CN115304909A - Novel polyamide composite material for outdoor use and preparation method thereof - Google Patents
Novel polyamide composite material for outdoor use and preparation method thereof Download PDFInfo
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- CN115304909A CN115304909A CN202111085443.1A CN202111085443A CN115304909A CN 115304909 A CN115304909 A CN 115304909A CN 202111085443 A CN202111085443 A CN 202111085443A CN 115304909 A CN115304909 A CN 115304909A
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- polyamide
- composite material
- resin
- light stabilizer
- polyamide composite
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 78
- 229920002647 polyamide Polymers 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004611 light stabiliser Substances 0.000 claims abstract description 37
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000007822 coupling agent Substances 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- -1 unsaturated fatty acid titanate Chemical class 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 22
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 19
- 125000004423 acyloxy group Chemical group 0.000 claims description 18
- 229910052680 mordenite Inorganic materials 0.000 claims description 17
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 17
- 229920002292 Nylon 6 Polymers 0.000 claims description 16
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 16
- 239000010445 mica Substances 0.000 claims description 16
- 229910052618 mica group Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 2
- 229920006152 PA1010 Polymers 0.000 claims description 2
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims 2
- 239000000194 fatty acid Substances 0.000 claims 2
- 229930195729 fatty acid Natural products 0.000 claims 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 31
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 15
- UONCERAQKBPLML-UHFFFAOYSA-N (6-ethoxypyridin-3-yl)boronic acid Chemical compound CCOC1=CC=C(B(O)O)C=N1 UONCERAQKBPLML-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- GQBHYWDCHSZDQU-UHFFFAOYSA-N 4-(2,4,4-trimethylpentan-2-yl)-n-[4-(2,4,4-trimethylpentan-2-yl)phenyl]aniline Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1NC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 GQBHYWDCHSZDQU-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the technical field of C08L high polymer materials, and particularly provides an outdoor novel polyamide composite material and a preparation method thereof. The invention provides a novel polyamide composite material for outdoor use, which is prepared from polyamide resin, a filler, a titanate coupling agent, a light stabilizer, an antioxidant, a toughness improver, a conductive modifier and other auxiliaries. Compared with the prior art, the novel polyamide composite material prepared by the invention has excellent mechanical properties, good antistatic property and light aging resistance, and simple synthesis process, and is beneficial to large-scale production and popularization of the polyamide composite material.
Description
Technical Field
The invention relates to the technical field of C08L high polymer materials, and particularly provides an outdoor novel polyamide composite material and a preparation method thereof.
Background
The polyamide material has good tensile strength, impact resistance, wear resistance and oil resistance, and is widely applied to the fields of foaming materials, oil pipelines, mechanical parts, cable protective sleeves and the like. However, with the rapid development of the industrial science and technology field, the polyamide materials in the prior art can not meet the requirements for the performance in the industrial production, so that the development of a polyamide composite material with good performance becomes one of the research hotspots of researchers in recent years.
The invention discloses a wear-resistant antistatic polyamide composite material, which is disclosed in Chinese patent publication No. CN106967293A, wherein the wear-resistant performance and the antistatic performance of the polyamide composite material are remarkably improved by adding silicon carbide with a capsule structure and modified hexagonal boron nitride micro-tablets, but the scheme has the problem of complex synthesis process, is not beneficial to industrial large-scale production of the polyamide composite material prepared by the scheme, and is not beneficial to large-scale popularization and use of the polyamide composite material.
The patent publication No. CN105038199A of Chinese invention discloses a fiber-reinforced wear-resistant polyamide composite material, and a preparation method and application thereof, wherein glass fibers are used as reinforcements in the disclosed patent, so that the problems of poor tensile strength and wear resistance of the polyamide composite material are solved, but the light aging resistance, antistatic property and flexibility of the polyamide composite material are not reflected obviously.
Therefore, the development of a novel polyamide composite material with excellent wear resistance, aging resistance, flexibility and antistatic performance has potential application value.
Disclosure of Invention
In order to solve the problems, the invention provides a novel polyamide composite material for outdoor use, which comprises the following raw materials in parts by weight: 40-80 parts of polyamide resin, 15-25 parts of filler, 0.5-1 part of titanate coupling agent, 0.5-1.5 parts of light stabilizer, 0.5-2 parts of antioxidant, 12-26 parts of toughness improver, 2-5 parts of conductive modifier and 1-3 parts of assistant.
