CN114437541A - Polyamide composite material and preparation method and application thereof - Google Patents
Polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN114437541A CN114437541A CN202111516781.6A CN202111516781A CN114437541A CN 114437541 A CN114437541 A CN 114437541A CN 202111516781 A CN202111516781 A CN 202111516781A CN 114437541 A CN114437541 A CN 114437541A
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- composite material
- polyamide
- melamine cyanurate
- polyamide composite
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 52
- 229920002647 polyamide Polymers 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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 62
- 239000002245 particle Substances 0.000 claims abstract description 31
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000000314 lubricant Substances 0.000 claims description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 5
- -1 PA56 Polymers 0.000 claims description 5
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 5
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 5
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 2
- 101000701286 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Alkanesulfonate monooxygenase Proteins 0.000 claims description 2
- 101000983349 Solanum commersonii Osmotin-like protein OSML13 Proteins 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 2
- 229920006396 polyamide 1012 Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 22
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 7
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical compound O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 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 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001312297 Selar Species 0.000 description 1
- 229920003365 Selar® Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229940083916 aluminum distearate Drugs 0.000 description 1
- RDIVANOKKPKCTO-UHFFFAOYSA-K aluminum;octadecanoate;hydroxide Chemical compound [OH-].[Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RDIVANOKKPKCTO-UHFFFAOYSA-K 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229920006374 copolyamide PA6I/6T Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyamide composite material and a preparation method and application thereof. The polyamide composite material comprises the following components in parts by weight: 85-95 parts of polyamide resin; 5-15 parts of melamine cyanurate; wherein the sum of the weight parts of the polyamide resin and the melamine cyanurate is 100 parts; the pH value of the melamine cyanurate is 5.0-7.5. The invention selects the melamine cyanurate within a certain pH range, selects proper process conditions in the preparation process of the material, and can control the TVOC content of the material and the particle size distribution of the melamine cyanurate in the material, thereby effectively improving the IPT performance (the IPT value can reach 1500V) of the polyamide material, meeting the use requirements of products with high electrical performance requirements, being particularly suitable for electronic products with the rated voltage of 1000 plus 1500V, and further widening the application of the polyamide material in the field of electronic and electric appliances.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a polyamide composite material and a preparation method and application thereof.
Background
The polyamide flame-retardant modified by Melamine Cyanurate (MCA) has the characteristics of high electrical property, low cost, good flame retardant property and the like, and is widely applied to the electronic and electrical industry. The conventional electronic and electric product measures the electrical property of the material, generally the comparative tracking index CTI is taken as a standard, and the material with the CTI reaching 600V can meet the use requirement of the conventional electronic and electric product. However, for products such as large-scale battery energy storage systems, the voltage involved is as high as 1000-1500V, which requires the material to have more excellent electrical properties. According to the provisions of UL 4128, the product involves voltages of 600-2000V and a creepage distance of less than 16mm, the slope tracking (IPT) performance must be tested. However, the prior researches on how to improve the IPT performance of MCA flame-retardant polyamide are less, so that the application of the polyamide material in some fields with high electrical property requirements is limited.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a polyamide composite material with high electrical property.
Another object of the present invention is to provide a method for preparing the above polyamide composite material.
It is a further object of the present invention to provide the use of the above polyamide composite material
The invention is realized by the following technical scheme:
the polyamide composite material comprises the following components in parts by weight:
85-95 parts of polyamide resin;
5-15 parts of melamine cyanurate;
wherein the sum of the weight parts of the polyamide resin and the melamine cyanurate is 100 parts;
the pH value of the melamine cyanurate is 5.0-8.0.
Preferably, the polyamide composite material comprises the following components in parts by weight:
88-92 parts of polyamide resin;
8-12 parts of melamine cyanurate.
Preferably, the melamine cyanurate has a pH of 5.5 to 7.5.
