CN117700985A - PA/PPE composite material and preparation method and application thereof - Google Patents
PA/PPE composite material and preparation method and application thereof Download PDFInfo
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- CN117700985A CN117700985A CN202311807882.8A CN202311807882A CN117700985A CN 117700985 A CN117700985 A CN 117700985A CN 202311807882 A CN202311807882 A CN 202311807882A CN 117700985 A CN117700985 A CN 117700985A
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 63
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 38
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 38
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 38
- 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 abstract description 37
- 239000003063 flame retardant Substances 0.000 claims abstract description 37
- 239000002135 nanosheet Substances 0.000 claims abstract description 25
- 239000003365 glass fiber Substances 0.000 claims abstract description 18
- 238000012360 testing method Methods 0.000 claims description 29
- 229920006122 polyamide resin Polymers 0.000 claims description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 57
- 239000000463 material Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 7
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002064 nanoplatelet Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 defoamers Substances 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920003317 Fusabond® Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- 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 PA/PPE composite material, a preparation method and application thereof, belonging to the technical field of high polymer materials, wherein the product comprises the following components in parts by weight: 26-28.5 parts of PA resin, 25-35 parts of polyphenyl ether resin, 5-7 parts of compatilizer, 8-13 parts of flame retardant, 10-30 parts of glass fiber and 6-10 parts of magnesium hydroxide nano sheet; the average grain diameter of the magnesium hydroxide nano-sheet is 3-5 mu m, and the average thickness is 0.05-0.08 mu m. The product can realize the 0-grade CTI level under the condition of lower introduction amount by taking the specific magnesium hydroxide nano-sheet as a modified component, and has excellent flame retardant effect and no obvious difference in mechanical property compared with the existing conventional product.
Description
Technical Field
The invention relates to the technical field of high polymer alloy materials, in particular to a PA/PPE composite material and a preparation method and application thereof.
Background
The PPE resin (polyphenylene ether resin) is theoretically more promising than other types of plastic materials because of its excellent heat resistance, solvent resistance, water resistance, etc., but has poor processability, and because the PPE resin has high carbonatability and flame-retardant self-extinguishing properties, it forms flashover discharge at 300V voltage, further forms carbide on the surface and forms a conductive path, eventually leading to poor actual CTI performance of the PPE resin.
For this reason, PA resins (polyamide resins) and PPE resins are blended, and the characteristics of poor carbonatability and excellent processability of PA resins are utilized to complement the PPE resins. However, the existing PA/PPE composite materials still have difficulty in achieving ideal CTI performance, and particularly for black products, the existing products have no way to achieve the level of 0 CTI; on the other hand, PA resins are often used in the field of external protection, and thus the appearance of the product must be secured.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide the PA/PPE composite material, which can realize the 0-grade CTI level under the condition of lower introduction amount by taking the specific magnesium hydroxide nano-sheet as a modified component, has excellent flame retardant effect and has no obvious difference in mechanical property compared with the prior conventional product.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the PA/PPE composite material comprises the following components in parts by weight:
25-40 parts of polyamide resin, 8-32 parts of polyphenyl ether resin, 4-8 parts of compatilizer, 7-15 parts of flame retardant and 5-12 parts of magnesium hydroxide nano-sheet;
the average grain diameter of the magnesium hydroxide nano-sheet is 3-5 mu m, and the average thickness is 0.05-0.08 mu m.
Preferably, the PA/PPE composite material comprises the following components in parts by weight:
28-35 parts of polyamide resin, 10-28 parts of polyphenyl ether resin, 5-7 parts of compatilizer, 8-13 parts of flame retardant and 6-10 parts of magnesium hydroxide nano-sheet.
In the prior conventional PPE composite materials, inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide are also used for improving CTI performance of products, but the final improvement range is not ideal, and for some non-black products, although the CTI performance of the products can be improved to an expected value by improving the addition amount of the inorganic hydroxides, the mechanical performance of the products can be obviously reduced due to the fact that the inorganic hydroxides are powder fillers in nature, and in the technical scheme of the invention, the inventor selects the magnesium hydroxide nano-sheets with the specific size structure as a modified component, compared with magnesium hydroxide nano-sheets with other sizes and magnesium hydroxide and inorganic hydroxides with other types, the CTI level of the products can be obviously improved to 0 level under the condition of relatively less addition amount of the composite matrix resin, and meanwhile, the flame retardant performance and the mechanical performance of the products can not be obviously influenced, and the mechanical performance of the products are equivalent to those of the composite materials prepared by the conventional magnesium hydroxide modifier, so that the composite materials can be completely replaced.
