding, cooling, pelletizing gets final product to obtain halogen-free flame-retardant polyamide material; Wherein the temperature of twin screw extruder from feed zone to head is respectively: 210-240 DEG C, 230-275 DEG C, 245-280 DEG C, 245-275 DEG C, 240-270 DEG C, 235-265 DEG C, 230-265 DEG C and 230-260 DEG C, die head temperature 235-270 DEG C.
Advantage of the present invention and beneficial effect are: a kind of halogen-free flame-retardant polyamide material and preparation method thereof is provided, reduce the usage quantity of halogen-free flame retardants hypophosphite by adding fire retarding synergist stannic acid silicon, flame retardant properties and mechanical property are more excellent than the fire retardant material that does not add stannic acid silicon, and cost is reduced; Do not add the fire retardant material of stannic acid silicon, although fire retardant hypophosphite content is very high, GWIT does not still accomplish 960 DEG C, and the present invention is by adding stannic acid silicon, makes the GWIT(glow-wire ignition temperature of material) be increased dramatically, substantially can reach 960 DEG C.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is further described.Following examples are only for technical scheme of the present invention is more clearly described, and can not limit the scope of the invention with this.
The raw material using in various embodiments of the present invention is:
PA66 is purchased from tafelberg Shen Ma limited-liability company, and model is EPR24, and relative viscosity is 2.45 ± 0.03.
PA6 is purchased from Jiangsu Rui Meifu Industrial Co., Ltd., and model is M1013B, and relative viscosity is 2.43 ± 0.03.
Hypophosphite is purchased from a gram Lay benefactor department, and model is that OP1312(silicone content is 30%-60%).
Alkali free glass fibre is the ECS301HP of Shanghai Lang Yu Industrial Co., Ltd..
Embodiment 1
1) first 40 parts of polymeric amide EPR24,1 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.5 part of antioxidant 168 of 0.5 part of antioxidant are mixed, add again 15 parts of hypophosphite OP1312,3 parts of stannic acid silicon to mix, obtain mixture;
2) mixture is added from the main spout of twin screw extruder, then 40 parts of reinforced modifier alkali free glass fibre ECS301HP are added from the side spout of forcing machine, through melt extruding, cooling, pelletizing gets final product to obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder from feed zone to head is respectively 240 DEG C, 275 DEG C, 280 DEG C, 275 DEG C, 270 DEG C, 265 DEG C, 265 DEG C and 260 DEG C, 270 DEG C of die head temperatures.
Embodiment 2
1) first 58 parts of polymeric amide M1013B, 0.2 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.2 part of antioxidant 168 of 0.1 part of antioxidant are mixed, add again 10 parts of halogen-free flame retardants hypophosphite OP1312,6.5 parts of stannic acid silicon to mix, mixture;
2) mixture is added from the main feeding of twin screw extruder, then 25 parts of reinforced modifier alkali free glass fibre ECS301HP are added from the survey spout of forcing machine, through melt extruding, cooling, pelletizing can obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder is respectively to head by feed zone: 210 DEG C, 230 DEG C, 245 DEG C, 245 DEG C, 240 DEG C, 235 DEG C, 230 DEG C and 230 DEG C, and 235 DEG C of die head temperatures.
Embodiment 3
1) first 40 parts of polymeric amide EPR24 and 32 parts of M1013B, 0.4 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.3 part of antioxidant 168 of 0.3 part of antioxidant are mixed, add again 15 parts of halogen-free flame retardants hypophosphite OP1312,9 parts of stannic acid silicon to mix, obtain mixture;
2) mixture is added from the main feeding of twin screw extruder, through melt extruding, cooling, cut profit and can obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder is respectively to head by feed zone: 220 DEG C, 260 DEG C, 265 DEG C, 265 DEG C, 260 DEG C, 255 DEG C, 260 DEG C and 260 DEG C, and 260 DEG C of die head temperatures.
