CN114921091B - Glass fiber reinforced nylon composite material and preparation method and application thereof - Google Patents
Glass fiber reinforced nylon composite material and preparation method and application thereof Download PDFInfo
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- CN114921091B CN114921091B CN202210289236.6A CN202210289236A CN114921091B CN 114921091 B CN114921091 B CN 114921091B CN 202210289236 A CN202210289236 A CN 202210289236A CN 114921091 B CN114921091 B CN 114921091B
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 45
- 239000004677 Nylon Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 229920001778 nylon Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 13
- 229920001955 polyphenylene ether Polymers 0.000 claims description 19
- -1 PA56 Polymers 0.000 claims description 10
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 5
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 5
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229920006119 nylon 10T Polymers 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 2
- 238000013016 damping Methods 0.000 abstract description 24
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- 229920000265 Polyparaphenylene Polymers 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920006389 polyphenyl polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012899 standard injection Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (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 provides a glass fiber reinforced nylon composite material, which comprises the following components in parts by weight: 50 parts of polyamide resin; 7.5-30 parts of polyphenyl ether resin; 2.4-8 parts of maleic anhydride grafted elastomer; 2.4-8 parts of maleic anhydride grafted polyphenyl ether; 0.2-2.5 parts of epoxy resin; 30-70 parts of glass fiber. According to the invention, by adopting the compounding of polyamide resin and polyphenyl ether resin, and further adding maleic anhydride grafted elastomer and maleic anhydride grafted polyphenyl ether resin as compatilizer and epoxy resin lifting damping agent, the high damping glass fiber reinforced nylon composite material can be obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a glass fiber reinforced nylon composite material, and a preparation method and application thereof.
Background
With the development of industries related to vibration such as aerospace, rail transit and automobiles, the problems of vibration reduction and noise reduction are increasingly remarkable. The polymer plastic material has strong plasticity and wide application range, and is also increasingly applied to the industries.
Damping is a process of converting generalized vibration energy into internal loss energy, and the high polymer material can convert external vibration energy received by the material through intermolecular acting force, chemical bond and other acting forces by utilizing the actions of deformation, heat absorption and the like, so that the purposes of vibration reduction and noise reduction are achieved. For the high molecular damping material, several modification methods such as blending, copolymerization and formation of interpenetrating network structure are generally available at present. The blending method can utilize different glass transition temperatures of various materials, thereby widening the damping temperature range of the materials. The copolymerization method can form different rigid and flexible chain segments in a molecular chain, and improves the energy consumption in the material. The interpenetrating network structure can effectively utilize a cross-linked network to form microphase separation, thereby playing a role in increasing damping.
The nylon material is an excellent rigid-tough balance material and has chemical resistance and heat resistance. The glass transition temperature of aliphatic nylon is between 40-70 ℃ and coincides with the ambient temperature when most mechanical motors or mechanical parts are operated. Chinese patent publication No. CN103788629A discloses a high wear-resistant low-noise glass fiber reinforced nylon composite material composition and a preparation method thereof, and the damping factor of the material reaches about 0.04, and still hardly meets the requirements of automobile drying.
Disclosure of Invention
The invention aims to provide a glass fiber reinforced nylon composite material, which has the advantage of high damping.
The invention further aims at providing a preparation method and application of the glass fiber reinforced nylon composite material.
The invention is realized by the following technical scheme:
the glass fiber reinforced nylon composite material comprises the following components in parts by weight:
50 parts of polyamide resin;
7.5-30 parts of polyphenyl ether resin;
2.4-8 parts of maleic anhydride grafted elastomer;
2.4-8 parts of maleic anhydride grafted polyphenyl ether;
0.2-2.5 parts of epoxy resin;
30-70 parts of glass fiber.
Preferably, the composition comprises the following components in parts by weight:
50 parts of polyamide resin;
15-25 parts of polyphenyl ether resin;
4-6 parts of maleic anhydride grafted elastomer;
4-6 parts of maleic anhydride grafted polyphenyl ether;
0.5-1.3 parts of epoxy resin;
30-70 parts of glass fiber.
The polyamide resin is at least one selected from aliphatic polyamide resin and semi-aromatic polyamide resin; the aliphatic polyamide resin is obtained by polymerizing aliphatic diamine and aliphatic diacid, and is selected from at least one of PA6, PA66, PA56, PA612, PA1010 and PA 1012; the semi-aromatic polyamide resin is obtained by polymerizing aromatic diacid and aliphatic diamine and is selected from at least one of PA10T, PA6T, PA 6I. Aliphatic polyamides are preferred from the viewpoint of increasing the damping factor.