In addition, the inventor discovers that the introduction of the magnesium hydroxide nano-sheet not only can improve CTI performance of a product, but also can ensure appearance performance of the product, and the conventional inorganic hydroxide serving as a modifier cannot realize the same performance degree under the same addition amount.
The particle size and thickness testing method of the magnesium hydroxide nano-sheet is to calcine the product and separate glass fiber and other impurities in the ash, and then directly observe and test the product by a scanning electron microscope, wherein the number of the tested particles is more than or equal to 10.
Preferably, the sum of the mass contents of the PA resin and the PPE resin in the PA/PPE composite is not less than 50wt%.
Preferably, the components of the PA/PPE composite material also comprise 0.01 to 0.8 part of pigment.
In the PA/PPE composite material, due to the effect of the specific magnesium hydroxide nano-sheet, the product can still keep the expected CTI level under the condition of introducing pigments of different color systems (the color systems are different and the performance results of the composite resin in the CTI test process are different), so that the product can design plastic products of different color systems according to actual requirements and has wide application range.
Preferably, the colorant is an organic colorant.
More preferably, the colorant is a black colorant.
More preferably, the coloring material is at least one of dye black and aniline black.
More preferably, the colorant is nigrosine.
Through experiments of the inventor, under the condition that mechanical properties are not considered, a large amount of inorganic hydroxide (such as magnesium hydroxide powder of a conventional specification) is introduced into some non-black PA/PPE composite materials, so that the CTI level of a product reaches 0 level, but for black system products, even if a sufficient amount of conventional modified components are introduced, the products still cannot reach standards, and under the condition of specific system components, even if black pigment is introduced into the products, the products can still reach similar comprehensive performance effects of other color systems.
Preferably, the mass ratio of the polyamide resin to the polyphenylene ether resin is (0.8 to 3.1): 1.
more preferably, the mass ratio of the polyamide resin to the polyphenylene ether resin is (0.83 to 2): 1.
compared with the conventional functional filler or common magnesium hydroxide powder, the magnesium hydroxide nano sheet has low strength and relatively thin size, and when the proportion of the matrix resin is maintained within the range, the CTI performance of the product is effectively improved, and meanwhile, the flame retardant performance of the product can be maintained at a better level.
Preferably, the polyamide resin is at least one of PA6 resin, PA66 resin, PA46 resin, PA6T resin, PA9T resin, PA10T resin.
Preferably, the polyamide resin has a relative viscosity of 2 to 3.4 according to GB/T12006.1-2009 under 25℃sulfuric acid solution test conditions.
More preferably, the polyamide resin has a relative viscosity of 2.3 to 3.2 according to GB/T12006.1-2009 under 25℃sulfuric acid solution test conditions.
More preferably, the polyamide resin has a relative viscosity of 2.4 to 2.8 according to GB/T12006.1-2009 under 25℃sulfuric acid solution test conditions.
Preferably, the polyphenylene ether resin has a melt mass flow rate of 2 to 25g/10min at 280℃under 5kg test conditions according to GB/T3682-2000.
More preferably, the polyphenylene ether resin has a melt mass flow rate of 5 to 20g/10min at 280℃under 5kg test conditions according to GB/T3682-2000.
More preferably, the polyphenylene ether resin has a melt mass flow rate of 8 to 12g/10min at 280℃under 5kg test conditions according to GB/T3682-2000.
Preferably, the compatilizer is at least one of maleic anhydride grafted SEBS, maleic anhydride grafted POE and maleic anhydride grafted PPE.
Preferably, the compatilizer is a maleic anhydride graft, and the grafting rate of the compatilizer is 0.5-2%.
More preferably, the compatilizer is maleic anhydride grafted SEBS, and the grafting rate is 0.9-1.2%.
Preferably, the flame retardant is at least one of a phosphorus flame retardant and a phosphorus-nitrogen flame retardant.
More preferably, the flame retardant is a phosphorus-based flame retardant.
More preferably, the phosphorus-based flame retardant is red phosphorus.
More preferably, the phosphorus flame retardant may be added in the manner disclosed in the prior art, for example, in the form of microcapsule-coated master batch, in the form of inert resin-coated master batch, under the condition of high-protective atmosphere environmental treatment, and under the condition of weak shearing mode, so long as the processing or the environmental condition of the phosphorus flame retardant can be ensured to exert the expected flame retardant effect.