The pH of the melamine cyanurate according to the invention can be determined by the following method: 5.0g of melamine cyanurate was dispersed in 100ml of deionized water at 23 ℃, subjected to ultrasonic treatment for 1min, and then allowed to stand for 3min, and the pH of the supernatant was measured using a pH meter.
The TVOC content of the polyamide composite material is less than 15g/kg, and the D10 particle size of melamine cyanurate in the polyamide composite material is 0.15-1.0 μm, and the D90 particle size is 0.5-2.0 μm; preferably, the TVOC content of the polyamide composite material is less than 8g/kg, and the D10 particle size of melamine cyanurate in the polyamide composite material is 0.15-0.35 μm, and the D90 particle size is 0.5-0.75 μm.
The testing method of the TVOC content comprises the following steps: weighing a certain amount of polyamide composite material, recording m1 (accurate to 0.0001 g), placing in an oven at 150 ℃ for 12h, taking out, cooling to room temperature, weighing, recording m2 (accurate to 0.0001 g), calculating the TVOC content: TVOC content = (m1-m2)/m2, and the unit is g/kg.
The invention provides an analysis method for the particle size distribution condition of melamine cyanurate in a polyamide composite material, which comprises the following steps: and (3) injection molding the polyamide composite material into a cantilever beam notch impact spline (with the standard of ISO 180-2000), completely cooling the cantilever beam notch impact spline by using liquid nitrogen, punching the cantilever beam notch impact spline according to the ISO180-2000 standard, and observing the section by using a scanning electron microscope to count the D10 particle size and the D90 particle size of the melamine cyanurate.
The polyamide resin is selected from any one or more of aliphatic polyamide or semi-aromatic polyamide. The aliphatic polyamide is any one or more of polyamide resin obtained by condensation polymerization of diamine and dicarboxylic acid, polyamide resin obtained by ring-opening polymerization of lactam or polyamide resin obtained by self-condensation of aminocarboxylic acid. The semi-aromatic polyamide is any one or more of polyamide resins obtained by polycondensation of aliphatic diamine and aromatic diacid or aliphatic diacid and aromatic diamine.
Preferably, the aliphatic polyamide is selected from any one or more of PA6, PA66, PA56, PA610, PA612, PA1010, PA1012, PA106, PA1212, PA92, PA102, PA7, PA11, PA12, PA13, PA6/66, PA6/11, PA6/12 or PA 6/13; the semi-aromatic polyamide is selected from any one or more of MXD6, PA6T/6I, PA6T/66 or PA 66/6T; more preferably, the polyamide resin is selected from one or more of PA6 or PA 66.
According to the material performance requirement, the polyamide composite material also comprises 0.1-1 part of processing aid in parts by weight.
The processing aid is selected from one or more of an antioxidant or a lubricant.
The antioxidant is selected from one or more of hindered phenol thermal antioxidant, amine antioxidant or phosphate antioxidant.
The lubricant is selected from one or more of amide stearate lubricants, alcohol stearate lubricants, stearate lubricants or long-chain saturated linear carboxylate lubricants.
The invention has no special requirements on the types and sources of the antioxidant and the lubricant, and the skilled person can select the antioxidant and the lubricant to be added according to the requirements of actual conditions.
The invention also provides a preparation method of the polyamide composite material, which comprises the following steps:
according to the proportion, putting the components into a mixer for mixing until the components are uniform to obtain a premix; and then, carrying out melt mixing on the obtained premix from a first twin-screw extruder, and carrying out extrusion granulation to obtain the polyamide composite material. Wherein the extrusion temperature is 150-260 ℃; the diameter of the extrusion screw is 40-75mm, and the length-diameter ratio is (36-60): 1; in the extrusion process, the rotation speed of the screw is controlled to be 300-500rpm, and the feeding speed is controlled to be 80-800 kg/h.