In a preferred embodiment of the present invention, the polyamide resin is at least one of polyamide 6 resin, polyamide 66 resin, polyamide 610 resin, and polyamide 1010 resin.
In a more preferred embodiment of the present invention, the polyamide resin is polyamide 6 resin or polyamide 610 resin, and the mass ratio of the polyamide 6 resin to the polyamide 610 resin is (1-3): (0.5-1.5).
In a most preferred embodiment of the present invention, the mass ratio of the polyamide 6 resin to the polyamide 610 resin is 2.5:1.
as a preferable technical scheme of the invention, the filler is at least one of diatomite, mordenite, silica gel, activated carbon, talcum powder and mica powder.
As a more preferable technical scheme of the invention, the filler is mordenite, mica powder and talcum powder, and the mass ratio of the mordenite to the mica powder to the talcum powder is (0.4-1.2): (1-2.2): (0.2-0.6).
As a most preferred technical scheme of the invention, the mass ratio of the mordenite, the mica powder and the talcum powder is 0.6:1.4:0.4.
as a preferable technical scheme of the invention, the titanate coupling agent is at least one of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, isopropyl dioleate acyloxy dioctyl phosphate acyloxy titanate and monoalkoxyl unsaturated fatty acid titanate.
As a more preferable technical scheme of the invention, the titanate coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and monoalkoxy unsaturated fatty acid titanate, and the mass ratio of the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate to the monoalkoxy unsaturated fatty acid titanate is (1-3): (0.5-1.5).
As a most preferable technical scheme of the invention, the mass ratio of the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate to the monoalkoxyl unsaturated fatty acid titanate is 2.2:1.1.
the applicant finds that when mordenite, mica powder and talcum powder are added into a system, the mechanical property of the polyamide composite material is correspondingly enhanced, but the problems of high water absorption, easy agglomeration of fillers and poor system stability occur, and the application range of the polyamide material in practical use is limited. In order to solve the above problems, the applicant has unexpectedly found that when a mass ratio of 2.2:1.1 when the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and the mono-alkoxy unsaturated fatty acid titanate interact with mica powder, talcum powder and polyamide resin in a system, the stability of the system and the wear resistance of the polyamide composite material can be obviously improved, and the phenomenon of deformation of the polyamide composite material caused by rainwater can be effectively relieved. The applicant conjectures the possible reason that isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and mono-alkoxy unsaturated fatty acid titanate interact with polar groups on the surface of the talcum powder, so that on one hand, the pores among the talcum powder particles are enhanced, the phenomenon that the talcum powder is easy to agglomerate in the system is effectively relieved, and the system stability of the polyamide resin is improved; on the other hand, the surface of the talcum powder is modified, the talcum powder interacts with active ingredients in the polyamide, and groups with a certain carbon chain length are introduced into a polyamide structure chain, so that the hydrophobicity of the polyamide resin is enhanced, and the defect that the polyamide composite material deforms due to overlarge water absorption of the polyamide composite material is effectively relieved.
In a preferred embodiment of the present invention, the light stabilizer is at least one of a salicylate light stabilizer, a benzophenone light stabilizer, and a benzotriazole light stabilizer.
As a more preferable technical solution of the present invention, the light stabilizer is a benzophenone light stabilizer, a benzotriazole light stabilizer, and the mass ratio of the benzophenone light stabilizer to the benzotriazole light stabilizer is (1.2 to 2.6): (0.2-0.8).
As a most preferred technical scheme of the invention, the mass ratio of the benzophenone light stabilizer to the benzotriazole light stabilizer is 1.4:0.6.
in a preferred embodiment of the present invention, the benzophenone-based light stabilizer is at least one of 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octoxybenzophenone.
In a preferred embodiment of the present invention, the benzotriazole-based light stabilizer is at least one of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole and 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole.
The applicant has surprisingly found that when a mass ratio of 1.4:0.6 of 2-hydroxy-4-n-octoxybenzophenone and 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole can interact with other components in the system, so that the mechanical strength of the polyamide composite material is remarkably improved, and the light aging resistance of the polyamide composite material is also enhanced. The applicant conjectures that 2-hydroxy-4-n-octoxy benzophenone and 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole are adsorbed on the surface of mordenite, and mordenite loaded with a light stabilizer is uniformly dispersed in a polyamide resin system, so that on one hand, in the process of using the polyamide composite material outdoors, 2-hydroxy-4-n-octoxy benzophenone and 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole are cooperated with isopropyl phenyl p-diphenylamine and dioctadecyl diphosphite pentaerythritol ester in the system, thereby remarkably reducing the corrosion of the polyamide composite material in the outdoor environment, improving the light aging resistance of the polyamide composite material, effectively solving the problem that the polyamide composite material is prone to color change after long-time illumination, and simultaneously prolonging the service life of the polyamide composite material when being used outdoors; on the other hand, a group with larger steric hindrance is introduced into the structure of the polyamide resin, so that the rotation degree of the molecular structure of the polyamide resin is reduced, the stability of the molecular structure of the polyamide resin is enhanced, the shock resistance of the polyamide composite material is improved, and the gaps among the molecules in the polyamide resin are reduced, so that the hydrophobicity of the polyamide composite material is improved, and the comprehensive quality of the polyamide composite material is improved.