More preferably, the flame retardant is a phosphorus flame retardant added in the form of microcapsule coated master batch, and the phosphorus content is 40-60 wt%.
Preferably, the components of the PA/PPE composite material further comprise 15-30 parts of glass fiber.
Preferably, the glass fibers have an average diameter of 1 to 20 μm and an average length of 1 to 10mm.
More preferably, the glass fibers have an average diameter of 8 to 12 μm and an average length of 2 to 4mm.
More preferably, the glass fibers have an average diameter in the range of any one or both of 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 15 μm, 20 μm.
It should be noted that, without damaging the technical effects of the PA/PPE composite material of the present invention, the components of the product of the present invention may further include additives such as lubricants, defoamers, antistatic agents, antioxidants, etc. that are conventionally used, and the technical solution of the present invention is not particularly limited to the exclusive formulation solution of PA resin, polyphenylene ether resin, compatilizer, flame retardant, glass fiber, magnesium hydroxide nanosheets, and coloring materials.
The invention also aims to provide a preparation method of the PA/PPE composite material, which comprises the following steps:
and uniformly mixing all components except the glass fiber, and then carrying out melting and granulating treatment on the obtained mixture and the glass fiber to obtain the PA/PPE composite material.
The preparation method of the PA/PPE composite material has simple operation steps and can realize industrialized mass production.
Preferably, the speed at the time of mixing is 1000 to 2000rpm.
Preferably, the melting is carried out in a twin-screw extruder, the temperature of the zones in the twin-screw extruder being set to: the temperature of the first area is 210-230 ℃, the temperature of the second area is 230-250 ℃, the temperature of the third area is 240-260 ℃, the temperature of the fourth area is 250-270 ℃, the temperature of the fifth area is 250-270 ℃, the temperature of the sixth area is 250-270 ℃, the temperature of the seventh area is 250-270 ℃, the temperature of the eighth area is 240-260 ℃, the temperature of the ninth area is 230-250 ℃, the temperature of the tenth area is 190-210 ℃, and the screw rotating speed of the twin-screw extruder is 330-360 rpm.
It is a further object of the present invention to provide the use of the PA/PPE composite material in the preparation of insulating flame retardant plastic articles.
The product of the invention has excellent flame retardant effect, can realize the level of 0 CTI, is a PA/PPE composite material which is developed to the level for the first time in the industry, and has mechanical properties equivalent to the prior product, so the product can completely replace the prior product to be applied to plastic products with higher requirements on insulation and flame retardant properties.
The invention has the beneficial effects that the invention provides the PA/PPE composite material, the material can realize the 0-grade CTI level under the condition of lower introduction amount by taking the specific magnesium hydroxide nano-sheet as the modified component, and meanwhile, the flame retardant effect is excellent, and the mechanical property is not obviously different from that of the existing conventional product.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
Examples 1 to 10
The composition of the PA/PPE composite material, the preparation method and the application example of the PA/PPE composite material are shown in the table 1.
The preparation method of the PA/PPE composite material comprises the following steps:
and uniformly mixing all the components except the glass fiber for 2min, and then melting and granulating the obtained mixture and the glass fiber (added from a side feeding port) to obtain the PA/PPE composite material.
The rate at the time of mixing was 1500rpm.
The melting is carried out in a twin-screw extruder, the temperature of the zones in the twin-screw extruder being set as: the temperature of the first area is 215-225 ℃, the temperature of the second area is 235-245 ℃, the temperature of the third area is 245-255 ℃, the temperature of the fourth area is 255-265 ℃, the temperature of the fifth area is 255-265 ℃, the temperature of the sixth area is 255-265 ℃, the temperature of the seventh area is 255-265 ℃, the temperature of the eighth area is 245-255 ℃, the temperature of the ninth area is 235-245 ℃, the temperature of the tenth area is 195-205 ℃, and the screw rotating speed of the double screw extruder is 340rpm.
Comparative examples 1 to 7
The comparative examples differ from the examples only in the kinds and proportions of the components, as shown in Table 2.