The invention has no special requirements on the diameter and the length-diameter ratio of the screw of the extruder, and can be selected and used according to actual production conditions. When the diameter of the extrusion screw is selected to be 52mm and the length-diameter ratio is 40:1, preferably, in the extrusion process, the rotating speed of the screw is controlled to be 300-; more preferably, the screw rotation speed is controlled to be 350-450rpm, and the feeding speed is controlled to be 200-280kg/h during the extrusion process.
The invention also provides application of the polyamide composite material in the field of electronic appliances, and particularly can be used for electronic products with the rated voltage of 1000-1500V, such as large-scale battery energy storage systems.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the melamine cyanurate within a certain pH range is selected, and meanwhile, proper process conditions (controlling the screw rotation speed and the feeding speed) are selected in the material preparation process, so that the TVOC content of the material can be controlled to be less than 15g/kg, the D10 particle size of the melamine cyanurate in the material is 0.15-1.0 μm, and the D90 particle size of the melamine cyanurate in the material is 0.5-2.0 μm, and the IPT performance of the polyamide material is effectively improved; the prepared high IPT polyamide composite material (the IPT value can reach 1500V), can meet the use requirement of products with high electrical performance requirements, is particularly suitable for electronic products with the rated voltage of 1000-1500V, and further widens the application of the polyamide material in the field of electronic appliances.
Drawings
FIG. 1 is a scanning electron micrograph of a cross section of an injection molded specimen of the polyamide composite material of comparative example 4.
FIG. 2 is a scanning electron micrograph of a cross section of an injection molded specimen of the polyamide composite material of example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
polyamide resin 1: PA66 EP-158, Zhejiang Huafeng group;
polyamide resin 2: PA6 HY-2500A, Jiangsu Haiyang chemical fibers Co., Ltd;
polyamide resin 3: PA6I/6T, Selar PA 3426, available from DuPont;
melamine cyanurate 1: pH 5.0, Shandong Shouguangdong chemical Co., Ltd;
melamine cyanurate 2: pH 6.0, Shandong Shouguang Weidong chemical Co., Ltd;
melamine cyanurate 3: pH 6.5, Shandong Shouguang Weidong chemical Co., Ltd;
melamine cyanurate 4: pH 7.0, Shandong Shouguang Weidong chemical Co., Ltd;
melamine cyanurate 5: pH 8.0, Shandong Shouguang Weidong chemical Co., Ltd;
melamine cyanurate 6: pH 3.0, Shandong Shouguang Weidong chemical Co., Ltd;
melamine cyanurate 7: pH 9.0, Shandong Shouguang Weidong chemical Co., Ltd;
processing aid 1: antioxidant Irganox1098, commercially available;
processing aid 2: the lubricant, aluminum distearate, M-132 HG, is commercially available.
Preparation of examples and comparative examples:
according to the mixture ratio of table 1/table 2, putting the components into a mixer for mixing until the components are uniform to obtain a premix; then, melting and mixing the obtained premix in a first section of double-screw extruder, and extruding and granulating to obtain the polyamide composite material; wherein the diameter of the extrusion screw is 52mm, and the length-diameter ratio is 40: 1; the extrusion temperature is 150 ℃ in the first zone, 240 ℃ in the second zone, 260 ℃ in the third zone, 240 ℃ in the fourth zone, 230 ℃ in the fifth zone, 230 ℃ in the sixth zone, 230 ℃ in the seventh zone, 230 ℃ in the eighth zone, 240 ℃ in the ninth zone and 260 ℃ in the tenth zone; the screw rotation speed and feed rate during extrusion are shown in Table 1/Table 2.
TVOC (Total Voltage Organic Compound) content test: weighing a certain amount of polyamide composite material, recording m1 (accurate to 0.0001 g), placing in an oven at 150 ℃ for 12h, taking out, cooling to room temperature, weighing, recording m2 (accurate to 0.0001 g), calculating the TVOC content: TVOC content = (m1-m2)/m2, and the unit is g/kg.
