CN114806164A - Halogen-free flame-retardant PA66 and preparation method thereof - Google Patents
Halogen-free flame-retardant PA66 and preparation method thereof Download PDFInfo
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- CN114806164A CN114806164A CN202210577004.0A CN202210577004A CN114806164A CN 114806164 A CN114806164 A CN 114806164A CN 202210577004 A CN202210577004 A CN 202210577004A CN 114806164 A CN114806164 A CN 114806164A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 title abstract description 58
- 239000004677 Nylon Substances 0.000 claims abstract description 84
- 229920001778 nylon Polymers 0.000 claims abstract description 84
- 229920001971 elastomer Polymers 0.000 claims abstract description 49
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 41
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 41
- 239000000806 elastomer Substances 0.000 claims abstract description 41
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 31
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 31
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 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 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 23
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 23
- 239000000314 lubricant Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 17
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 125000003368 amide group Chemical group 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 29
- 238000001514 detection method Methods 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- 239000005060 rubber Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229920006124 polyolefin elastomer Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000012745 toughening agent Substances 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 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
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a halogen-free flame-retardant PA66 and a preparation method thereof, wherein the halogen-free flame-retardant PA66 comprises the following raw materials: PA 6675-85 parts; 8-15 parts of melamine cyanurate; 5-10 parts of a thermoplastic nylon elastomer; 0.5-2 parts of polytetrafluoroethylene; 0.1-0.3 part of maleic anhydride; 0.2-0.5 part of antioxidant; 0.3-0.5 part of lubricant. The preparation method comprises the following steps: weighing the raw materials, uniformly mixing the raw materials in a high-speed mixer, adding the mixture into a double-screw extruder, and extruding and granulating the mixture, wherein the extrusion temperature is 250-270 ℃, and the screw rotation speed is 400-600 rpm. The amide group in the thermoplastic nylon elastomer has good compatibility with nylon, and has better toughness modification effect when added into a nylon formula system; meanwhile, the thermoplastic nylon elastomer has a nylon block as a rigid chain segment, so that the strength reduction of a nylon toughening system can be slowed down, namely the rigidity is not reduced; and because of the existence of the nylon block, the melting point of the thermoplastic nylon elastomer can reach about 200 ℃, so that the risk of dripping ignition can be reduced.
Description
Technical Field
The invention belongs to the field of modified engineering plastics, and particularly relates to halogen-free flame retardant PA66 and a preparation method thereof.
Background
The nylon flame retardant material is widely applied to industries such as automobile industry, electronic and electric appliance industry and the like, and the nylon flame retardant mainly comprises a brominated flame retardant, a red phosphorus flame retardant, a nitrogen-phosphorus flame retardant and the like. Wherein the red phosphorus flame retardant has the problems that the use scene is limited due to the color problem and phosphine is corroded, and the nitrogen-phosphorus flame retardant has unstable flame retardant effect and high production difficulty. The bromine-based flame retardant generates toxic smoke during combustion due to the flame retardant mechanism. Therefore, the nitrogen flame retardant melamine cyanurate MCA is most commonly adopted in the non-reinforced nylon material, and has the advantages of environmental protection, good flame retardant effect, stable color and the like, but the toughness is insufficient, which is also the common defect of the flame retardant material.
In some electrical appliance connectors, the flame-retardant nylon material is required to have good toughness, and the grafted POE/PE toughening agent is required to be added into the formula to improve the toughness of the flame-retardant nylon material. However, the olefin toughening agent is mostly in an amorphous structure or has a low melting point, so that dropping ignition cotton wool is easily generated in a vertical burning test, and the flame retardance is greatly influenced.
For example, chinese patent application publication No. CN107129679A discloses a toughened, modified and flame-retardant nylon corrugated pipe, which is prepared from the following substances in parts by mass: 100 parts of nylon; 5-10 parts of toughening modifier; 10-20 parts of a flame retardant; 5-15 parts of a processing aid. The toughening modified flame-retardant nylon corrugated pipe can effectively overcome the toughness problem of the existing corrugated pipe in the use process, but due to the fact that toughening agents such as grafted POE (polyolefin elastomer) are matched with a flame retardant for use, although the toughness of the material is improved, the flame retardance can only reach UL94V-2 level.