As a preferable technical scheme, the antioxidant is at least one of aromatic amine antioxidant, hindered phenol antioxidant and phosphite antioxidant.
As a preferred technical scheme of the invention, the antioxidant is an aromatic amine antioxidant and a phosphite antioxidant, and the mass ratio of the amine antioxidant to the phosphite antioxidant is (0.8-1.5): (0.2-1).
As a preferable technical scheme, the mass ratio of the aromatic amine antioxidant to the phosphite antioxidant is 1.2:0.4.
as a preferable technical scheme of the invention, the aromatic amine antioxidant is at least one of isopropylphenyl p-diphenylamine and 4,4' -di-tert-octyldiphenylamine.
As a preferred technical scheme of the invention, the phosphite ester antioxidant is at least one of dioctadecyl pentaerythritol diphosphite, tris (nonylphenyl) phosphite and tris (2,4-di-tert-butylphenyl) phosphite.
As a preferable technical scheme, the toughness improver is at least one of butadiene rubber, butyl rubber, nitrile rubber and styrene butadiene rubber.
As a preferable technical scheme of the invention, the conductive modifier is at least one of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and trihydroxyethyl quaternary ammonium methyl sulfate.
As a preferable technical scheme of the invention, the auxiliary agent is at least one of an anti-dripping agent and a plasticizer.
As a preferable technical scheme of the invention, the auxiliary agent is a plasticizer.
In a preferred embodiment of the present invention, the plasticizer is at least one of DMP, DEP, DBP, and DOP.
The second aspect of the invention provides a preparation method of a novel outdoor polyamide composite material, which comprises the following steps:
(1) Weighing polyamide resin, light stabilizer, antioxidant, toughness improver, conductive modifier and auxiliary agent according to a proportion, and stirring for 10-30min at 220-270 ℃ to obtain a mixture;
(2) And (2) adding a filler and a titanate coupling agent into the mixture obtained in the step (1), and extruding and granulating by using a double-screw extruder to obtain the novel outdoor polyamide composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. the novel polyamide composite material prepared by the invention is prepared by adding the following components in a mass ratio of 2.2:1.1, the isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and the monoalkoxy unsaturated fatty acid titanate can solve the problem that talcum powder in the system is easy to agglomerate on one hand, enhance the hydrophobicity of polyamide resin on the other hand, and effectively relieve the defect that the polyamide composite material deforms due to overlarge water absorption;
2. the novel polyamide composite material prepared by the invention is prepared by adding the following components in a mass ratio of 1.4:0.6 of 2-hydroxy-4-n-octoxybenzophenone and 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole can interact with other components in the system, so that the mechanical strength of the polyamide composite material is remarkably improved, the light aging resistance of the polyamide composite material is enhanced, and the problem that the polyamide composite material is easy to discolor after long-time illumination is effectively solved;
3. the novel polyamide composite material prepared by the invention is prepared by adding the following components in a mass ratio of 1.2:0.4 of isopropylphenyl p-diphenylamine and dioctadecyl diphosphite pentaerythritol ester, which are mutually synergistic with a light stabilizer in a system while ensuring the excellent mechanical property of the polyamide composite material, obviously improve the light aging resistance of the polyamide composite material, prolong the service life of the polyamide composite material, expand the application range of the polyamide composite material and are widely applied to the fields of outdoor fitness equipment and the like;
4. according to the novel polyamide composite material prepared by the invention, the nitrile rubber is added into the system and interacts with the polar groups of the components in the system, so that the flexibility of the polyamide composite material is improved, the interconnection of the components in the system is promoted, the acting force among the components is enhanced, and the wear resistance and the impact resistance of the polyamide composite material are improved;
5. according to the novel polyamide composite material prepared by the invention, the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is added into the system and interacts with the polyamide resin in the system, so that the antistatic performance of the polyamide composite material is obviously improved, the molecular weight of the polyamide resin is enhanced, the viscosity of the system is improved, the forming viscosity of the polyamide composite material is reduced, the difficulty of a synthesis process is reduced, and the large-scale production and popularization of the polyamide composite material are facilitated.