Embodiment 4
1) first 10 parts of polymeric amide EPR24 and 44 parts of M1013B, 0.5 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.3 part of antioxidant 168 of 0.2 part of antioxidant are mixed, add again 8 parts of halogen-free flame retardants hypophosphite OP1312,7 parts of stannic acid silicon to mix, obtain mixture;
2) mixture is added from the main feeding of twin screw extruder, then 30 parts of reinforced modifier alkali free glass fibre ECS301HP is added from the survey spout of forcing machine, through melt extruding, cooling, cut profit and can obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder is respectively to head by feed zone: 220 DEG C, 260 DEG C, 260 DEG C, 255 DEG C, 255 DEG C, 255 DEG C, 250 DEG C and 250 DEG C, and 250 DEG C of die head temperatures.
Embodiment 5
1) first 60.5 parts of polymeric amide EPR24,0.7 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.4 part of antioxidant 168 of 0.4 part of antioxidant are mixed, add again 13 parts of halogen-free flame retardants hypophosphite OP1312,5 parts of stannic acid silicon to mix, obtain mixture;
2) mixture is added from the main feeding of twin screw extruder, then 20 parts of reinforced modifier alkali free glass fibre ECS301HP is added from the survey spout of forcing machine, through melt extruding, cooling, cut profit and can obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder is respectively to head by feed zone: 240 DEG C, 275 DEG C, 280 DEG C, 275 DEG C, 270 DEG C, 265 DEG C, 265 DEG C and 260 DEG C, and 270 DEG C of die head temperatures.
In addition, be the flame retardant properties that reaches modified polyamide with halogen-free flame retardants according to prior art halogen-free flame-retardant polyamide material, prepare following comparative example:
Comparative example 1
1) first 10 parts of polymeric amide EPR24 and 44 parts of M1013B, 0.5 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.3 part of antioxidant 168 of 0.2 part of antioxidant are mixed, add again 15 parts of halogen-free flame retardants hypophosphite OP1312 to mix, obtain mixture;
2) mixture is added from the main feeding of twin screw extruder, then 30 parts of reinforced modifier alkali free glass fibre ECS301HP is added from the survey spout of forcing machine, through melt extruding, cooling, cut profit and can obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder is respectively to head by feed zone: 220 DEG C, 260 DEG C, 260 DEG C, 255 DEG C, 255 DEG C, 255 DEG C, 250 DEG C and 250 DEG C, and 250 DEG C of die head temperatures.
Comparative example 2
1) first 60.5 parts of polymeric amide EPR24,0.7 part of lubricant ethylene bis stearic acid amide EBS (P-130), 1098,0.4 part of antioxidant 168 of 0.4 part of antioxidant are mixed, add again 18 parts of halogen-free flame retardants hypophosphite OP1312 to mix, obtain mixture;
2) mixture is added from the main feeding of twin screw extruder, then 20 parts of reinforced modifier alkali free glass fibre ECS301HP is added from the survey spout of forcing machine, through melt extruding, cooling, cut profit and can obtain Flameproof polyamide material; Wherein the temperature of twin screw extruder is respectively to head by feed zone: 240 DEG C, 275 DEG C, 280 DEG C, 275 DEG C, 270 DEG C, 265 DEG C, 265 DEG C and 260 DEG C, and 270 DEG C of die head temperatures.
The concrete proportioning raw materials of above-described embodiment 1-5 and comparative example 1-2 is shown in Table 1:
Table 1 proportioning raw materials table (weight part)
Formula table Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
EPR24 40 - 40 10 60.5 10 60.5
M1013B - 58 32 44 - 44 -
OP1312 15 10 15 8 13 15 18
Stannic acid silicon 3 6.5 9 7 5 - -
EBS(P-130) 1 0.2 0.4 0.5 0.7 0.5 0.7
1098 0.5 0.1 0.3 0.2 0.4 0.2 0.4
168 0.5 0.2 0.3 0.3 0.4 0.3 0.4
ECS 301HP 40 25 - 30 20 30 20
According to the proportioning composition of embodiment 1-5 in upper table 1 and comparative example 1-2, utilize conventional Method and process difference extruding pelletization on screw extrusion press of producing polyamide material, again particle is injection molded into various battens, and batten is tested to the performances such as its every machinery, fire-retardant and GWIT according to corresponding examination criteria, the standard of performance test is as follows:
Tensile strength is according to ISO527 standard testing, and draw speed is 5mm/min;
Flexural strength is according to ISO178 standard testing, and rate of bending is 2mm/min;
Modulus in flexure is according to ISO178 standard testing, and rate of bending is 2mm/min;
Simply supported beam notch shock is according to ISO179-1 standard testing;
Flame retardant resistance is according to UL94 standard testing, and batten thickness is 1.6mm;
GWIT is according to IEC60695-2-13 standard testing, and batten thickness is 2mm.