In order to solve the problem of balance between flame retardance and toughness of MCA flame retardant material, Chinese patent application with publication number CN102051044A discloses a halogen-free flame retardant high-toughness polyamide composition and a preparation method thereof, wherein the composition comprises 100 parts by weight of polyamide resin, 5-25 parts by weight of melamine compound, 0-8 parts by weight of char forming agent and 5-25 parts by weight of composite powder rubber. Wherein the char-forming agent is selected from at least one of polyhydroxy compound with high char content and/or organic resin containing hydroxyl; the composite powder rubber is powder acrylate rubber compounded with organic montmorillonite; wherein the weight ratio of the rubber phase to the organic montmorillonite is (1-4) to 1, and the gel content of the rubber phase is 60% by weight or more. The composite powder rubber is prepared by uniformly mixing irradiated or non-irradiated acrylate rubber latex and organic montmorillonite slurry according to a required dry weight proportion and drying. The polyamide composition of the invention has good flame retardancy; however, the composite powder rubber and the like are adopted to improve the toughness of the MCA flame-retardant nylon material, and the compatibility between the rubber and the nylon is poor, so that the effect of improving the performance, particularly the toughness, of the MCA flame-retardant nylon material is limited.
Disclosure of Invention
Aiming at the problem that the flame retardance and toughness of a nylon material in the prior art are difficult to achieve the balanced and excellent performance, the invention provides the halogen-free flame-retardant PA66 and the preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the halogen-free flame retardant PA66 comprises the following raw materials in parts by weight:
preferably, the relative viscosity of the PA66 is in the range of 2.2-3.4, too low a viscosity will reduce the toughness of the material, while too high a viscosity will be detrimental to the processing and dispersion of the flame retardant.
Preferably, the particle size of the melamine cyanurate is less than 2um, the particle size has an important influence on the flame retardant effect of the flame retardant, and an excessively large particle size affects the dispersion effect of the flame retardant, so that an inert gas cannot be rapidly generated during combustion.
Preferably, the thermoplastic nylon elastomer is at least one of polyester nylon elastomer and polyether nylon elastomer, and the polyether nylon elastomer is preferred. Compared with other thermoplastic elastomers, the thermoplastic nylon elastomer has the following advantages when used for modifying nylon due to the polyamide segment in the chain segment: 1. the compatibility with nylon resin is very good; 2. the melting point is relatively high.
Preferably, the molecular weight of the polytetrafluoroethylene is in the range of 400 to 500 ten thousand. A molecular weight that is too low does not appear fibrous in the system, while a molecular weight that is too high is difficult to prepare and process.
Preferably, the antioxidant is a compound of antioxidant 1098 and antioxidant 168. Further preferably, the antioxidant 1098: the weight ratio of the antioxidant 168 is 0.5: 1-1: 1.
preferably, the lubricant is one or a compound of more than two of calcium stearate, zinc stearate, ethylene bis stearamide, polyethylene wax and polydimethylsiloxane.
The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials in proportion, uniformly mixing the raw materials in a mixer, adding the mixture into a double-screw extruder, and extruding and granulating the mixture, wherein the extrusion temperature is 250-270 ℃, and the screw rotation speed is 400-600 rpm.
Has the advantages that:
the amide group in the thermoplastic nylon elastomer has good compatibility with nylon, and has better toughness modification effect when added into a nylon formula system; meanwhile, the thermoplastic nylon elastomer has a nylon block as a rigid chain segment, so that the strength reduction of a nylon toughening system can be slowed down, namely the rigidity is not reduced; and because of the existence of the nylon block, the melting point of the thermoplastic nylon elastomer can reach about 200 ℃, so that the risk of dripping ignition can be reduced.
In addition, the thermoplastic nylon elastomer has a high melting point, is connected with nylon resin through a maleic anhydride cross-linking agent to form a network structure, is matched with high molecular weight polytetrafluoroethylene, and the high molecular weight polytetrafluoroethylene is fibrous in the nylon resin, so that molten drops are slowed down when the nylon burns, the dripping phenomenon in a flame-retardant test can be greatly improved, and the flame retardance of the material is ensured.