The analysis method for the particle size distribution of melamine cyanurate in the polyamide composite material comprises the following steps: and (3) injection molding the polyamide composite material into a cantilever beam notch impact spline (with the standard of ISO 180-2000), completely cooling the cantilever beam notch impact spline by using liquid nitrogen, punching the cantilever beam notch impact spline according to the ISO180-2000 standard, and observing the section by using a scanning electron microscope to count the D10 particle size and the D90 particle size of the melamine cyanurate. FIG. 1 in the drawings of the specification is a scanning electron microscope image of a cross section of an injection molded sample bar of the polyamide composite material of comparative example 4, wherein the D10 particle size is greater than 0.35 μm, and the D90 particle size is greater than 0.75 μm; FIG. 2 is a scanning electron micrograph of a cross section of an injection molded specimen of the polyamide composite material of example 2, in which D10 particle size is in the range of 0.15 to 0.35 μm and D90 particle size is in the range of 0.5 to 0.75 μm.
And (3) IPT performance test: the test was carried out according to the standard ASTM D2303-2013, using the constant pressure method.
Table 1: examples 1-18 ingredient ratios (in parts by weight) and IPT Performance test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Polyamide resin 1 | 90 | 90 | 90 | 90 | 90 | 85 | 95 |
| Polyamide resin 2 | |||||||
| Polyamide resin 3 | |||||||
| Melamine cyanurate 1 | 10 | ||||||
| Melamine cyanurate 2 | 10 | ||||||
| Melamine cyanurate 3 | 10 | ||||||
| Melamine cyanurate 4 | 10 | 15 | 5 | ||||
| Melamine cyanurate 5 | 10 | ||||||
| Processing aid 1 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Processing aid 2 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Screw rotation speed | 400rpm | 400rpm | 400rpm | 400rpm | 400rpm | 400rpm | 400rpm |
| Feed rate | 220kg/h | 220kg/h | 220kg/h | 220kg/h | 220kg/h | 220kg/h | 220kg/h |
| TVOC | 10.1 | 7.8 | 7.4 | 7.1 | 8.8 | 9.2 | 8.5 |
| D10 particle size/. mu.m | 0.30 | 0.29 | 0.29 | 0.31 | 0.30 | 0.42 | 0.30 |
| D90 particle size/. mu.m | 0.68 | 0.70 | 0.69 | 0.69 | 0.70 | 0.88 | 0.70 |
| IPT | 1250V | 1500V | 1500V | 1500V | 1250V | 1250V | 1250V |
The following table 1:
| example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| Polyamide resin 1 | 68 | 90 | |||||
| Polyamide resin 2 | 92 | 20 | 92 | 92 | 92 | ||
| Polyamide resin 3 | 90 | ||||||
| Melamine cyanurate 1 | |||||||
| Melamine cyanurate 2 | 8 | 8 | 8 | 8 | |||
| Melamine cyanurate 3 | |||||||
| Melamine cyanurate 4 | 10 | 12 | 10 | ||||
| Melamine cyanurate 5 | |||||||
| Processing aid 1 | 0.2 | 0.2 | 0.2 | / | 0.2 | 0.2 | 0.2 |
| Processing aid 2 | 0.4 | 0.4 | 0.4 | / | 0.4 | 0.4 | 0.4 |
| Screw rotation speed | 400rpm | 400rpm | 400rpm | 400rpm | 400rpm | 400rpm | 400rpm |
| Feed rate | 220kg/h | 220kg/h | 220kg/h | 220kg/h | 180kg/h | 260kg/h | 350kg/h |
| TVOC/g/kg | 6.5 | 7.8 | 7.5 | 7.2 | 9.0 | 7.5 | 7.0 |
| D10 particle size/. mu.m | 0.31 | 0.28 | 0.30 | 0.30 | 0.21 | 0.34 | 0.45 |