It has been found through experimentation that the object of the present invention can be achieved when the grafting ratio of the maleic anhydride-grafted elastomer is 0.1 to 2.5wt%, preferably the grafting ratio of the maleic anhydride-grafted elastomer is 0.3 to 1wt%.
The preparation method of the maleic anhydride grafted elastomer comprises the following steps: the material is prepared by a double-screw extruder by adopting a melt blending extrusion method, wherein the temperature range of the extruder is 150-180-170-160-150-130-130-130-130-150 ℃ and the rotating speed is 250-450rpm. The formula is at least one of thermoplastic elastomer and maleic anhydride, the thermoplastic elastomer is GMA, POE, EPDM, SEBS, and the addition amount of each material is calculated according to the grafting rate.
The grafting ratio test method of the maleic anhydride grafted elastomer and the maleic anhydride grafted polyphenyl ether comprises the following steps: after xylene purification, acid-base titration was performed with phenolphthalein indicator.
The maleic anhydride grafted elastomer is at least one selected from the group consisting of maleic anhydride grafted SBS, maleic anhydride grafted POE, maleic anhydride grafted EPDM and maleic anhydride grafted SEBS.
It has been found through experiments that the object of the present invention can be achieved when the grafting ratio of the maleic anhydride-grafted polyphenylene ether is 0.2 to 2.5% by weight, and preferably the grafting ratio of the maleic anhydride-grafted polyphenylene ether is 0.5 to 1.5% by weight.
The preparation method of the maleic anhydride grafted polyphenyl ether comprises the following steps: and calculating the addition amount of the maleic anhydride and the polyphenyl ether resin according to the grafting ratio, uniformly mixing, and adopting a melt blending extrusion method through a double-screw extruder, wherein the temperature range of the extruder is 180-280-270-260-250-230-230-230-230-250 ℃, and the rotating speed is 250-450rpm.
The epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin, hydroxymethyl bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, o-cresol formaldehyde epoxy resin and resorcinol formaldehyde epoxy resin.
Bisphenol a type epoxy resin is preferable from the viewpoint of strength of the nylon composite.
Preferably, the glass fibers are selected from flat glass fibers, and the ratio of the major axis to the minor axis is in the range of 2:1 to 5:1.
The melt index of the polyamide resin and the polyphenylene ether resin is not particularly limited in the present invention, and it has been found through experiments that when the relative viscosity of the polyamide resin is 2.0 to 3.0, the intrinsic viscosity of the polyphenylene ether resin is in the range of 0.32 to 0.55cm 3 And/g, all of which achieve the object of the present invention. The relative viscosity of the polyamide resin was measured in an Ubbelohde viscometer at 25℃using 96% concentrated sulfuric acid as a solvent. The intrinsic viscosity of the polyphenylene ether resin was measured according to HG/T2364 using chloroform as a solvent at 25 ℃.
The preparation method of the glass fiber reinforced nylon composite material comprises the following steps: according to the proportion, the components except the glass fiber are uniformly mixed, extruded and granulated by a double-screw extruder, and the glass fiber is fed and added at the side to obtain the nylon composite material, wherein the temperature range of the screw is 180-270 ℃ and the rotating speed range is 250-350rpm.
The glass fiber reinforced nylon composite material is applied to aircraft parts and vehicle-mounted parts.
The invention has the following beneficial effects:
according to the invention, the polyamide/polyphenyl ether is further added with the maleic anhydride grafted elastomer and the maleic anhydride grafted polyphenyl ether as compatilizer and the epoxy resin to lift the damping agent, so that the high-damping glass fiber reinforced nylon composite material can be obtained, and meanwhile, the strength and the rigidity of the composite material can be improved.
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 present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The sources of the raw materials used in the invention are as follows:
PA6: HY-2500A, relative viscosity 2.5, jiangsu sea yang chemical fiber Co., ltd;
PA66: PA 66U 4800, relative viscosity 2.8, inflight chemical;
PA10T: vinyl 6100p nc013, relative viscosity 2.1, zhuhai wan general special engineering plastics limited;
PA610: PA 610F 120, relative viscosity 2.2, shandong guang boundary new material limited;
polyphenylene ether resin a: PPE LXR035, intrinsic viscosity 0.35cm 3 /g, nantong star synthetic materials Co., ltd;
polyphenylene ether resin B: PPE LXR050, intrinsic viscosity 0.50cm 3 /g, nantong star synthetic materials Co., ltd;
maleic anhydride grafted SBS-1: the grafting rate of maleic anhydride is 0.1wt percent, and the product is self-made.