The invention can be applied to electric devices, improves the plugging times of the electronic and electric appliance connector made of the flame-retardant nylon material and prolongs the service life.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below may be considered as part of the inventive subject matter unless such concepts are mutually inconsistent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
The use of "first," "second," and similar terms in the description and in the claims does not indicate any order, quantity, or importance, but rather is used to distinguish one element from another. Similarly, the singular forms "a," "an," or "the" do not denote a limitation of quantity, but rather denote the presence of at least one, unless the context clearly dictates otherwise. The terms "comprises," "comprising," or the like, mean that the elements or items listed before "comprises" or "comprising" encompass the features, integers, steps, operations, elements, and/or components listed after "comprising" or "comprising," and do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. "upper", "lower", "left", "right", and the like are used only to indicate relative positional relationships, and when the absolute position of the object to be described is changed, the relative positional relationships may also be changed accordingly.
The invention takes the nylon block in the thermoplastic nylon elastomer as a rigid chain segment, and is connected with the nylon resin through the maleic anhydride cross-linking agent to form a network structure, and the high molecular weight polytetrafluoroethylene is matched, and the content of each component is adjusted, so that the composite material has excellent and stable flame retardance and good toughness.
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight:
in some embodiments, the PA66 has a relative viscosity in the range of 2.2 to 3.4, too low a viscosity may reduce material toughness, while too high a viscosity may be detrimental to processing and dispersion of the flame retardant.
In some embodiments, the melamine cyanurate has a particle size of less than 2um, which has an important effect on the flame retardant effect of the flame retardant, and an excessively large particle size affects the dispersion effect of the flame retardant, and thus, an inert gas cannot be rapidly generated during combustion.
In some embodiments, the thermoplastic nylon elastomer is at least one of a polyester nylon elastomer and a polyether nylon elastomer, wherein the polyether nylon elastomer is preferred. Compared with other thermoplastic elastomers, the nylon elastomer has the following advantages when used for modifying nylon due to the polyamide segment in the segment: 1. the compatibility with nylon resin is very good; 2. the melting point is relatively high.
In some embodiments, the polytetrafluoroethylene has a molecular weight in the range of 400 to 500 million. A molecular weight that is too low does not appear fibrous in the system, while a molecular weight that is too high is difficult to prepare and process.
In some embodiments, the antioxidant is a combination of antioxidant 1098 and antioxidant 168. Further preferably, the antioxidant compound is prepared from the following components in percentage by weight: antioxidant 168 ═ 0.5: 1-1: 1.
in some embodiments, the lubricant is one or a mixture of two or more of calcium stearate, zinc stearate, ethylene bis stearamide, polyethylene wax and polydimethylsiloxane.
The present invention is further illustrated by the following specific examples.
Example 1
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6684.3 parts with relative viscosity of 2.2, 8 parts of melamine cyanurate with particle size of 1um, 5 parts of polyether type thermoplastic nylon elastomer, 400 ten thousand of relative molecular weight, 2 parts of polytetrafluoroethylene, 0.1 part of maleic anhydride, 0.2 part of antioxidant (1680.1 parts of antioxidant, 10980.1 parts of antioxidant) and 0.4 part of lubricant calcium stearate. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing the PA66, the melamine cyanurate, the thermoplastic nylon elastomer, the polytetrafluoroethylene, the maleic anhydride, the antioxidant and the lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-600rpm, and performing injection molding detection.
Example 2
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6682.3 parts with relative viscosity of 3.4, 10 parts of melamine cyanurate with particle size of 1um, 5 parts of polyether type thermoplastic nylon elastomer, 400 ten thousand of relative molecular weight, 2 parts of polytetrafluoroethylene, 0.1 part of maleic anhydride, 0.2 part of antioxidant (1680.1 parts of antioxidant, 10980.1 parts of antioxidant) and 0.4 part of lubricant calcium stearate. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing the PA66, the melamine cyanurate, the thermoplastic nylon elastomer, the polytetrafluoroethylene, the maleic anhydride, the antioxidant and the lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-600rpm, and performing injection molding detection.
Example 3
A halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6679.1 parts with relative viscosity of 2.8, 8 parts of melamine cyanurate with particle size of 1um, 10 parts of polyether type thermoplastic nylon elastomer, 400 ten thousand of relative molecular weight, 2 parts of polytetrafluoroethylene, 0.1 part of maleic anhydride, 0.3 part of antioxidant (1680.2 parts of antioxidant, 10980.1 parts of antioxidant) and 0.5 part of lubricant calcium stearate. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing PA66, melamine cyanurate, a thermoplastic nylon elastomer, polytetrafluoroethylene, maleic anhydride, an antioxidant and a lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-700rpm, and performing injection molding detection.