| D90 particle size/. mu.m | 0.70 | 0.69 | 0.70 | 0.70 | 0.65 | 0.74 | 1.21 |
| IPT | 1500V | 1500V | 1500V | 1500V | 1250V | 1500V | 1250V |
Table 1 is shown below:
| example 15 | Example 16 | Example 17 | Example 18 | |
| Polyamide resin 1 | 68 | 68 | 68 | 68 |
| Polyamide resin 2 | 20 | 20 | 20 | 20 |
| Polyamide resin 3 | ||||
| Melamine cyanurate 1 | ||||
| Melamine cyanurate 2 | ||||
| Melamine cyanurate 3 | ||||
| Melamine cyanurate 4 | 12 | 12 | 12 | 12 |
| Melamine cyanurate 5 | ||||
| Processing aid 1 | 0.2 | 0.2 | 0.2 | 0.2 |
| Processing aid 2 | 0.4 | 0.4 | 0.4 | 0.4 |
| Screw rotation speed | 300rpm | 350rpm | 400rpm | 500rpm |
| Feed rate | 220kg/h | 220kg/h | 220kg/h | 220kg/h |
| TVOC/g/kg | 6.8 | 7.0 | 7.8 | 12.6 |
| D10 particle size/. mu.m | 0.41 | 0.34 | 0.20 | 0.19 |
| D90 particle size/. mu.m | 0.85 | 0.73 | 0.66 | 0.55 |
| IPT | 1250V | 1500V | 1500V | 1250V |
Table 2: comparative examples 1-6 in parts by weight and IPT performance test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Polyamide resin 1 | 90 | 90 | 68 | 68 | ||
| Polyamide resin 2 | 92 | 92 | 20 | 20 | ||
| Melamine cyanurate 1 | ||||||
| Melamine cyanurate 2 | 8 | 8 | ||||
| Melamine cyanurate 3 | ||||||
| Melamine cyanurate 4 | 12 | 12 | ||||
| Melamine cyanurate 5 | ||||||
| Melamine cyanurate 6 | 10 | |||||
| Melamine cyanurate 7 | 10 | |||||
| Processing aid 1 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Processing aid 2 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Screw rotation speed | 400rpm | 400rpm | 400rpm | 400rpm | 250rpm | 550rpm |
| Feed rate | 220kg/h | 220kg/h | 100kg/h | 500kg/h | 220kg/h | 220kg/h |
| TVOC/g/kg | 16.8 | 15.2 | 17.0 | 5.8 | 6.3 | 15.2 |
| D10 particle size/. mu.m | 0.32 | 0.31 | 0.12 | 1.2 | 1.5 | 0.13 |
| D90 particle size/. mu.m | 0.72 | 0.72 | 0.50 | 3.0 | 3.4 | 0.52 |
| IPT | 750V | 1000V | 750V | 750V | 1000V | 750V |
As can be seen from the above examples and comparative examples, the TVOC content of the material can be controlled to be less than 15g/kg by selecting the melamine cyanurate within a certain pH range and selecting proper process conditions in the preparation process of the material, and the D10 particle size of the melamine cyanurate in the material is 0.15-1.0 μm and the D90 particle size is 0.5-2.0 μm, so that the material has excellent IPT performance (the IPT value of the material can reach 1250V, even reach 1500V).
Claims (10)
1. The polyamide composite material is characterized by comprising the following components in parts by weight:
85-95 parts of polyamide resin;
5-15 parts of melamine cyanurate;
wherein the sum of the weight parts of the polyamide resin and the melamine cyanurate is 100 parts;
the pH value of the melamine cyanurate is 5.0-8.0;
the TVOC content of the polyamide composite material is less than 15g/kg, and the D10 particle size of melamine cyanurate in the polyamide composite material is 0.15-1.0 μm, and the D90 particle size is 0.5-2.0 μm.
2. The polyamide composite material as claimed in claim 1, comprising the following components in parts by weight:
88-92 parts of polyamide resin;
8-12 parts of melamine cyanurate.