Detailed Description
Example 1
Embodiment 1 provides a novel polyamide composite material for outdoor use, which is prepared from the following raw materials in parts by weight: 40 parts of polyamide resin, 15 parts of filler, 0.5 part of titanate coupling agent, 0.5 part of light stabilizer, 0.5 part of antioxidant, 12 parts of toughness improver, 2 parts of conductive modifier and 1 part of assistant.
The polyamide resin is polyamide 6 resin or polyamide 610 resin; the mass ratio of the polyamide 6 resin to the polyamide 610 resin is 2.5:1; polyamide 6 resin available from Naxin plastics, inc. of Suzhou under model number BKV50H2.0; polyamide 610 resin was obtained from Di Jie plastication, suzhou, under the model number CM2001;
the filler is mordenite, mica powder and talcum powder; the mass ratio of the mordenite to the mica powder to the talcum powder is 0.6:1.4:0.4; mordenite was purchased from Heyi City Hengyuan mineral chemical Co., ltd; mica powder was purchased from the national company of Antai mining, inc., lingshu county; talcum powder is available from Dendong Tianci flame retardant materials science and technology Limited;
the titanate coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and monoalkoxyl unsaturated fatty acid titanate; the mass ratio of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate to monoalkoxy unsaturated fatty acid titanate is 2.2:1.1; the CAS number of isopropyl tris (dioctyl pyrophosphato acyloxy) titanate is 67691-13-8; mono-alkoxy unsaturated fatty acid titanate is purchased from Qi Bang chemical Co., ltd, of Fushan city, and the type is titanate coupling agent 105;
the light stabilizer is 2-hydroxy-4-n-octoxybenzophenone or 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole; the mass ratio of the 2-hydroxy-4-n-octoxybenzophenone to the 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole is 1.4:0.6; CAS number of 2-hydroxy-4-n-octoxy benzophenone is 1843-05-6; CAS number of 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole is 3846-71-7;
the antioxidant is isopropylphenyl p-diphenylamine and dioctadecyl diphosphite pentaerythritol ester; the mass ratio of the isopropylphenyl p-diphenylamine to the dioctadecyl diphosphite pentaerythritol ester is 1.2:0.4; the CAS number of the isopropylphenyl p-diphenylamine is 101-72-4; dioctadecyl pentaerythrityl diphosphite is purchased from Shanghai Panhua chemical Co., ltd;
the toughness improver is nitrile rubber; nitrile rubber was purchased from denna cheng rui chemical limited;
the conductivity improver is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate; the CAS number of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is 86443-82-5;
the auxiliary agent is DMP, and the CAS number of the DMP is 131-11-3.
The preparation method of the outdoor novel polyamide composite material comprises the following steps:
(1) Weighing polyamide resin, light stabilizer, antioxidant, toughness improver, conductive modifier and auxiliary agent according to a proportion, and stirring for 20min at 265 ℃ to obtain a mixture;
(2) And (2) adding a filler and a titanate coupling agent into the mixture obtained in the step (1), and extruding and granulating by using a double-screw extruder to obtain the novel outdoor polyamide composite material.
Example 2
Embodiment 2 provides a novel polyamide composite material for outdoor use, which comprises the following raw materials in parts by weight: 80 parts of polyamide resin, 25 parts of filler, 1 part of titanate coupling agent, 1.5 parts of light stabilizer, 2 parts of antioxidant, 26 parts of toughness improver, 5 parts of conductive modifier and 3 parts of assistant.