Among the components described in each example and comparative example,
the polyamide resin 1 is M2400 (PA 6) produced by Neumeda, and the relative viscosity is 2.4 under the test condition of 25 ℃ sulfuric acid solution according to GB/T12006.1-2009;
the polyamide resin 2 is EP-158 (PA 66) produced by Huafeng, and the relative viscosity is 2.6 under the test condition of sulfuric acid solution at 25 ℃ according to GB/T12006.1-2009;
the polyphenyl ether resin 1 is LXR035 (poly (2, 6-dimethyl-1, 4-phenylene) ether) produced by Shanxi blue star, and the melt mass flow rate under the test condition of 5kg at the temperature of 280 ℃ according to GB/T3682-2000 is 12g/10min;
the polyphenyl ether resin 2 is LXR040 (poly (2, 6-dimethyl-1, 4-phenylene) ether) produced by Shanxi blue star, and the mass flow rate of the polyphenyl ether resin is 8g/10min according to the melt mass flow rate under the test condition of 5kg at 280 ℃;
the flame retardant 1 is microcapsule coated red phosphorus master batch, the brand FR9950T, the red phosphorus content is 50wt%, and Tung City information is available from the company Limited;
the magnesium hydroxide nano-sheet 1 is 10A produced by Japanese Kogyo, the average grain diameter is 4 mu m, and the average thickness is 0.06 mu m;
the magnesium hydroxide nano-sheet 2 is LY1-S produced by Japanese Kogyo, the average particle diameter is 0.9 μm, and the average thickness is 0.2 μm;
the magnesium hydroxide nano-sheet 3 is LY1-X produced by Japanese Kogyo, the average particle diameter is 3 μm, and the average thickness is 0.5 μm;
the magnesium hydroxide powder is 2500-G produced by barrage ring ball powder, and has particle diameter D 50 3.5 μm;
the glass fiber is ECS10-03-568H produced by the huge stone group, the average diameter is 10 mu m, and the average length is 3mm;
the compatilizer 1 is SEBS FG 1901 produced by Korotten, and the grafting rate of maleic anhydride grafting SEBS is 1%;
the compatilizer 2 is FUSABOND N493 produced by DuPont in U.S.A., the grafting rate of maleic anhydride grafted POE and FUSABOND N493 is 0.4%;
the compatilizer 3 is SH024, maleic anhydride grafted PPO and SH024 produced by Dongguan plastic company, and the grafting rate is 2%;
the pigment 1 is commercial aniline black;
the pigment 2 is a commercial dye black;
the pigment 3 is cobalt green sold in the market;
the raw materials of the components used in each of the examples and comparative examples of the present invention were all commercially available raw materials unless otherwise specified, and the raw materials of the components used in each of the parallel experiments were all the same.
TABLE 1
TABLE 2
| The weight portions of the components | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 |
| Polyamide resin 1 | 30 | 30 | 30 | 30 | 30 | 30 | 30 |
| Polyphenylene ether resin 1 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
| Glass fiber | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Flame retardant 1 | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Magnesium hydroxide nanosheets 1 | 3 | 18 | |||||
| Magnesium hydroxide nanosheets 2 | 8 | ||||||
| Magnesium hydroxide nanosheets 3 | 8 | ||||||
| Magnesium hydroxide powder | 8 | 10 | 20 | ||||
| Compatibilizing agent 1 | 6 | 6 | 6 | 6 | 6 | 6 | 6 |
| Pigment 1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Average particle diameter (μm) of magnesium hydroxide nanoplatelets in product | 4.2 | 3.9 | 0.92 | 3.1 | 3.5 | 3.6 | 3.5 |
| Average thickness (μm) of magnesium hydroxide nanoplatelets in product | 0.05 | 0.06 | 0.18 | 0.52 | / | / | / |
Effect example 1
In order to verify the performance of the PA/PPE composite material of the invention, the following performance tests are carried out on the products prepared in each example and comparative example, and the specific steps are as follows:
(1) CTI performance test: according to GB/T4207-2022, an anti-tracking test is carried out, a certain voltage is applied between two electrodes, and a drop of standard electrolyte solution is dripped on the surface of an insulating material every 30 seconds, wherein the test sample is subjected to 50 drops of solution or the test sample is damaged by adopting 0.1% of ammonium chloride solution. The test was repeated with lower or higher voltages applied to the other test points of the sample until the highest voltage value was reached that did not destroy 50 drops of the solution at 5 different test points: i.e. the CTI value, wherein when the highest voltage value of CTI is greater than 600V, it is the CTI 0 level.