The performance test results is shown in Table 2:
The test of table 2 product performance
Performance Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Comparative example 1 Comparative example 2
Tensile strength MPa 170 130 72 139 107 128 105
Flexural strength MPa 255 180 100 210 178 195 175
Modulus in flexure MPa 9210 6970 2650 7800 6550 7420 6480
Simply supported beam notched Izod impact strength kJ/m 2 98 7.0 5.5 7.8 6.3 7.5 6.0
Flame retardant resistance (1.6mm) V-0 V-0 V-0 V-0 V-0 V-1 V-0
GWIT (2mm)/℃ 960 960 960 960 960 750 800
From table 2, embodiment 1-5 and comparative example 1-2 can see, add the usage quantity that has reduced hypophosphite OP1312 after stannic acid silicon, and flame retardant properties and mechanical property are more excellent than the fire retardant material that does not add stannic acid silicon, and cost is lower; Do not add the fire retardant material of stannic acid silicon, although fire retardant OP1312 content is very high, GWIT does not still accomplish 960 DEG C, substantially can accomplish 960 DEG C, so the GWIT of material is increased dramatically and added the GWIT of material after stannic acid silicon.
It is pointed out that polymeric amide of the present invention is not limited to PA66 and/or PA6, polymeric amide of the present invention can be a kind of in following polymeric amide or several mixture arbitrarily wherein: polycaprolactam (nylon 6), poly hexamethylene adipamide Aden diamines (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (NYLON610), poly-dodecane two acyl hexa-methylene amine (nylon 612), poly hexamethylene adipamide 11 methylene diamine (nylon 11 6), poly-11 lactan (nylon 11), nylon 12 (nylon 12), PPTA, poly(isophthaloyl metaphenylene diamine), poly-paraphenylene terephthalamide's trimethylhexamethylenediamine, poly-isophthaloyl hexamethylene-diamine (nylon 6I), poly-paraphenylene terephthalamide's nine methylene diamine (nylon 9 T), poly-paraphenylene terephthalamide's hexamethylenediamine (nylon 6T), nylon 10T, nylon 12T, nylon 10T/1012, nylon 6/6T, nylon 46/10T, two (4-aminocyclohexyl) methane (nylon PACM12) of poly-dodecane two acyls.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (6)

1. halogen-free flame-retardant polyamide material, is characterized in that, its main component comprises by weight:
40~72 parts of polymeric amide,
8~15 parts of halogen-free flame retardantss,
3~9 parts of fire retarding synergists,
0.5~2 part of processing aid,
0~40 part of reinforced modifier;
Wherein,
Described halogen-free flame retardants is hypophosphite;
Described fire retarding synergist is that silicone content is the stannic acid silicon of 30%-60%.
2. halogen-free flame-retardant polyamide material according to claim 1, it is characterized in that, described polymeric amide is a kind of in following polymeric amide or several mixture arbitrarily wherein: nylon 6, poly hexamethylene adipamide Aden diamines, nylon 66, polyhexamethylene sebacamide, poly-dodecane two acyl hexa-methylene amine, poly hexamethylene adipamide 11 methylene diamine, poly-11 lactan, nylon 12, PPTA, poly(isophthaloyl metaphenylene diamine), poly-paraphenylene terephthalamide's trimethylhexamethylenediamine, poly-isophthaloyl hexamethylene-diamine, poly-paraphenylene terephthalamide's nine methylene diamine, poly-paraphenylene terephthalamide's hexamethylenediamine, nylon 10T, nylon 12T, nylon 10T/1012, nylon 6/6T, nylon 46/10T, two (4-aminocyclohexyl) methane of poly-dodecane two acyls.