The polyamide resin is polyamide 6 resin or polyamide 610 resin; the mass ratio of the polyamide 6 resin to the polyamide 610 resin is 2.5:1; polyamide 6 resin available from Naxin plastics, inc. of Suzhou under model number BKV50H2.0; polyamide 610 resin was obtained from Di Jie plastication, suzhou, under the model number CM2001;
the filler is mordenite, mica powder and talcum powder; the mass ratio of the mordenite to the mica powder to the talcum powder is 0.6:1.4:0.4; mordenite was purchased from Heyi City Hengyuan mineral chemical Co., ltd; mica powder was purchased from the national company of Antai mining, inc., lingshu county; talcum powder is available from Dendong Tianci flame retardant materials science and technology Limited;
the titanate coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and monoalkoxyl unsaturated fatty acid titanate; the mass ratio of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate to monoalkoxy unsaturated fatty acid titanate is 2.2:1.1; the CAS number of isopropyl tris (dioctyl pyrophosphato acyloxy) titanate is 67691-13-8; mono-alkoxy unsaturated fatty acid titanate is purchased from Qi Bang chemical Co., ltd, of Fushan city, and the type is titanate coupling agent 105;
the light stabilizer is 2-hydroxy-4-n-octoxybenzophenone or 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole; the mass ratio of the 2-hydroxy-4-n-octoxybenzophenone to the 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole is 1.4:0.6; the CAS number of the 2-hydroxy-4-n-octoxy benzophenone is 1843-05-6; CAS number of 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole is 3846-71-7;
the antioxidant is isopropylphenyl p-diphenylamine and dioctadecyl diphosphite pentaerythritol ester; the mass ratio of the isopropylphenyl p-diphenylamine to the dioctadecyl diphosphite pentaerythritol ester is 1.2:0.4; the CAS number of isopropylphenyl p-diphenylamine is 101-72-4; the dioctadecyl pentaerythrityl diphosphite is purchased from Shanghai Panhua chemical Co., ltd;
the toughness improver is nitrile rubber; nitrile rubber was purchased from denna cheng rui chemical limited;
the conductivity improver is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate; the CAS number of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is 86443-82-5;
the auxiliary agent is DMP, and the CAS number of the DMP is 131-11-3.
The preparation method of the novel outdoor polyamide composite material is the same as that of example 1.
Example 3
Embodiment 3 provides a novel polyamide composite material for outdoor use, which comprises the following raw materials in parts by weight: 60 parts of polyamide resin, 20 parts of filler, 0.7 part of titanate coupling agent, 1 part of light stabilizer, 1.4 parts of antioxidant, 20 parts of toughness improver, 3 parts of conductive modifier and 2 parts of assistant.
The polyamide resin is polyamide 6 resin or polyamide 610 resin; the mass ratio of the polyamide 6 resin to the polyamide 610 resin is 2.5:1; polyamide 6 resin available from Naxin plastics, inc. of Suzhou under model number BKV50H2.0; polyamide 610 resin available from Di Jie plastication, suzhou, model number CM2001;
the filler is mordenite, mica powder and talcum powder; the mass ratio of the mordenite to the mica powder to the talcum powder is 0.6:1.4:0.4; mordenite was purchased from Heyi City Hengyuan mineral chemical Co., ltd; mica powder was purchased from the national company of Antai mining, inc., lingshu county; talcum powder is available from Dendong Tianci flame retardant materials science and technology Limited;
the titanate coupling agent is isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and monoalkoxyl unsaturated fatty acid titanate; the mass ratio of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate to monoalkoxy unsaturated fatty acid titanate is 2.2:1.1; the CAS number of isopropyl tri (dioctyl pyrophosphate acyloxy) titanate is 67691-13-8; mono-alkoxy unsaturated fatty acid titanate is purchased from Qi Bang chemical Co., ltd, of Fushan city, and the type is titanate coupling agent 105;
the light stabilizer is 2-hydroxy-4-n-octoxybenzophenone or 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole; the mass ratio of the 2-hydroxy-4-n-octoxybenzophenone to the 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole is 1.4:0.6; CAS number of 2-hydroxy-4-n-octoxy benzophenone is 1843-05-6; CAS number of 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole is 3846-71-7;
the antioxidant is isopropylphenyl p-diphenylamine and dioctadecyl diphosphite pentaerythritol ester; the mass ratio of the isopropylphenyl p-diphenylamine to the dioctadecyl diphosphite pentaerythritol ester is 1.2:0.4; the CAS number of isopropylphenyl p-diphenylamine is 101-72-4; dioctadecyl pentaerythrityl diphosphite is purchased from Shanghai Panhua chemical Co., ltd;
the toughness improver is nitrile rubber; nitrile rubber was purchased from denna cheng rui chemical limited;
the conductive improver is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate; the CAS number of the octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate is 86443-82-5;
the auxiliary agent is DMP, and the CAS number of the DMP is 131-11-3.
The preparation method of the novel outdoor polyamide composite material is the same as that of example 1.
Comparative example 1
Comparative example 1 the specific embodiment is the same as example 3 except that no titanate coupling agent is added.