Maleic anhydride grafted SBS-2: the grafting rate of maleic anhydride is 0.3wt percent, and the product is self-made.
Maleic anhydride grafted SBS-3: the grafting rate of maleic anhydride is 1.0wt percent, and the product is self-made.
Maleic anhydride grafted SBS-4: the grafting rate of maleic anhydride is 2.5wt percent, and the product is self-made.
Maleic anhydride grafted POE: the grafting rate of maleic anhydride is 0.8wt percent, and the product is self-made.
Maleic anhydride grafted EPDM: the grafting rate of maleic anhydride is 1.2wt percent, and the product is self-made.
Maleic anhydride grafted SEBS: the grafting rate of maleic anhydride is 1.0wt percent, and the product is self-made.
Maleic anhydride grafted polyphenylene ether-1: the grafting rate of maleic anhydride is 0.2 weight percent, and the preparation is self-made;
maleic anhydride grafted polyphenylene ether-2: the grafting rate of maleic anhydride is 0.5 weight percent, and the preparation is self-made;
maleic anhydride grafted polyphenylene ether-3: the grafting rate of maleic anhydride is 1.5wt percent, and the preparation is self-made;
maleic anhydride grafted polyphenylene ether-4: the grafting rate of maleic anhydride is 2.5wt percent, and the preparation is self-made;
epoxy resin a: YD-019, bisphenol A type, national chemical Co., ltd;
epoxy resin B: NPEF-170, bisphenol F type, taiwan south Asia chemical industry;
epoxy resin C: YX8034, hydrogenated bisphenol a epoxy resin, shanghai mass company limited;
glass fiber a: glass fiber ECS301HP-3-M4, flat glass fiber, the ratio of the major axis to the minor axis is 2:1-5:1, chongqing International composite material Co., ltd;
glass fiber B: ECS301HP-3-H, round glass fiber, chongqing International composite Co., ltd.
Preparation method of nylon composite materials of examples and comparative examples: according to the proportion, the components except the glass fiber are uniformly mixed, extruded and granulated by a double-screw extruder, and the glass fiber is fed and added at the side to obtain the nylon composite material, wherein the temperature range of the screw is 180-270 ℃ and the rotating speed range is 250-350rpm.
The testing method comprises the following steps:
(1) Flexural modulus: sample size and test standard reference ISO 178, load rate 2mm/min. The dry flexural modulus is the test result of standard injection molded bars after conditioning at 23 ℃/50% rh for 48 hours.
(2) Tensile strength: the sample size and test standard are referred to ISO 527-2, the draw rate being 10mm/min. The dry tensile strength is the test result of standard injection molded bars after conditioning at 23 ℃/50% RH for 48 hours.
(3) Damping factor: and adopting a DMA three-point bending test, wherein the frequency is 1Hz, the temperature range is-30-120 ℃, the temperature rise rate is 3 ℃/min, and the tan theta peak value of the material is obtained within the range of 60-80 ℃.
Table 1: examples 1-7 nylon composite component content (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| PA6 | 50 | 50 | 50 | 50 | |||
| PA66 | 50 | ||||||
| PA10T | 50 | ||||||
| PA610 | 50 | ||||||
| Polyphenylene ether resin A | 20 | 20 | 20 | 20 | 7.5 | 15 | |
| Polyphenylene ether resin B | 20 | ||||||
| Maleic anhydride grafted SBS-1 | 5 | 5 | 5 | 5 | 5 | 2.4 | 4 |
| Maleic anhydride grafted polyphenyl ether-1 | 4 | 4 | 4 | 4 | 4 | 2.4 | 4 |
| Epoxy resin A | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.2 | 0.5 |
| Glass fiber A | 50 | 30 | 70 | 50 | 50 | 50 | 50 |
| Flexural modulus, MPa | 10850 | 7983 | 14375 | 9739 | 9647 | 13986 | 11349 |
| Tensile strength, MPa | 190.1 | 178.5 | 201.5 | 188.7 | 185.3 | 197.9 | 192.5 |
| Damping factor, tan theta | 0.084 | 0.073 | 0.059 | 0.072 | 0.076 | 0.053 | 0.073 |
From examples 1 to 4, it is understood that the semi-aromatic polyamide resin composite material has higher strength, and the aliphatic polyamide resin composite material has higher damping factor, and from the viewpoint of improving the damping factor, the aliphatic polyamide resin is preferable.