Example 4
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6684.1 parts with relative viscosity of 2.2, 8 parts of melamine cyanurate with particle size of 1um, 5 parts of polyester type thermoplastic nylon elastomer, 400 ten thousand of relative molecular weight, 2 parts of polytetrafluoroethylene, 0.3 part of maleic anhydride, 0.2 part of antioxidant (1680.1 parts of antioxidant, 10980.1 parts of antioxidant) and 0.4 part of lubricant calcium stearate. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing PA66, melamine cyanurate, a thermoplastic nylon elastomer, polytetrafluoroethylene, maleic anhydride, an antioxidant and a lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-700rpm, and performing injection molding detection.
Example 5
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6684.3 parts with relative viscosity of 2.2, 8 parts of melamine cyanurate with particle size of 0.5um, 5 parts of polyether type thermoplastic nylon elastomer, 400 ten thousand of relative molecular weight, 2 parts of polytetrafluoroethylene, 0.1 part of maleic anhydride, 0.2 part of antioxidant (1680.1 parts of antioxidant, 10980.1 parts of antioxidant) and 0.4 part of lubricant ethylene bis stearamide. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing PA66, melamine cyanurate, a thermoplastic nylon elastomer, polytetrafluoroethylene, maleic anhydride, an antioxidant and a lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-700rpm, and performing injection molding detection.
Comparative example 1
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA6693.4 parts with relative viscosity of 2.2, melamine cyanurate with particle size of 1um, melamine cyanurate 8 parts, antioxidant 0.2 parts (antioxidant 1680.1 parts, antioxidant 10980.1 parts) and ethylene bis stearamide 0.4 parts. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing the PA66, the melamine cyanurate, the antioxidant and the lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-700rpm, and performing injection molding detection.
Comparative example 2
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6686.4 parts with relative viscosity of 2.2, melamine cyanurate with particle size of 1um 8 parts, maleic anhydride grafted POE 5 parts, antioxidant 0.2 parts (antioxidant 1680.1 parts, antioxidant 10980.1 parts) and ethylene bis stearamide 0.4 parts. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing PA66, melamine cyanurate, a thermoplastic nylon elastomer, polytetrafluoroethylene, maleic anhydride, an antioxidant and a lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-700rpm, and performing injection molding detection.
Comparative example 3
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6686.4 parts with relative viscosity of 2.2, 8 parts of melamine cyanurate with particle size of 0.5um, 5 parts of polyether type thermoplastic nylon elastomer, 0.2 part of antioxidant (1680.1 parts of antioxidant, 10980.1 parts of antioxidant) and 0.4 part of lubricant ethylene bis stearamide. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing PA66, melamine cyanurate, a thermoplastic nylon elastomer, polytetrafluoroethylene, maleic anhydride, an antioxidant and a lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-700rpm, and performing injection molding detection.
Comparative example 4
The halogen-free flame retardant PA66 comprises the following raw materials in parts by weight: PA 6682.3 parts with relative viscosity of 3.7, 10 parts of melamine cyanurate with particle size of 1um, 5 parts of polyether type thermoplastic nylon elastomer, 400 ten thousand of relative molecular weight, 2 parts of polytetrafluoroethylene, 0.1 part of maleic anhydride, 0.2 part of antioxidant (1680.1 parts of antioxidant, 10980.1 parts of antioxidant) and 0.4 part of lubricant calcium stearate. The preparation method of the halogen-free flame-retardant nylon material comprises the following steps: weighing the raw materials, uniformly mixing the PA66, the melamine cyanurate, the thermoplastic nylon elastomer, the polytetrafluoroethylene, the maleic anhydride, the antioxidant and the lubricant in a high-speed mixer, adding the mixture into a double-screw extruder, extruding and granulating, wherein the extrusion temperature is 250-270 ℃, the screw rotation speed is 400-600rpm, and performing injection molding detection.
The results of the tests of the above examples and comparative examples are as follows (bar thickness 0.8mm, UL94 standard):
the experimental results are as follows:
1. in terms of toughening effect, the conventional grafted POE toughening agent has the best effect under the same addition proportion, but has very obvious side effect on the flame retardant effect;
2. the thermoplastic nylon elastomer can greatly improve the toughness of the material on the premise of not influencing the flame-retardant effect, and is preferably polyether;
3. the viscosity of the nylon resin is too high, so that the dispersion of the flame retardant is not facilitated, and the flame retardance can be negatively influenced to a certain extent;
4. the grain size of the MCA flame retardant has certain influence on the flame retardant effect, and the smaller the grain size is, the better the flame retardant effect is;
5. the polytetrafluoroethylene and the maleic anhydride also have certain influence on the flame retardant property of the material, and the addition of the maleic anhydride can improve the flame retardant property and the toughness of the flame retardant material to a certain extent.