Comparative example 2
Comparative example 2 the specific embodiment is the same as example 3 except that no light stabilizer is added.
Comparative example 3
Comparative example 3a specific embodiment is the same as example 3 except that no conductivity modifier is added.
Evaluation of Performance
The novel polyamide composite materials for outdoor use prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to a performance test.
(1) And (3) testing the antistatic property:
according to GB/T1410-2006 volume resistivity and surface resistivity experimental method of solid insulating materials, the higher the surface resistivity is, the better the antistatic property of the novel polyamide composite material is, and the measured data are shown in Table 1;
(2) And (3) testing the light aging resistance:
the outdoor novel polyamide composite materials prepared in examples 1-3 and comparative examples 1-3 were irradiated with 370W ultraviolet light with a wavelength of 290-320nm at 50 ℃ for 500 hours, and observed for color difference,
if no color difference exists, the color difference is A level;
if no color difference exists, the measured data are shown in the table 1.
TABLE 1
| Surface resistivity/omega | Light aging resistance | |
| Example 1 | 8.2×10 10 | Class A |
| Example 2 | 8.0×10 10 | Class A |
| Example 3 | 8.6×10 10 | Class A |
| Comparative example 1 | 6.7×10 10 | Class B |
| Comparative example 2 | 7.3×10 10 | Class B |
| Comparative example 3 | 4.2×10 10 | Class B |
Claims (10)
1. The novel polyamide composite material for outdoor use is characterized by comprising the following raw materials in parts by weight: 40-80 parts of polyamide resin, 15-25 parts of filler, 0.5-1 part of titanate coupling agent, 0.5-1.5 parts of light stabilizer, 0.5-2 parts of antioxidant, 12-26 parts of toughness improver, 2-5 parts of conductive modifier and 1-3 parts of assistant.
2. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the polyamide resin is at least one of polyamide 6 resin, polyamide 66 resin, polyamide 610 resin and polyamide 1010 resin.
3. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the filler is at least one of diatomaceous earth, mordenite, silica gel, activated carbon, talcum powder and mica powder.
4. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the polyamide resin is polyamide 6 resin, polyamide 610 resin, and the mass ratio of polyamide 6 resin to polyamide 610 resin is (1-3): (0.5-1.5).
5. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the titanate coupling agent is at least one of isopropyl tris (dioctylpyrophosphate) titanate, isopropyl dioleate acyloxy dioctylphosphate titanate, and monoalkoxy unsaturated fatty acid titanate.
6. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the titanate coupling agent is isopropyltris (dioctylpyrophosphate) titanate, monoalkoxyunsaturated fatty acid titanate, and the mass ratio of isopropyltris (dioctylpyrophosphate) titanate to monoalkoxyunsaturated fatty acid titanate is (1-3): (0.5-1.5).
7. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the light stabilizer is at least one of a salicylate light stabilizer, a benzophenone light stabilizer and a benzotriazole light stabilizer.
8. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the light stabilizer is a benzophenone-based light stabilizer, a benzotriazole-based light stabilizer, and the mass ratio of the benzophenone-based light stabilizer to the benzotriazole-based light stabilizer is (1.2-2.6): (0.2-0.8).
9. The novel polyamide composite material for outdoor use as claimed in claim 1, wherein the conductivity modifier is at least one of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and trihydroxyethyl quaternary ammonium methyl sulfate.
10. A method for preparing a novel outdoor polyamide composite material as claimed in any one of claims 1 to 9, which comprises the following steps:
(1) Weighing polyamide resin, light stabilizer, antioxidant, toughness improver, conductive modifier and auxiliary agent according to a proportion, and stirring for 10-30min at 220-270 ℃ to obtain a mixture;
(2) And (2) adding a filler and a titanate coupling agent into the mixture obtained in the step (1), and extruding and granulating by using a double-screw extruder to obtain the novel outdoor polyamide composite material.
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| CN102690514A (en) * | 2011-03-15 | 2012-09-26 | 上海雷博司电器有限公司 | Electromagnetic shielding nylon composite material |
| CN103146189A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon modified plastic |
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| CN102690514A (en) * | 2011-03-15 | 2012-09-26 | 上海雷博司电器有限公司 | Electromagnetic shielding nylon composite material |
| WO2014104471A1 (en) * | 2012-12-31 | 2014-07-03 | 제일모직주식회사 | Thermoplastic resin composition with excellent discoloration-resistance at high temperature and molded product using same |
| CN103146189A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon modified plastic |
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