(2) Appearance: injection molding of the color plate (84 x 54 x 2.0 mm), observation of the material flowers on the surface of the color plate, evaluation according to the material flower condition of the surface of the color plate, and classification into 4 grades, wherein no material flowers, insignificant material flowers (the area ratio of the material flowers is lower than 5% and shallower without affecting the appearance of the surface of the color plate), significant material flowers (the area ratio of the material flowers is 5-20%, only good appearance can be maintained), and more material flowers (the area ratio of the material flowers is more than 20%, and the appearance of the surface of the color plate is obviously affected);
(3) Mechanical property test: flexural modulus: testing was performed according to ISO 178:2001 standard; impact strength: testing according to ISO 180:2000 standard, wherein the notch type is IZOD A type notch;
the test results are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 |
| CTI | 375V | ＞600V | 520V | 425V | 375V | 425V | 475V |
| Impact Strength (KJ/m) 2 ) | 8.4 | 4.2 | 8.5 | 9.5 | 8.2 | 7.6 | 5.4 |
| Flexural modulus (MPa) | 6600 | 6150 | 6110 | 6270 | 6540 | 6450 | 6150 |
| Appearance of | The material flower is not obvious | The material flower is not obvious | The material flower is not obvious | The material flower is not obvious | Obvious material flower | Obvious material flower | Obvious material flower |
As can be seen from tables 3 and 4, the PA/PPE composite material of the present invention has excellent comprehensive properties, each product can reach a CTI level of 0 grade, and the impact property can be maintained at 5KJ/m 2 The above; in addition, the flexural modulus of the product can be maintained above 6000MPa, the use requirement of basic mechanics is met, and the appearance material flower of the product is basically not obvious. It can be seen from examples 9 and 10 that the PA/PPE composites of the present invention are not limited to a single color system, and that other colors or products without color can achieve the same excellent combination of properties as would be achieved if the black system, which is the least likely to achieve the desired effect, could achieve the desired level. Compared with the examples 4, 7 and 8, on the premise of using the specific magnesium hydroxide nano-sheet as a CTI level modification component, the maleic anhydride grafted SEBS is used as a compatilizer based on the specific configuration, so that good dispersibility and uniformity can be realized in a PA/PPE composite resin system with glass fibers, and the mechanical property of the final product is better. As can be seen from comparative example 1, examples 3 to 5 and comparative example 2, when too little magnesium hydroxide nanoplatelets are introduced, the CTI level of the product is poor, and as the content of the component is gradually increased, the CTI level of the product reaches level 0; however, if the component is excessively added, the impact properties of the product are greatly reduced, and thus it is necessary to maintain the addition amount thereof at 5 to 12 parts. It can be seen from comparative examples 3 to 4 that magnesium hydroxide nanoplatelets of not any size can achieve the expected CTI performance improvement in black-based PA/PPE composite systems, whereas for ordinary magnesium hydroxide powders, as comparedExamples 5 to 7 show that, although the CTI performance of the product is improved under the condition of introducing a large content, the CTI level of 0 grade still cannot be achieved, and the appearance performance of the product cannot be improved. Similarly, the inventors have found through experiments that the products of comparative examples 3 to 4 also fail to reach the level of the product of examples after the magnesium hydroxide nanoplatelets 2 or 3 are introduced, indicating that the component needs to be maintained at a specific size to function effectively.
In addition, the products of each example were tested for flame retardant rating according to UL94, and the results were all V-0, indicating that each product had good flame retardancy.
Effect example 2
In order to investigate the influence of the proportion of polyamide resin and polyphenylene ether resin in the product of the present invention on the performance of the product, control groups 1 to 6 were set, the formulations were shown in Table 5, the product was prepared according to the method of example, CTI performance test was performed according to the method of effect example 1, appearance and flame retardant rating test was performed, and appearance test was the same as effect example 1.
The results are shown in Table 6.