The experiment shows that by adopting the technical scheme of the invention, the thermoplastic nylon elastomer is used as the toughening agent of the MCA flame-retardant PA66 material, and the anti-dripping agent PTFE and the maleic anhydride are simultaneously added, so that the halogen-free flame-retardant PA66 material with the flame retardancy grade of 0.8mm or even 0.6mmV-0 and high toughness can be prepared, wherein the selection and the proportion of the raw materials have great influence on the invention.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be defined by the appended claims.
Claims (10)
1. The halogen-free flame retardant PA66 is characterized by comprising the following raw materials in parts by weight:
2. the halogen-free flame retardant PA66 according to claim 1, wherein the PA66 relative viscosity is in the range of 2.2-3.4.
3. Halogen free flame retardant PA66 according to claim 1, characterized in that the melamine cyanurate has a particle size below 2 um.
4. The halogen-free flame retardant PA66 of claim 1 wherein the thermoplastic nylon elastomer is at least one of polyester nylon elastomer and polyether nylon elastomer.
5. The halogen-free flame retardant PA66 of claim 4 wherein the thermoplastic nylon elastomer is a polyether nylon elastomer.
6. The halogen-free flame retardant PA66 of claim 1 wherein the molecular weight of the polytetrafluoroethylene is in the range of 400-500 ten thousand.
7. The halogen-free flame retardant PA66 according to claim 1, wherein the antioxidant is a combination of antioxidant 1098 and antioxidant 168.
8. The halogen-free flame retardant PA66 as claimed in claim 7, wherein the weight ratio of the antioxidant 1098 to the antioxidant 168 is 0.5: 1-1: 1.
9. the halogen-free flame retardant PA66 of claim 1, wherein the lubricant is one or a mixture of two or more of calcium stearate, zinc stearate, ethylene bis stearamide, polyethylene wax and polydimethylsiloxane.
10. The preparation method of the halogen-free flame retardant PA66 based on claim 1 is characterized by comprising the following steps: weighing the raw materials in proportion, uniformly mixing in a mixer, adding into a double-screw extruder, and extruding and granulating at the extrusion temperature of 250-270 ℃ and the screw rotation speed of 400-600 rpm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115612295A (en) * | 2022-10-24 | 2023-01-17 | 安徽威普达材料科技有限公司 | Halogen-free flame-retardant PA66 with strong heat resistance and warping resistance and preparation method thereof |
| CN115746548A (en) * | 2022-11-29 | 2023-03-07 | 沧州旭阳化工有限公司 | Flame-retardant polyamide elastomer material and preparation method and application thereof |
| WO2024125233A3 (en) * | 2022-12-14 | 2024-08-08 | 金发科技股份有限公司 | Polyamide composite material, and preparation method therefor and use thereof |
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| CN112980183A (en) * | 2019-12-18 | 2021-06-18 | 南京聚隆科技股份有限公司 | Precipitation-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof |
| CN114231026A (en) * | 2021-12-21 | 2022-03-25 | 天津金发新材料有限公司 | Polyamide composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112980183A (en) * | 2019-12-18 | 2021-06-18 | 南京聚隆科技股份有限公司 | Precipitation-resistant halogen-free flame-retardant reinforced nylon material and preparation method thereof |
| CN114231026A (en) * | 2021-12-21 | 2022-03-25 | 天津金发新材料有限公司 | Polyamide composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115612295A (en) * | 2022-10-24 | 2023-01-17 | 安徽威普达材料科技有限公司 | Halogen-free flame-retardant PA66 with strong heat resistance and warping resistance and preparation method thereof |
| CN115746548A (en) * | 2022-11-29 | 2023-03-07 | 沧州旭阳化工有限公司 | Flame-retardant polyamide elastomer material and preparation method and application thereof |
| WO2024125233A3 (en) * | 2022-12-14 | 2024-08-08 | 金发科技股份有限公司 | Polyamide composite material, and preparation method therefor and use thereof |
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