3. halogen-free flame-retardant polyamide material according to claim 1 and 2, is characterized in that, described processing aid is lubricant and oxidation inhibitor.
4. halogen-free flame-retardant polyamide material according to claim 3, is characterized in that, described reinforced modifier is alkali free glass fibre.
5. halogen-free flame-retardant polyamide material according to claim 4, is characterized in that, described polymeric amide is nylon 6 and/or nylon 66.
6. the preparation method of halogen-free flame-retardant polyamide material described in any one in claim 1-5, is characterized in that, comprises the steps:
1) get the raw materials ready according to weight part;
2) first polymeric amide, processing aid are mixed, then add halogen-free flame retardants, fire retarding synergist to mix, obtain mixture;
3) mixture is added from the main spout of twin screw extruder, then reinforced modifier is added from the side spout of forcing machine, through melt extruding, cooling, pelletizing gets final product to obtain halogen-free flame-retardant polyamide material; Wherein the temperature of twin screw extruder from feed zone to head is respectively: 210-240 DEG C, 230-275 DEG C, 245-280 DEG C, 245-275 DEG C, 240-270 DEG C, 235-265 DEG C, 230-265 DEG C and 230-260 DEG C, die head temperature 235-270 DEG C.
CN201410331829.XA 2014-07-14 2014-07-14 Halogen-free flame retardant polyamide material and preparation method thereof Pending CN104072981A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410331829.XA CN104072981A (en) 2014-07-14 2014-07-14 Halogen-free flame retardant polyamide material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410331829.XA CN104072981A (en) 2014-07-14 2014-07-14 Halogen-free flame retardant polyamide material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104072981A true CN104072981A (en) 2014-10-01

Family

ID=51594603

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410331829.XA Pending CN104072981A (en) 2014-07-14 2014-07-14 Halogen-free flame retardant polyamide material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104072981A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109306176A (en) * 2018-08-10 2019-02-05 东华大学 Flame resistant polyamide resin composition and preparation method thereof
CN109535637A (en) * 2018-11-28 2019-03-29 广东威林工程塑料股份有限公司 A kind of flame-proof ABS laser engraving material of low cost and preparation method thereof
CN114752212A (en) * 2022-05-23 2022-07-15 江苏瑞美福新材料有限公司 Flame-retardant environment-friendly nylon 6 modified material
CN115058116A (en) * 2022-04-14 2022-09-16 万华化学(宁波)有限公司 Halogen-free flame-retardant corrugated pipe material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280105A (en) * 2008-04-11 2008-10-08 卢文生 Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material
CN102108204A (en) * 2009-12-24 2011-06-29 合肥杰事杰新材料有限公司 Plastic case material for breaker and preparation method thereof
CN102167904A (en) * 2011-04-29 2011-08-31 东莞市意普万工程塑料有限公司 Halogen-free flame-retardant nano reinforced nylon composite material and preparation method thereof
US20120177858A1 (en) * 2011-01-10 2012-07-12 E.I. Du Pont De Nemours And Company Polyamide compositions for flow molding
CN102952399A (en) * 2012-12-04 2013-03-06 上海日之升新技术发展有限公司 Environment-friendly flame retardant glass fiber reinforced polyamide 66 (PA66) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof
CN103087518A (en) * 2013-02-04 2013-05-08 惠州市华聚塑化科技有限公司 Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101280105A (en) * 2008-04-11 2008-10-08 卢文生 Preparation of halogen-free flame-proof nylon 66 having high-mechanical property and composite material
CN102108204A (en) * 2009-12-24 2011-06-29 合肥杰事杰新材料有限公司 Plastic case material for breaker and preparation method thereof
US20120177858A1 (en) * 2011-01-10 2012-07-12 E.I. Du Pont De Nemours And Company Polyamide compositions for flow molding
CN102167904A (en) * 2011-04-29 2011-08-31 东莞市意普万工程塑料有限公司 Halogen-free flame-retardant nano reinforced nylon composite material and preparation method thereof