TABLE 5
| The weight portions of the components | Control group 1 | Control group 2 | Control group 3 | Example 4 | Control group 4 | Control group 5 | Control group 6 |
| Polyamide resin 1 | 10 | 20 | 25 | 30 | 35 | 40 | 55 |
| Polyphenylene ether resin 1 | 45 | 35 | 30 | 25 | 20 | 15 | 0 |
| Flame retardant | 10 | 10 | 10 | 10 | 10 | 10 | 10 |
| Glass fiber | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Magnesium hydroxide nanosheets 1 | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| Compatibilizing agent 1 | 6 | 6 | 6 | 6 | 6 | 6 | 6 |
| Pigment 1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
TABLE 6
| Test item | Control group 1 | Control group 2 | Control group 3 | Example 4 | Control group 4 | Control group 5 | Control group 6 |
| CTI | 400V | 575V | >600V | >600V | >600V | >600V | >600V |
| Appearance of | The material flowers are more | Obvious material flower | The material flower is not obvious | The material flower is not obvious | The material flower is not obvious | The material flower is not obvious | The material flower is not obvious |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | NA |
As can be seen from table 6, when the total addition amount of the polyamide resin and the polyphenylene ether resin is unchanged but the addition ratio is changed, the properties of the product are also changed, when the polyamide in the product is less, the product is not only poor in CTI properties but also has obvious appearance defects, and as the polyamide resin is increased, the flame retardance of the product starts to decrease, and when the ratio of the two is maintained at (0.8 to 2): when the range of 1 is within, the product has ideal flame retardant and CTI performance, meanwhile, the flame retardant performance is good, the V-0 grade can be achieved, the appearance is good, the practicability is better, and if the matching proportion exceeds the limit range of the invention, the CTI performance or the dimensional stability of the product can be greatly reduced.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The PA/PPE composite material is characterized by comprising the following components in parts by weight:
25-40 parts of polyamide resin, 8-32 parts of polyphenyl ether resin, 4-8 parts of compatilizer, 7-15 parts of flame retardant and 5-12 parts of magnesium hydroxide nano-sheet;
the average grain diameter of the magnesium hydroxide nano-sheet is 3-5 mu m, and the average thickness is 0.05-0.08 mu m.
2. The PA/PPE composite of claim 1 further comprising 0.01-0.8 parts of a colorant in the components of the PA/PPE composite; the pigment is at least one of dye black and aniline black.
3. The PA/PPE composite material according to claim 1, characterized in that the mass ratio of the polyamide resin and the polyphenylene ether resin is (0.8 to 3.1): 1.
4. the PA/PPE composite material of claim 1, wherein the polyamide resin has a relative viscosity of 2 to 3.4 according to GB/T12006.1-2009 under 25 ℃ sulfuric acid solution test conditions.
5. The PA/PPE composite of claim 1, wherein the polyphenylene ether resin has a melt mass flow rate of 2 to 25g/10min at 280 ℃ under 5kg test conditions according to GB/T3682-2000.
6. The PA/PPE composite of claim 1 wherein the compatibilizer is at least one of maleic anhydride grafted SEBS, maleic anhydride grafted POE, maleic anhydride grafted PPE.
7. The PA/PPE composite of claim 1 wherein the flame retardant is at least one of a phosphorus flame retardant, a phosphorus nitrogen flame retardant.
8. The PA/PPE composite of claim 1, wherein the components of the PA/PPE composite further comprise 8-32 parts glass fibers having an average diameter of 1-20 μm and an average length of 1-10 mm.
9. The method for preparing a PA/PPE composite material according to any one of claims 1 to 8, comprising the steps of:
and uniformly mixing all components except the glass fiber, and then carrying out melting and granulating treatment on the obtained mixture and the glass fiber to obtain the PA/PPE composite material.
10. Use of the PA/PPE composite material according to any one of claims 1 to 8 for the preparation of insulating flame retardant plastic articles.
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| JP2001081272A (en) * | 1999-09-13 | 2001-03-27 | Asahi Kasei Corp | Flame-retardant resin composition |
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| CN116812953A (en) * | 2023-07-08 | 2023-09-29 | 潍坊泽隆新材料有限公司 | Preparation method of hexagonal magnesium hydroxide and application of hexagonal magnesium hydroxide in low-smoke halogen-free cable material |
| CN116875044A (en) * | 2023-07-26 | 2023-10-13 | 中山海明中科新材料有限公司 | Composite reinforced flame-retardant nylon material for new energy automobile and preparation method thereof |
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| JP2001081272A (en) * | 1999-09-13 | 2001-03-27 | Asahi Kasei Corp | Flame-retardant resin composition |
| CN114410010A (en) * | 2021-11-23 | 2022-04-29 | 天津金发新材料有限公司 | Flame-retardant polypropylene material and preparation method thereof |
| CN115895261A (en) * | 2022-11-28 | 2023-04-04 | 苏州纳磐新材料科技有限公司 | Polyphenylene sulfide composite material with high CTI performance and preparation method thereof |
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