CN101085864A - Halogen-free phosphor-free environmental protection inflaming retarding polyamide resin and preparation method thereof - Google Patents
Halogen-free phosphor-free environmental protection inflaming retarding polyamide resin and preparation method thereof Download PDFInfo
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- CN101085864A CN101085864A CNA2007100746642A CN200710074664A CN101085864A CN 101085864 A CN101085864 A CN 101085864A CN A2007100746642 A CNA2007100746642 A CN A2007100746642A CN 200710074664 A CN200710074664 A CN 200710074664A CN 101085864 A CN101085864 A CN 101085864A
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- free
- halogen
- environmental protection
- polyamide resin
- inflaming retarding
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000000979 retarding effect Effects 0.000 title claims description 20
- 229920006122 polyamide resin Polymers 0.000 title claims description 19
- 230000007613 environmental effect Effects 0.000 title claims description 18
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004952 Polyamide Substances 0.000 claims abstract description 13
- 229920002647 polyamide Polymers 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003063 flame retardant Substances 0.000 claims description 31
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229920002292 Nylon 6 Polymers 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000012747 synergistic agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- -1 pentaerythritol ester Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- 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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
-
- 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
- B29C2948/92514—Pressure
-
- 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
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a non- halegeno and non- phosphorus phpolyamide resin and the preparation method. The comprised raw material of phpolyamide resin and their proportion are as follows: polyamide 68- 92%, melamine cyanurate 5- 15%, flexibilizer 2- 15%, anti-oxidant0.1- 1%, heat stabilizer 0.1- 2%, crystallizing promoter 0.1- 2%. The product is characterized by good physical property, outstanding flame proof performance, low raw material price, simple preparation process and low production cost.
Description
[technical field]
The present invention relates to polyamide resin material, relate in particular to polyamide resin of a kind of halogen-free phosphor-free environmental protection inflaming retarding and preparation method thereof.
[background technology]
Polyamide resin (polyamide is called for short PA), first of five large-engineering plastics, its performance characteristics is: the physical strength height, the softening temperature height, good heat resistance, wear-resistant, self lubricity, shock absorption and noise reduction, oil resistant, weak acid resistant, alkaline-resisting, electrical insulating property is good, thereby polymeric amide is the preferred material of electronics, electric elements aspect, and this series products is very high for the requirement of the flame retardant properties of material, and the oxygen index of polymeric amide is approximately 25%, to reach the UL94-V2 level, obviously can't meet the demands only.Therefore it is very necessary polymeric amide to be carried out fire-retardant finish.The normal flame-retardant system that adopts of fire-retardant nylon is nearly three kinds at present: 1) the bromine Sb system fire retardant 2) phosphorus flame retardant, 3) the inorganic hydroxide fire retardant.Because the ROHS that European Union announces instruction (TheRestriction of the use of certain Hazardous substances inElectnical and Electronic Equipment limits in electronic electric equipment and uses some objectionable impurities instruction) and WEEE instruction (instruction of Waste from Electrical andElectronic Equipment waste electronic andelectrical equipment) make bromide fire retardant progressively withdraw from the market; Phosphorus type flame retardant has greatly limited its widespread use for the severe corrosive of mould; The addition of inorganic hydroxide fire retardant is very big, and is poor with the polymeric amide consistency, bigger to the physical and mechanical property influence and the destruction of material, makes material lose a lot of use value.And at present, this field is in the initial stage of development stage, does not have matured product to come out up to now as yet, so the halogen-free phosphorus-free inflaming retarding polyamide material has great market development value.
[summary of the invention]
The technical problem to be solved in the present invention provides a kind of halogen-free phosphor-free environmental protection inflaming retarding, and physical and mechanical property is polyamide resin and preparation method thereof preferably.The present invention also will provide a kind of preparation method of this kind polyamide resin.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is that a kind of polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding is mixed with by following proportion raw material:
Polyamide 6 8-92%;
Melamine cyanurate 5-25%;
Toughner 2-15%;
Oxidation inhibitor 0.1-1%;
Thermo-stabilizer 0.1-2%;
Crystallization promoter 0.1-2%.
The polyamide resin of above-described halogen-free phosphor-free environmental protection inflaming retarding preferably is mixed with by following proportion raw material:
Polyamide 6 8-76%;
Melamine cyanurate 8-18%;
Toughner 4-5%;
Oxidation inhibitor 0.1-0.3%;
Thermo-stabilizer 0.2-0.4%;
Crystallization promoter 0.1-0.5%.