Table 2: examples 8-14 Nylon composite component content (parts by weight) and test results
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| PA6 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Polyphenylene ether resin A | 25 | 30 | 20 | 20 | 20 | 20 | 20 |
| Maleic anhydride grafted SBS-1 | 6 | 8 | |||||
| Maleic anhydride grafted SBS-2 | 5 | ||||||
| Maleic anhydride grafted SBS-3 | 5 | ||||||
| Maleic anhydride grafted SBS-4 | 5 | ||||||
| Maleic anhydride grafted POE | 5 | ||||||
| Maleic anhydride grafted EPDM | 5 | ||||||
| Maleic anhydride grafted polyphenyl ether-1 | 6 | 8 | 4 | 4 | 4 | 4 | 4 |
| Epoxy resin A | 1.3 | 2.5 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
| Glass fiber A | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Flexural modulus, MPa | 10520 | 9158 | 10405 | 10551 | 10633 | 9224 | 9375 |
| Tensile strength, MPa | 191.8 | 186.2 | 187.1 | 189.4 | 192.6 | 183.8 | 185.5 |
| Damping factor, tan theta | 0.098 | 0.104 | 0.089 | 0.090 | 0.082 | 0.085 | 0.079 |
As is clear from 1/6-9, the damping factor is well balanced with tensile strength and flexural modulus in the preferable blending range.
As is evident from examples 1/10 to 15, the maleic anhydride-grafted elastomer preferably has a grafting ratio of 0.3 to 1.0wt% and a higher damping factor.
Table 3: examples 15-20 Nylon composite component content (parts by weight) and test results
| Example 15 | Example 16 | Example 17 | Example 18 | Examples19 | Example 20 | |
| PA6 | 50 | 50 | 50 | 50 | 50 | 50 |
| Polyphenylene ether resin A | 20 | 20 | 20 | 20 | 20 | 20 |
| Maleic anhydride grafted SEBS | 5 | |||||
| Maleic anhydride grafted SBS-1 | 5 | 5 | 5 | 5 | 5 | |
| Maleic anhydride grafted polyphenyl ether-1 | 4 | 4 | 4 | |||
| Maleic anhydride grafted polyphenyl ether-2 | 4 | |||||
| Maleic anhydride grafted polyphenylene ether-3 | 4 | |||||
| Maleic anhydride grafted polyphenylene ether-4 | 4 | |||||
| Epoxy resin A | 0.8 | 0.8 | 0.8 | 0.8 | ||
| Epoxy resin B | 0.8 | |||||
| Epoxy resin C | 0.8 | |||||
| Glass fiber A | 50 | 50 | 50 | 50 | 50 | 50 |
| Flexural modulus, MPa | 9375 | 9513 | 9510 | 9525 | 9503 | 9509 |
| Tensile strength, MPa | 184.9 | 189.3 | 190.5 | 192.6 | 187.1 | 187.8 |
| Damping factor, tan theta | 0.881 | 0.093 | 0.096 | 0.089 | 0.084 | 0.085 |
As is clear from examples 1, 16 to 18, the grafting ratio of maleic anhydride-grafted polyphenylene ether is preferably 0.5 to 1.5% by weight, and the damping factor is higher.
As is clear from examples 1/19 to 20, bisphenol A type epoxy resin is preferable from the viewpoint of the strength of the nylon composite.
Table 4: comparative example nylon composite component content (parts by weight) and test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| PA6 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Polyphenylene ether resin A | 0 | 35 | 20 | 20 | 20 | 20 | 20 | 20 |
| Maleic anhydride grafted SBS-1 | 5 | 5 | 5 | 5 | 5 | 5 | 0 | 10 |
| Maleic anhydride grafted polyphenyl ether-1 | 4 | 4 | 4 | 4 | 0 | 10 | 4 | 4 |
| Epoxy resin A | 0.8 | 0.8 | 4 | 0.8 | 0.8 | 0.8 | 0.8 | |
| Glass fiber A | 50 | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| Flexural modulus, MPa | 10183 | 8519 | 8782 | 8994 | 8693 | 8645 | 8671 | 8530 |
| Tensile strength, MPa | 199.4 | 178.6 | 180.2 | 181.7 | 178.5 | 177.3 | 177.8 | 175.4 |
| Damping factor, tan theta | 0.035 | 0.023 | 0.034 | 0.025 | 0.033 | 0.027 | 0.031 | 0.029 |
As is clear from comparative example 1/3, the absence of the addition of polyphenylene ether resin or epoxy resin resulted in a low damping factor.