3. Polyamide composite material according to claim 1, characterized in that the melamine cyanurate has a pH of 5.5-7.5.
4. Polyamide composite material according to claim 1, characterized in that the polyamide composite material has a TVOC content of less than 8g/kg and that the melamine cyanurate in the polyamide composite material has a particle size of D10 of 0.15-0.35 μm and a particle size of D90 of 0.5-0.75 μm.
5. The polyamide composite material according to claim 1, wherein the polyamide resin is selected from any one or more of aliphatic polyamide and semi-aromatic polyamide; the aliphatic polyamide is selected from any one or more of PA6, PA66, PA56, PA610, PA612, PA1010, PA1012, PA106, PA1212, PA92, PA102, PA7, PA11, PA12, PA13, PA6/66, PA6/11, PA6/12 or PA 6/13; the semi-aromatic polyamide is selected from any one or more of MXD6, PA6T/6I, PA6T/66 or PA 66/6T; preferably, the polyamide resin is selected from one or more of PA6 or PA 66.
6. The polyamide composite material according to claim 1, further comprising 0.1 to 1 part by weight of a processing aid; the processing aid is selected from one or more of an antioxidant or a lubricant; the antioxidant is selected from one or more of hindered phenol thermal antioxidant, amine antioxidant or phosphate antioxidant; the lubricant is selected from one or more of amide stearate lubricants, alcohol stearate lubricants, stearate lubricants or long-chain saturated linear carboxylate lubricants.
7. Process for the preparation of a polyamide composite material according to any one of claims 1 to 6, characterized in that it comprises the following steps:
according to the proportion, putting the components into a mixer for mixing until the components are uniform to obtain a premix; then, melting and mixing the obtained premix in a first section of double-screw extruder, and extruding and granulating to obtain the polyamide composite material; wherein the extrusion temperature is 150-260 ℃; the diameter of the extrusion screw is 40-75mm, and the length-diameter ratio is (36-60): 1; in the extrusion process, the rotation speed of the screw is controlled to be 300-500rpm, and the feeding speed is controlled to be 80-800 kg/h.
8. The method for producing a polyamide composite material as claimed in claim 7, wherein the extrusion screw has a diameter of 52mm and an aspect ratio of 40: 1; in the extrusion process, the rotating speed of the screw is controlled to be 300-; preferably, the screw rotation speed is controlled to be 350-450rpm, and the feeding speed is controlled to be 200-280kg/h during the extrusion process.
9. Use of a polyamide composite material according to any one of claims 1 to 6 in the field of electronics.
10. The application of the polyamide composite material in the field of electronic and electric appliances as claimed in claim 9 is characterized by being used for electronic products with the rated voltage of 1000-1500V.
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| CN108148407A (en) * | 2017-12-25 | 2018-06-12 | 江苏金发科技新材料有限公司 | High tenacity MCA flame-retardant PA 66 composite materials and preparation method thereof |
| CN108165002A (en) * | 2017-12-25 | 2018-06-15 | 江苏金发科技新材料有限公司 | MCA fire-retardant Nylon 66 composite materials and preparation method thereof |
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| JP6523650B2 (en) * | 2014-10-16 | 2019-06-05 | 旭化成株式会社 | Polyamide resin composition, molded product thereof, and method for producing polyamide resin composition |
| CN107903624B (en) * | 2017-11-30 | 2020-06-26 | 安特普工程塑料（苏州）有限公司 | High-temperature-aging-resistant halogen-free flame-retardant polyamide material and preparation method thereof |
| CN113372711A (en) * | 2021-06-25 | 2021-09-10 | 天津长芦海晶集团有限公司 | Nitrogen-series flame-retardant modified nylon material and preparation method thereof |
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| CN108165002A (en) * | 2017-12-25 | 2018-06-15 | 江苏金发科技新材料有限公司 | MCA fire-retardant Nylon 66 composite materials and preparation method thereof |
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