Wherein, described polymeric amide is the mixture of polyhexamethylene adipamide and polycaprolactam, and relative density is 1.12-1.15g/cm
3, fusing point is 255-265 ℃, melt viscosity is 0.3-3.Described thermo-stabilizer is the oxidation inhibitor of a class copper composition and the mixture of synergistic agent.Described toughner is thermoplastic elastomer.Described thermoplastic elastomer is ethylene-propylene rubber(EPR) grafts or thermoplastic poly polyolefine.Described crystallization promoter is the careful powdered mixture of a kind of organic composition and inorganic components.Described flame-retardant system is made up of following component: melamine cyanurate, crystallization promoter, thermo-stabilizer.
The preparation method of the polyamide resin of above-mentioned halogen-free phosphor-free environmental protection inflaming retarding may further comprise the steps:
Take by weighing raw material by weight: polyamide (PA) 58-92%, melamine cyanurate 5-2 5%, toughner 2-15%, oxidation inhibitor 0.1-1%, thermo-stabilizer 0.1-2%, crystallization promoter 0.1-2%;
With polymeric amide, toughner, antioxidant, thermo-stabilizer, dispersed oil in moderate-speed mixers premix 2-3 minute, and then add melamine cyanurate mixing 5-10 minute;
Raw materials mixed is placed the dual-screw-stem machine of specific screw combinations, through melt extruding, granulation, its technology is: twin screw one district temperature 210-230 ℃, two district temperature 230-250 ℃, three district temperature 250-270, four district temperature 260-280; In barrel residence time 1-2 minute, melt pressure was 10-20MPa.
The invention has the beneficial effects as follows: by adding melamine cyanurate, crystallization promoter, thermo-stabilizer three component composite flame-retardant agents, can improve the oxygen index of polymeric amide effectively, simultaneously because it is organic polymer material, good with the consistency of polymeric amide, so the influence to its over-all properties is little, so prepared fire retardant material good combination property, and compliance with environmental protection requirements have a extensive future; The halogen-free phosphor-free environmental protection inflaming retarding system that the present invention is made of melamine cyanurate, crystallization promoter, thermo-stabilizer in the halogen-free phosphorus-free inflaming retarding polyamide material, make the physical and mechanical property of polyamide material good, flame retardant properties is excellent, and good thermostability arranged; Auxiliary agent of the present invention as components such as melamine cyanurate, crystallization promoter, thermo-stabilizer, toughner and oxidation inhibitor, is cheap commercially available prod, and the production cost of material is lower; The preparation technology of halogen-free flameproof PA matrix material proposed by the invention is simple, cost is low.
[embodiment]
Below by embodiment the present invention is further set forth:
In implementing composite-material formula, polymeric amide is the mixture of polyhexamethylene adipamide (PA66) and polycaprolactam (PA6), and relative density is 1.1 2-1.15g/cm
3, fusing point is 255-265 ℃, melt viscosity is 0.3-3; Toughner is a kind of grafted ethylene copolymer, and for Dupont company produces, trade names are the graft copolymer of 493D; Thermo-stabilizer is the oxidation inhibitor of copper composition and the mixture of synergistic agent, and for BRUGGOLEN company produces, trade names are H3373; Crystallization promoter is that German Clariant company produces, and trade names are CAV102, and the oxidation inhibitor chemical name is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, produces as Ciba company, and trade names are Irganox 1010.
Embodiment 1
With weight ratio be PA66---79.7%, PA6---10%, 493D---4.5%, MCA---5%, CAV102---0.3%, 1010---0.2%, H3373---0.3% in moderate-speed mixers under room temperature state premix 3 minutes, and then add fire retardant and mixed 5 minutes, then through melt extrude, granulation makes matrix material.220 ℃ of twin screw one district's temperature, 240 ℃ of two district's temperature, three district's temperature, 260, four district's temperature 270; 1.5 minutes residence time in barrel, melt pressure is 16MPa.
Embodiment 2
With weight ratio be PA66---74.7%, PA6---10%, 493D---4.5%, MCA---10%, CAV102---0.3%, 1010---0.2%, H3373---0.3% in moderate-speed mixers under room temperature state premix 3 minutes, and then add fire retardant and mixed 5 minutes, then through melt extrude, granulation makes matrix material.220 ℃ of twin screw one district's temperature, 240 ℃ of two district's temperature, three district's temperature, 260, four district's temperature 270; 1.5 minutes residence time in barrel, melt pressure is 16MPa.