As is clear from comparative examples 2/4, if the addition amount of the polyphenylene ether resin or the epoxy resin is too high, the damping factor is lowered.
As is clear from comparative examples 5 to 8, the addition amount of the maleic anhydride-grafted elastomer (or maleic anhydride-grafted polyphenylene ether) was not excessively high, the damping factor was low, and the strength was low.
Claims (12)
1. The glass fiber reinforced nylon composite material is characterized by comprising the following components in parts by weight:
50 parts of polyamide resin;
7.5-30 parts of polyphenyl ether resin;
2.4-8 parts of maleic anhydride grafted elastomer;
2.4-8 parts of maleic anhydride grafted polyphenyl ether;
0.2-2.5 parts of epoxy resin;
30-70 parts of glass fiber;
the polyamide resin is at least one selected from aliphatic polyamide resin and semi-aromatic polyamide resin;
the grafting rate of the maleic anhydride grafted elastomer is 0.1-2.5wt%, and the grafting rate of the maleic anhydride grafted polyphenyl ether is 0.2-2.5wt%;
the epoxy resin is at least one selected from bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, resorcinol epoxy resin, hydroxymethyl bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, o-cresol formaldehyde epoxy resin and resorcinol formaldehyde epoxy resin.
2. The glass fiber reinforced nylon composite of claim 1, comprising the following components in parts by weight:
50 parts of polyamide resin;
15-25 parts of polyphenyl ether resin;
4-6 parts of maleic anhydride grafted elastomer;
4-6 parts of maleic anhydride grafted polyphenyl ether;
0.5-1.3 parts of epoxy resin;
30-70 parts of glass fiber.
3. The glass fiber reinforced nylon composite of claim 1, wherein the aliphatic polyamide resin is selected from at least one of PA6, PA66, PA56, PA612, PA1010, PA 1012; the semi-aromatic polyamide resin is selected from at least one of PA10T, PA6T, PA 6I.
4. A glass fiber reinforced nylon composite according to claim 3, wherein the polyamide resin is selected from aliphatic polyamide resins.
5. The glass fiber reinforced nylon composite of claim 1, wherein the maleic anhydride grafted elastomer is at least one selected from the group consisting of maleic anhydride grafted SBS, maleic anhydride grafted POE, maleic anhydride grafted EPDM, and maleic anhydride grafted SEBS.
6. The glass fiber reinforced nylon composite of claim 1, wherein the maleic anhydride grafted elastomer has a grafting ratio of 0.3-1wt%.
7. The glass fiber reinforced nylon composite of claim 1, wherein the grafting ratio of the maleic anhydride grafted polyphenyl ether is 0.5-1.5wt%.
8. The glass fiber reinforced nylon composite of claim 1, wherein the epoxy resin is selected from bisphenol a epoxy resins.
9. The glass fiber reinforced nylon composite of claim 1, wherein the glass fibers are selected from the group consisting of flat glass fibers having a ratio of major axis to minor axis in the range of 2:1 to 5:1.
10. The glass fiber reinforced nylon composite of claim 1, wherein the polyamide resin has a relative viscosity of 2.0 to 3.0 and the polyphenylene ether resin has an intrinsic viscosity in the range of 0.32 to 0.55cm 3 /g。
11. The method for preparing the glass fiber reinforced nylon composite material according to any one of claims 1 to 10, comprising the following steps: according to the proportion, the components except the glass fiber are uniformly mixed, extruded and granulated by a double-screw extruder, and the glass fiber is fed and added at the side to obtain the nylon composite material, wherein the temperature range of the screw is 180-270 ℃ and the rotating speed range is 250-350rpm.
12. Use of a glass fiber reinforced nylon composite according to any of claims 1 to 10 for aircraft parts, vehicle parts.
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| CN104098885A (en) * | 2013-04-15 | 2014-10-15 | 上海杰事杰新材料(集团)股份有限公司 | Glass-fiber reinforced polyphenylene oxide /polyamide alloy material and preparation method thereof |
| CN113861671A (en) * | 2021-10-09 | 2021-12-31 | 中山市捷德新材料科技有限公司 | High-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and preparation method thereof |
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| CN104098885A (en) * | 2013-04-15 | 2014-10-15 | 上海杰事杰新材料(集团)股份有限公司 | Glass-fiber reinforced polyphenylene oxide /polyamide alloy material and preparation method thereof |
| CN113861671A (en) * | 2021-10-09 | 2021-12-31 | 中山市捷德新材料科技有限公司 | High-fluidity glass fiber reinforced polyphenyl ether polyamide composite material and preparation method thereof |
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