CN102952399A (en) * 2012-12-04 2013-03-06 上海日之升新技术发展有限公司 Environment-friendly flame retardant glass fiber reinforced polyamide 66 (PA66) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof
CN103087518A (en) * 2013-02-04 2013-05-08 惠州市华聚塑化科技有限公司 Glass-fiber-reinforced halogen-free flame-retardant nylon 46 composite material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109306176A (en) * 2018-08-10 2019-02-05 东华大学 Flame resistant polyamide resin composition and preparation method thereof
CN109306176B (en) * 2018-08-10 2020-05-05 东华大学 Flame-retardant polyamide resin composition and preparation method thereof
CN109535637A (en) * 2018-11-28 2019-03-29 广东威林工程塑料股份有限公司 A kind of flame-proof ABS laser engraving material of low cost and preparation method thereof
CN115058116A (en) * 2022-04-14 2022-09-16 万华化学(宁波)有限公司 Halogen-free flame-retardant corrugated pipe material and preparation method thereof
CN115058116B (en) * 2022-04-14 2023-09-19 万华化学(宁波)有限公司 Halogen-free flame-retardant corrugated pipe material and preparation method thereof
CN114752212A (en) * 2022-05-23 2022-07-15 江苏瑞美福新材料有限公司 Flame-retardant environment-friendly nylon 6 modified material

Similar Documents

Publication Publication Date Title
CN104231601B (en) Fire-retardant polyamide molding composition
CN100549095C (en) Polyamide resin of a kind of halogen-free phosphor-free environmental protection inflaming retarding and preparation method thereof
CN103351618A (en) Antistatic, halogen-free, and fire-retardant enhanced master batch dedicated for polyamide and preparation method thereof
CN102952399B (en) Environment-friendly flame retardant glass fiber reinforced polyamide 66 (PA66) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof
CN105273402B (en) A kind of preparation of high rigidity fire-retardant nylon timbering material and application
CN110540750B (en) Flame-retardant nylon 66 composite material and preparation method thereof
CN102108208A (en) High-strength flame-retardant polyamide composite material and preparation method
WO2010139369A1 (en) Flame-protected, partially aromatic polyamide molding compounds
CN107446349B (en) Ultraviolet aging resistant flame-retardant nylon composite material and preparation method thereof
CN101891953A (en) Halogen-free flame retardant reinforced polyamide composition and molded product thereof
WO2015019882A1 (en) Flame-retardant polyamide resin composition
CN104072981A (en) Halogen-free flame retardant polyamide material and preparation method thereof
CN103160111A (en) Halogen-free flame retardant thermoplastic polyamide composition
CN109438976B (en) Copolymerized nylon product and preparation method thereof
CN110591350B (en) Smoke-inhibiting polyamide composition and preparation method thereof
CN108070253B (en) High-temperature-resistant thermo-oxidative-aging-resistant polyamide composition and preparation method thereof
CN104098836A (en) Halogen-free flame-retardant reinforced polypropylene material containing polyamide charring agent and preparation method thereof
CN105176077A (en) Flame-retardant high modulus nylon material and preparation method and application thereof
CN110982254A (en) Flame-retardant fiber reinforced nylon 6 material and preparation method thereof
CN103059562A (en) High-glossiness anti-warping high-strength PA6 (polyamide 6) composite material, and preparation and application thereof
CN104861595A (en) Halogen-free flame retardant PBT material and preparation method thereof
CN107987516B (en) TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof
CN109735103B (en) Precipitation-resistant halogen-free flame-retardant polyamide composite material soaked in water and preparation method thereof
CN102363672A (en) MCA (Melamine Cyanurate) flame-retardant polycaprolactam compound material and preparation method thereof
CN101659788A (en) Special material of environment-friendly flame-retardant glass-fiber reinforced nylon 6 and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20141001