Embodiment 3
With weight ratio be PA66---69.7%, PA6---10%, 493D---4.5%, MCA---15%, CAV102---0.3%, 1010---0.2%, H337 3---0.3% in moderate-speed mixers under room temperature state premix 3 minutes, and then add fire retardant and mixed 5 minutes, then through melt extrude, granulation makes matrix material.220 ℃ of twin screw one district's temperature, 240 ℃ of two district's temperature, three district's temperature, 260, four district's temperature 270; 1.5 minutes residence time in barrel, melt pressure is 16MPa.
Embodiment 4
With weight ratio be PA66---64.7%, PA6---10%, 493D---4.5%, MCA---20%, CAV102---0.3%, 1010---0.2%, H3373---0.3% in moderate-speed mixers under room temperature state premix 3 minutes, and then add fire retardant and mixed 5 minutes, then through melt extrude, granulation makes matrix material.220 ℃ of twin screw one district's temperature, 240 ℃ of two district's temperature, three district's temperature, 260, four district's temperature 270; 1.5 minutes residence time in barrel, melt pressure is 16MPa.
Embodiment 5
With weight ratio be PA66---59.7%, PA6---1 0%, 493D---4.5%, MCA---25%, CAV102---0.3%, 1010---0.2%, H3373---0.3% in moderate-speed mixers under room temperature state premix 3 minutes, and then add fire retardant and mixed 5 minutes, then through melt extrude, granulation makes matrix material.220 ℃ of twin screw one district's temperature, 240 ℃ of two district's temperature, three district's temperature, 260, four district's temperature 270; 1.5 minutes residence time in barrel, melt pressure is 16MPa.
Comparative Examples 1
With weight ratio be PA66---70%, PA6---10%, 493D---4.5%, MCA---15%, 1010---0.2%, H3373---0.3% in moderate-speed mixers under room temperature state premix 3 minutes, and then add fire retardant and mixed 5 minutes, then through melt extrude, granulation makes matrix material.220 ℃ of twin screw one district's temperature, 240 ℃ of two district's temperature, three district's temperature, 260, four district's temperature 270; 1.5 minutes residence time in barrel, melt pressure is 16MPa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 100 ℃ convection oven dry 3-6 hour in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection machine, and the injection mold temperature control is about 100 ℃.
The tensile strength test is undertaken by ISO 527-2, and specimen size is 150 * 10 * 4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80 * 10 * 4, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO179, and specimen size is 55 * 6 * 4mm, and notch size is 1/3rd of a sample thickness; Flame retardant properties is undertaken by the UL94 method, and batten thickness is approximately 1.5mm.
Comprehensive mechanical property is passed judgment on by the numerical value of tensile strength, elongation at break, modulus in flexure and the shock strength of test gained; The flame retardant properties of material is passed judgment on by the standard of UL94.
The prescription of embodiment 1-5 and Comparative Examples 1-2 and Mechanics Performance Testing the results are shown in Table 1 and table 2;
The prescription of table 1 embodiment 1-5 and material property table
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| PA66(％) | 79.7 | 74.7 | 69.7 | 64.7 | 59.7 |
| PA6(％) | 10 | 10 | 10 | 10 | 10 |
| MCA(％) | 5 | 10 | 15 | 20 | 25 |
| 493D(％) | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 |
| CAV102(％) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| H3373(％) | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| 1010(％) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Notched Izod impact strength (KJ/M2) | 18 | 17.3 | 16.8 | 16.2 | 15.5 |
| Tensile strength (Mpa) | 80 | 82 | 78 | 80 | 76 |
| Elongation at break (%) | 15 | 13 | 16 | 15 | 16 |
| Modulus in flexure (Mpa) | 2300 | 2450 | 2400 | 2460 | 2430 |
| Long-term thermal stability (h) | 5 | 5.5 | 5 | 4.5 | 5 |
| Flame retardant resistance (UL94) | V0 | V0 | V0 | V0 | V0 |
The prescription of table 2 Comparative Examples 1-2 and material property table
| Form | Comparative Examples 1 | Comparative Examples 2 |
| PA66(％) | 70 | 29.7 |
| PA6(％) | 10 | 10 |
| MCA(％) | 15 | / |
| Magnesium hydroxide | / | 55 |
| 493D(％) | 4.5 | 4.5 |
| CAV102(％) | 0.3 | 0.3 |
| H3373(％) | 0.3 | |
| 1010(％) | 0.2 | 0.2 |
| Notched Izod impact strength (KJ/M2) | 15 | 6 |
| Tensile strength (Mpa) | 80 | 76 |
| Elongation at break (%) | 15 | 3 |
| Modulus in flexure (Mpa) | 2500 | 1500 |
| Long-term thermal stability (h) | 0.5 | 3.5 |
| Flame retardant resistance (UL94) | V0 | V0 |
Every performance analysis by table 1 embodiment 1-5 and table 2 Comparative Examples 1-2 as can be known, the comprehensive mechanical property of halogen-free phosphorus-free inflaming retarding polyamide compoiste material is better, its flame retardant properties has reached the standard of UL94V0.And every performance data from table 1 embodiment 1-5, three kinds of components of non-halogen non-phosphate composite flame retardant system lack wherein that a kind ofly all can't reach flame-retardant V 0-stage, and the crystallization velocity of resin has been quickened in the adding of crystallization promoter, formed crystal grain is tiny evenly, make and the intensity height of integral material be difficult for drippage.And the fire retardant addition too much can influence the comprehensive physical and mechanical property of material, also can cause occurring in the combustion processes drip phenomenon, and flame retardant properties can't reach the UL94-V0 level.The MCA addition is 15%, and CAV102 content is 0.3%, and thermo-stabilizer is that 0.3% o'clock comprehensive mechanical performance, flame retardant resistance and cost performance are all better, through the composite material combination property excellence of above modification processing.
The oxygen index of polyamides material of the present invention effectively improves, and characteristics such as it has, and preparation technology is simple, cost is moderate, every physical and chemical performance excellence, flame retardant properties are good can be used for technical fields such as electronics, electric elements, auto parts machinery.
Claims (9)
1. the polyamide resin of a halogen-free phosphor-free environmental protection inflaming retarding is characterized in that, is mixed with by following proportion raw material:
Polyamide 6 8-92%;
Melamine cyanurate 5-25%;
Toughner 2-15%;
Oxidation inhibitor 0.1-1%;
Thermo-stabilizer 0.1-2%;
Crystallization promoter 0.1-2%.
2. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 1 is characterized in that, is mixed with by following proportion raw material:
Polyamide 6 8-76%;
Melamine cyanurate 8-18%;
Toughner 4-5%;
Oxidation inhibitor 0.1-0.3%;
Thermo-stabilizer 0.2-0.4%;
Crystallization promoter 0.1-0.5%.
3. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 1, it is characterized in that: described polymeric amide is the mixture of polyhexamethylene adipamide and polycaprolactam, relative density is 1.12-1.15g/cm3, and fusing point is 255-265 ℃, and melt viscosity is 0.3-3.
4. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 1, it is characterized in that: described thermo-stabilizer is the oxidation inhibitor of a class copper composition and the mixture of synergistic agent.
5. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 1, it is characterized in that: described toughner is thermoplastic elastomer.
6. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 4, it is characterized in that: described thermoplastic elastomer is ethylene-propylene rubber(EPR) grafts or thermoplastic poly polyolefine.
7. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 1, it is characterized in that: described crystallization promoter is the careful powdered mixture of a kind of organic composition and inorganic components.
8. the polyamide resin of halogen-free phosphor-free environmental protection inflaming retarding according to claim 1, it is characterized in that: described flame-retardant system is made up of following component: melamine cyanurate, crystallization promoter, thermo-stabilizer.
9. the preparation method of the polyamide resin of a halogen-free phosphor-free environmental protection inflaming retarding is characterized in that, may further comprise the steps:
901, take by weighing raw material by weight: polyamide (PA) 58-92%, melamine cyanurate 5-25%, toughner 2-15%, oxidation inhibitor 0.1-1%, thermo-stabilizer 0.1-2%, crystallization promoter 0.1-2%;
902,, and then add melamine cyanurate mixing 5-10 minute with polymeric amide, toughner, antioxidant, thermo-stabilizer, dispersed oil in moderate-speed mixers premix 2-3 minute;
903, raw materials mixed is placed the dual-screw-stem machine of specific screw combinations, through melt extruding, granulation, its technology is: twin screw one district temperature 210-230 ℃, two district temperature 230-250 ℃, three district temperature 250-270, four district temperature 260-280; In barrel residence time 1-2 minute, melt pressure was 10-20MPa.
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